MIEDICAL 
 
 COLLEGE OF PHARMACY 
 
California College of Pharmacy 
 
WORKS OF DR. H. W. SCHIMPF 
 
 PUBLISHED BT 
 
 JOHN WILEY & SONS, Inc. 
 
 A Manual of Volumetric Analysis. 
 
 For the use of Pharmacists, Sanitary and Food 
 Chemists, as well as for Students in these 
 Branches. Fifth edition, rewritten and en- 
 larged, xx +725 pages. 6 by 9. 102 figures. 
 Cloth, $4.50 net. 
 
 Essentials of Volumetric Analysis. 
 
 An introduction to the subject adapted to the 
 needs of Students of Pharmaceutical Chemistry. 
 Third Edition, rewritten. xiii+366 pages. 
 SM by 8. 6 1 figures. Cloth, $2.00 net. 
 
 A Systematic Course of Qualitative Chemical 
 Analysis of Inorganic and Organic Sub- 
 stances. 
 
 With Explanatory Notes. Third Edition. 
 ix + i8? pages. 6 by 9. Cloth, $1.50 net. 
 
A SYSTEMATIC COURSE 
 
 OF 
 
 QUALITATIVE 
 CHEMICAL ANALYSIS 
 
 OP 
 
 INORGANIC AND ORGANIC SUBSTANCES 
 
 WITH EXPLANATORY NOTES 
 
 BY 
 
 HENRY W. SCHIMPF, Pn.G., M.D. 
 Professor of Analytical Chemistry in the Brooklyn College of Pharmacy. 
 
 California College of Pharmacy 
 
 THIRD EDITION, REVISED 
 TOTAL ISSUE, FIVE THOUSAND 
 
 NEW YORK 
 
 JOHN WILEY & SONS, INC. 
 LONDON: CHAPMAN & HALL, LIMITED 
 
 CALIFORNIA 
 
 of PHARMACY 
 
Authority to use for comment the Pharmacopoeia of the United 
 States of America, Eighth Decennial Revision, in this volume, 
 has been granted by the Board of Trustees of the United States 
 Pharmacopceial Convention, which Board of Trustees is in no way 
 responsible for the accuracy of any translations of the official 
 weights and measures or for any statements as to strength of official 
 preparations. 
 
 COPYRIGHT, 1906, 1917 
 
 BY 
 HENRY W. SCHIMPF 
 
 PRESS or 
 
 A /OQ BRAUNWORTH & CO. 
 
 BOOK MANUFACTURERS 
 BROOKLYN, N, Y, 
 
PREFACE TO THE THIRD EDITION. 
 
 THE exhaustion of the second edition of this book and the 
 greatly increased demand for it, have encouraged the author to 
 publish a new and revised edition. 
 
 In the latter, the features which made the former edition 
 valuable to students have been retained, but a careful revision 
 has been made and much new matter added. The scheme for 
 the acids is greatly improved and many charts have been 
 introduced which it is believed will add to the usefulness of the 
 book. 
 
 The author is very much indebted to Dr. Joseph S. Goldwag 
 for the considerable work he has done in the revision and for 
 the introduction of many new charts as well as for his careful 
 proofreading and indexing. 
 
 It is hoped that the new edition will meet with the same 
 generous appreciation as was accorded the former. 
 
 HENRY W. SCHIMPF. 
 
PREFACE TO FIRST EDITION. 
 
 THIS book has been prepared for students in pharmacy. 
 It is based mainly upon the lectures on analytical chemistry 
 and on the hectographed notes on the laboratory exercises which 
 have been delivered to the students of the Brooklyn College 
 of Pharmacy during the past few years. When a student 
 has but a few months to devote to the study of analytical 
 chemistry it is not advisable to burden his mind by compelling 
 a study of chemical peculiarities which are prominent only 
 because of their technical use in analysis, but rather to elimi- 
 nate them, and direct his studies to the more characteristic 
 chemical reactions. With this in view the author has en- 
 deavored to encompass in a small book most of the inorganic as 
 well as organic qualitative reactions that a student of pharmacy 
 is required to know. The first part of the book explains some 
 of the elementary principles of chemistry, notation and nomen- 
 clature, and prepares the student for what follows. The 
 second part describes the analytical reactions of the metals 
 and acids of pharmaceutical interest, and includes schemes 
 and tables for use in analytical work. 
 
 The third part treats of the qualitative analytical reactions 
 of organic substances, and includes tests for official alkaloids 
 and synthetic compounds, as well as other organic sub- 
 stances used in medicine; also schemes for the detection of 
 
vi PREFACE. 
 
 poisons, the analysis of urine, and an article on the prepa- 
 ration of reagents. 
 
 The final e is dropped from the names of halogens and 
 binary compounds, but is retained in the case of the alkaloids 
 so as to avoid confusing them with glucosides. Chemical 
 equations are given for most of the reactions in the inorganic 
 part and for many of the reactions of organic substances, as 
 it is believed that they greatly assist in gaining a clearer insight 
 into chemical action. The author has given credit in the 
 text wherever due, and besides this he acknowledges his in- 
 debtedness to the United States Pharmacoposia, Eighth Decen- 
 nial Revision, and to Prof. Elias H. Bartley and Dr. Joseph 
 Mayer, for their contributions and valued suggestions; and he 
 especially expresses his thanks to Dr. I. V. Stanley Stanislaus 
 for the considerable work he has done ^in the preparation of 
 this book. 
 
 H. W. S. 
 
 NEW YORK CITY, N. Y., 
 October, i905. 
 
CONTENTS. 
 
 PART I. 
 
 PAGE 
 
 DEFINITIONS AND GENERAL CONSIDERATIONS 1 
 
 Notation, Classification and Nomenclature 7 
 
 PART II. 
 
 IDENTIFICATION AND SEPARATION OF INORGANIC BASES AND ACIDS. . 17 
 
 The Metals 20 
 
 Group 1 24 
 
 Group II 30 
 
 Group III 48 
 
 Group IV 61 
 
 Group V 67 
 
 Preparation of a Solution for Analysis in the Wet Way 75 
 
 Alloys and Hard Metals 78 
 
 Table of Solubilities 81 
 
 The Acids 87 
 
 Systematic Analysis for the Acid 88 
 
 Characteristic Tests for Individual Acids 91 
 
 Group A 91 
 
 Group B 96 
 
 Group C 106 
 
 Group D 110 
 
 Group E 114 
 
 Group F 121 
 
 Group G 124 
 
 PART III. 
 
 QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES 127 
 
 Procedure for Detection of Ultimate Constituents of Organic 
 
 Substances 12 ^ 
 
 vii 
 
viii CONTENTS. 
 
 PAGE 
 
 Behavior of Organic Substances with Immiscible Solvents 128 
 
 Behavior of Organic Substances with Fehling's Solution 130 
 
 Chart for the Detection of the More Common Organic Com- 
 pounds of Pharmaceutical Interest 131 
 
 Identification of Scaled Iron Compounds 154 
 
 A Scheme for the Detection of Poisons 160 
 
 A Scheme for Uranalysis 162 
 
 Preparation of Reagents 176 
 
 LIST OF CHARTS. 
 
 CHART SHOWING EFFECT OF GROUP REAGENTS ON THE METALS 23 
 
 Group I : 
 
 Comparative Observation of the Reactions of Metals of. ... 27 
 
 Identification of Metal in a Simple Salt 28 
 
 Synopsis of Separation of 28 
 
 Separation of 29 
 
 Group II : 
 
 Comparative Observation of the Reactions of Metals of ... 39-40 
 
 Identification of Metal in a Simple Salt 41 
 
 Synopsis of Separation of 42 
 
 Separation of 43 
 
 Group III: 
 
 Comparative Observation of the Reactions of Metals of ... 54-55 
 
 Identification of Metal in a Simple Salt 56 
 
 For "Short Method" of Separation of Metal in a Simple 
 
 Salt 57 
 
 Synopsis of Separation of 57 
 
 Separation of 58 
 
 Group IV: 
 
 Comparative Observation of the Reactions of Metals of. ... 64 
 
 Identification of Metal in a Simple Salt 65 
 
 Synopsis of Separation of 65 
 
 Separation of 66 
 
 Group V: 
 
 Comparative Observation of the Reactions of Metals of . . . 71 
 
 Identification of Metal in a Simple Salt 72 
 
 Synopsis of Separation of 72 
 
 Separation of 73 
 
 Separation of Insoluble Phosphates 75 
 
CONTENTS. ix 
 
 PAGE 
 
 Separation of Alloys and Hard Metals. 78 
 
 Comparative Observation of the Reactions of Metals with 
 
 Three Commonly used Reagents 78-80 
 
 Solubilities 81 
 
 Separation of a Solution into Groups of Metals 82 
 
 Detection and Separation of a Mixture of Metals of the Five 
 Groups 83-86 
 
 Group A: 
 
 Comparative Observation of Reactions of Acids of 95 
 
 Group B : 
 
 Comparative Observation of Reactions of Acids of 105 
 
 Group C . 
 
 Comparative Observation of the Reaction of the Acids of . . 109 
 
 Group D : 
 
 Comparative Observation of the Reactions of the Acids of . . 113 
 Comparison of Gallic, Tannic and Pyrogallic Acids 117 
 
 Group E : 
 
 Comparative Observation of the Reactions of the Acids of. 119 
 
 Group F: 
 
 Comparative Observation of the Reactions of the Acids of. 123 
 
 Group G: 
 
 Comparative Observation of the Reactions of the Acids of. 126 
 Comparison of Phenol and Creosote 151 
 
QUALITATIVE CHEMICAL ANALYSIS. 
 
 PART I. 
 
 DEFINITIONS AND GENERAL CONSIDERATIONS. 
 
 1. Matter. The substance of which all bodies are con- 
 stituted is called matter. Examples: Earth, wood, stone, 
 air, vapor, water, etc. There are two kinds of matter, simple 
 and compound. 
 
 Matter exists in three states of aggregation; i.e., as solids, 
 liquids, and gases. 
 
 2. Continuity of Matter. Whenever a bar of any metal is 
 heated it expands; when cooled it contracts. These changes 
 are most reasonably accounted for by assuming that the metal 
 is composed of minute particles which are not in absolute 
 contact, and which may approach or recede from each other 
 with the withdrawal or application of heat. 
 
 This non-continuity is likewise proved, when two liquids 
 of different densities are mixed; for example, if 50 mils of 
 alcohol are mixed with 50 mils of water, the product is not 
 100 mils of mixture, but only 97 mils, showing a loss in volume 
 of 3 per cent. This reduction of volume clearly indicates 
 that between the particles of one of the two liquids there 
 must be open spaces which particles of the other liquid have 
 filled up. 
 
 There are many other considerations which lead us to 
 
2 QUALITATIVE CHEMICAL ANALYSIS. 
 
 believe that matter is not continuous as it appears to the 
 senses and as generally believed, but is composed of exceed- 
 ingly small particles which are not rigidly joined together, 
 but are at relatively considerable, though exceedingly minute, 
 distances apart ; and that these particles are in a state of per- 
 petual motion, which motion is increased by raising and de- 
 creased by lowering the temperature of the mass. 
 
 Matter is divided into three general divisions masses, 
 molecules, and atoms; and it is impenetrable and indestructible. 
 
 3. Mass, or body, is any distinct portion of matter appre- 
 ciable by the senses. 
 
 Molecules and Atoms. A molecule (a little mass) is " the 
 smallest particle of matter which can exist in a free state ". 
 
 The small particles referred to in paragraph 2 are called 
 molecules; and masses of matter large enough to be evident 
 to the senses are aggregations of molecules. 
 
 All compounds are made up of one or more distinct sub- 
 stances into which they may be split. Since every compound 
 can be split into at least two elements, it follows that its mole- 
 cule must consist of one particle of each element. Hence there 
 must be particles of matter smaller than the molecule itself. 
 
 These smaller elementary particles, called atoms, are defined 
 as " the smallest particle of matter that can enter a chemical 
 combination". Atoms are the constituents of molecules; they 
 are indivisible and indestructible; under ordinary conditions 
 they cannot exist free, but when forced from one combination 
 immediately enter another. 
 
 A collection of atoms forms a molecule, and a collection of 
 molecules forms a mass. 
 
 The molecules of compounds may consist of any number 
 of atoms; molecules of elements usually of only two. 
 
 4. Elements and Compounds. As stated in paragraph 1, 
 there are two kinds of matter, the simple and the compound. 
 
 Simple matter consists of only one elementary substance, 
 as iron, lead, oxygen, carbon. Compound matter is com- 
 
DEFINITIONS AND GENERAL CONSIDERATIONS. 3 
 
 posed of two or more kinds of matter in combination, as iron 
 oxid, which consists of iron and oxygen; and lead sulfate, 
 which consists of lead, sulfur, and oxygen. 
 
 Simple matter cannot be reduced to anything simpler by any 
 known means; it is therefore assumed to consist of but one 
 kind of matter, and is called an element. 
 
 About seventy-four different kinds of elementary matter, 
 or so-called elements, are now known, and it is almost certain 
 that others remain to be discovered. Out of these elementary 
 substances the entire universe is constructed. 
 
 The list of compounds, constantly increasing, is innumer- 
 able. 
 
 5. Definition of Chemistry. Chemistry is the science which 
 considers the composition of substances and changes of com- 
 position which they may undergo. 
 
 Practically, the study of chemistry consists in subjecting 
 materials to the action of certain substances called " re- 
 agents ", or to the action of heat, light, or electricity, and 
 noting the changes which may occur. These changes are 
 called " reactions ". 
 
 Chemistry deals with the atoms composing the molecules. 
 It studies the properties of atoms, their association into 
 molecules, their mutual attraction, the changes of their posi- 
 tions on the application of various forces, the compounds they 
 form when brought together with other atoms or molecules, etc. 
 
 6. Inorganic and Organic Chemistry. By Inorganic Chem- 
 istry we mean "the study of the compounds of mineral origin ". 
 By Organic Chemistry is meant the study of the compounds 
 formed in the tissues of plants or animals, and other " organ- 
 ized " compounds. It is usually defined as " the chemistry of 
 carbon compounds ". 
 
 7. Chemical and Physical Change. Our knowledge of 
 things is derived mostly by observing their specific properties, 
 such as color, hardness, fluidity, transparency, odor, etc., and 
 the changes which take place in them. 
 
 CALIFORNIA COLLEGE 
 of PHARMACY 
 
4 QUALITATIVE CHEMICAL ANALYSIS. 
 
 These changes are comprised under two general headings, 
 viz., physical changes and chemical changes. 
 
 A physical change is one in which the composition and 
 properties of a substance are not permanently altered. 
 
 A chemical change is one in which both composition and 
 properties are permanently altered and one or more new sub- 
 stances produced. 
 
 To illustrate the above-mentioned changes we will take 
 common salt. It is a solid; when put into water it dissolves a 
 physical change occurs; now we apply heat, vaporize the water, 
 and recover the original solid unchanged common salt. If 
 we now take the same salt and dissolve it in sulfuric acid, 
 a chemical change takes place, and the products of this change, 
 hydrochloric acid and sodium sulfate, are entirely unlike the 
 common salt from which they were formed. The acid and the 
 new salt formed are new compounds produced by a chemical 
 change. 
 
 8. Compounds and Mechanical Mixtures. These should 
 be differentiated: In a mechanical mixture there is no true 
 union of the elements; in a compound there is. As an example 
 we will take iron and sulfur. Reduce the iron in a mortar to 
 the finest possible powder; do likewise with the sulfur; now mix 
 the powders intimately until the mixture presents a uniform 
 appearance. Place a small quantity of it under a microscope 
 and small particles of iron and sulfur lying side by side will 
 be revealed. 
 
 Now if another portion of the mixture is taken and heated 
 to redness, a chemical change occurs, a true compound is formed, 
 in which neither the iron nor the sulfur can be revealed under 
 the microscope. 
 
 Before heating, therefore, the powder was but a mechanical 
 mixture, but after heating a true chemical compound, iron 
 sulfid, is found to have been produced. 
 
 9. Molecular Attraction and Chemism. Molecules attract 
 one another. When the molecules are of the same kind they 
 
DEFINITIONS AND GENERAL CONSIDERATIONS. 5 
 
 form a homogeneous mass, and the force acting between them is 
 called cohesion. When the molecules are not of the same kind 
 the force of attraction is called adhesion. A piece of lead 
 thrust into water comes out wet because of the water adhering 
 to it. Try now to pull the lead apart to smaller pieces: you 
 cannot, because cohesion keeps it together. Chemism is to 
 molecules what cohesion is to masses. It is the force which 
 attracts atoms to one another to form molecules. 
 
 10. Atomic and Molecular Weights. The atoms possess 
 definite weights of their own. The atomic weight of any 
 element is the number of times its atom is heavier than the 
 atom of hydrogen, which, being the lightest substance known, 
 is generally used as the standard of weight. Its atomic weight 
 is taken as one ; that is, it weighs one microcrith. 
 
 When, for example, oxygen is said to have the weight of 16, 
 it is understood that its atom has a weight of 16 microcriths, 
 or that it weighs 16 times as much as the hydrogen atom. Thus 
 we say nitrogen weighs 14, carbon 12, sodium 23, calcium 40, 
 etc. Atomic weights are now based on = 16, which is the stand- 
 ard adopted by the International Committee on Atomic Weights. 
 
 Molecular weight is the sum total of the atomic weights in 
 a molecule of a substance. Thus the molecular formula of cal- 
 cium carbonate is CaCOs; that is, it is composed of one atom of 
 calcium having the weight of 40, one atom of carbon weighing 12, 
 and three atoms of oxygen each weighing 16, or 48 for the three. 
 Adding these atomic weights (40 + 12+48) together we get the 
 sum of 100, which is the molecular weight of the calcium car- 
 bonate, or common chalk. 
 
 11. Valence, also called Quantivalence, or "Bonds.*" By 
 the " valence " of an element is meant " the combining power of 
 one of its atoms as compared with that of hydrogen." As will 
 be seen, hydrogen is also the " unit " of valence, as it is of weight. 
 
 Atoms of certain elements, such as chlorin, are found to be 
 equal in combining power to those of hydrogen; i.e., one atom 
 of chlorin unites with one atom of hydrogen. Hydrogen being 
 
6 QUALITATIVE CHEMICAL ANALYSIS. 
 
 the unit has the valency of 1, or one bond; it is also called 
 a "monad," or a "univalent" element. 
 
 When it is said that oxygen has the valency of 2, or that 
 oxygen is a dyad, it is meant that the combining value of its 
 atoms is twice that of the hydrogen atom, and that in order 
 to make these two combine, two atoms of hydrogen must be 
 
 employed to satisfy one atom of oxygen, thus: 
 
 Nitrogen, having the valence of 3, is a triad, and requires 3 
 
 /H 
 
 atoms of hydrogen to satisfy its atom, thus: N^H = NH3. 
 
 NH 
 
 From the above we will see that the chemical value of any 
 atom is equal to that of another atom which can replace it 
 in a molecule. Thus atoms are divided into monads, dyads, 
 triads, tetrads, pentads, hexads, heptads, etc., according as they 
 can replace 1, 2, 3, 4, 5, 6, or 7 atoms of hydrogen or its equiv- 
 alent in a molecule. 
 
 An element, while it always has the same valence in the 
 same compound, may have different valences in different com- 
 pounds or combinations. In ammonia (NH 3 ), for example, 
 the valence of nitrogen is always 3, but in nitrogen pentoxid 
 (N 2 5 ) it is always 5; many other elements have this variable 
 valence. 
 
 A monad is equivalent to a monad. 
 
 1 ' dyad " " . " 2 monads or 1 dyad. 
 
 " triad " " '".3 " " 1 monad and 1 dyad. 
 
 " tetrad " " " 4 " " 2 dyads or 1 monad) 
 
 and 1 triad. 
 
 ' pentad " " ' l 5 " " 1 tetrad and 1 monad, 
 
 " 1 triad and 2 monads, 
 " 2 dyads and 1 monad. 
 
 The valence of an atom is often indicated by accents placed 
 to the right of its symbol, thus: H', H"'; or by Latin 
 numerals, as 0", C IV , etc. 
 
DEFINITIONS AND GENERAL CONSIDERATIONS. 
 
 NOTATION, CLASSIFICATION, AND NOMENCLATURE OP 
 ELEMENTS AND INORGANIC COMPOUNDS. 
 
 12. Symbols. For convenience in writing chemical reac- 
 tions and for many other reasons, certain symbols are used 
 which represent or stand for the names of elements. These 
 symbols are the initials of their Latin names (H for hydrogen, 
 for oxygen, N for nitrogen, S for sulfur, etc.). When more 
 than one element has a name beginning with the same letter, 
 another characteristic letter is added. The first letter is always 
 a capital, the second is small (Hg for hydrargyrum, Os for 
 osmium, Ni for nickel, Sb for stibium, etc.). Each symbol 
 stands for one atom of the element, unless a figure is attached 
 to the upper or lower right-hand corner, which indicates a 
 greater number of atoms: H' = l atom of hydrogen, H 2 =2 
 atoms of hydrogen. 
 
 13. Metals are Classified according to their chemical 
 and physical relationship. The " Periodic System " groups 
 the elements progressively in accordance with their atomic 
 weights, thus exhibiting these relationships most perfectly. 
 
 The arrangement used in this book groups the elements 
 most advantageously for the practical work of the chemist. 
 
 The following tables include the most important elements 
 and acids. Students would do well to study carefully and 
 commit to memory the grouping, symbols, and valences. 
 
 In Table I we will find the Non-Metals classified. These 
 may be solid, liquid, or gaseous at ordinary temperatures. 
 They have no lustre, ductility, or malleability, are poor con- 
 ductors of heat and electricity, and are electronegative in 
 combinations. They are the Acid-forming Elements. 
 
 In Table II we find the Metals, or Base-forming Elements. 
 These are electropositive, solid (except mercury) at ordinary 
 temperatures; generally heavy bodies, good conductors of heat 
 and electricity, and possessing more or less lustre. 
 
8 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 In Table III the Acids are grouped according to their 
 valence or basicity. 
 
 An acid is denned as a " salt of hydrogen ". In reality 
 " acids are the hydroxids of the non-metals ", and while not 
 all the acids contain oxygen, every acid contains hydrogen. 
 
 Acids containing oxygen are called oxacids, of which nitric 
 acid (HNOs) is an example ; those in which oxygen is wanting are 
 classed as hydracids; thus hydrochloric acid (HC1) is a hydracid. 
 
 An acid consists of two parts : Replaceable or basic hydrogen, 
 and the acidulous radical. The hydrogen may be replaced by 
 a metal, and the acid radical may pass into another compound 
 without splitting into its elements. The basicity or valence 
 of an acid is determined by the number of replaceable hydrogen 
 atoms it contains; thus, H(C1) is a monobasic acid, H 2 (S04) 
 rs a dibasic acid, H 3 (P0 4 ) is a tribasic acid, etc.; the acidu- 
 lous radicals are in parenthesis. 
 
 14. 
 
 TABLE I NON-METALS. 
 
 Grouping. 
 
 Symbol. 
 
 Valences. 
 
 Atomic 
 Weights. 
 
 Hydrogen Group : 
 Hydrogen 
 
 H 
 
 1 
 
 1.008 
 
 Chlorin Group : 
 Chlorin . . 
 
 Cl 
 
 1, 3, 5 
 
 35.46 
 
 Brornin 
 
 Br 
 
 1, 3, 5 
 
 79.92 
 
 lodin 
 
 I 
 
 1, 3, 5 
 
 126.92 
 
 Fluorin 
 
 F 
 
 1 
 
 19.0 
 
 Sulfur Group : 
 Oxygen .... ... 
 
 o 
 
 2 
 
 16. 
 
 Sulfur 
 
 s 
 
 2, 4, 6 
 
 32.07 
 
 Selenium 
 
 Se 
 
 2, 4, 6 
 
 79.2 
 
 Tellurium 
 
 Te 
 
 246 
 
 127.5 
 
 Nitrogen Group : 
 Boron 
 
 B 
 
 3 
 
 11. 
 
 Nitrogen 
 
 N 
 
 3, 5 
 
 14.01 
 
 Arsenic 
 
 As 
 
 3 5 
 
 74 96 
 
 Antimony 
 
 Sb 
 
 3 5 
 
 120.2 
 
 Phosphorus 
 
 P 
 
 3 5 
 
 31.04 
 
 Carbon Group : 
 Carbon 
 
 c 
 
 2, 4 
 
 12. 
 
 Silicon 
 
 Si 
 
 2 
 
 28.3 
 
 
 
 
 
DEFINITIONS AND GENERAL CONSIDERATIONS. 
 
 15- 
 
 TABLE II. THE METALS. 
 
 
 Grouping. 
 
 Symbol. 
 
 Valence 
 in -ous 
 com- 
 pounds. 
 
 Valence 
 in -ic 
 com- 
 pounds. 
 
 Atomic. 
 Weight 
 
 Metals precipitated, by 
 
 { Firf^t Group : 
 
 
 
 
 
 dilute HC1, whose chkrids, 
 
 Silver 
 
 \<r 
 
 
 1 
 
 107.88 
 
 sulfids, hydroxids, and car- 
 bonates are insoluble in 
 
 1 Lead 
 I Mercurosum. 
 
 Pb 
 Hg" 
 
 1 
 
 2 
 
 207.1 
 200.6 
 
 Metals precipitated by 
 H 2 S in acid solution, whose 
 
 (Second Group Fir 
 Arsenic 
 
 & 
 
 t Di i 
 
 As 
 
 ion : 
 3 
 
 5 
 
 74.96 
 
 sulfids are soluble in 
 
 Antimony 
 
 Sb 
 
 3 
 
 5 
 
 120.2 
 
 (NH 4 ) 2 S. 
 
 I Tin ........ 
 
 Sn 
 
 2 
 
 4 
 
 119. 
 
 
 Second Group Sec 
 
 ond Di 
 
 ision : 
 
 
 
 Metals precipitated from 
 
 Bismuth 
 
 Pi 
 
 3 
 
 5 
 
 208. 
 
 acid solution by H 2 S, whose 
 sulfids are insoluble in 
 
 (NH 4 ) 2 S. 
 
 Copper 
 Mercuricum 
 
 Cu 
 Hg 
 
 1 
 
 2 
 2 
 
 63.57 
 200.6 
 
 
 Cadmium 
 
 Cd 
 
 
 2 
 
 112.4 
 
 
 Third Group First 
 
 Dirisi 
 
 on : 
 
 
 
 
 Iron 
 
 Fe 
 
 2 
 
 3 
 
 55.84 
 
 Metals not precipitated 
 
 Cobalt 
 
 Co 
 
 2 
 
 3 
 
 58.97 
 
 by H 2 S from acid solutions 
 but precipitated by 
 
 1 Nickel 
 Manganese .... 
 
 Ni 
 
 Mn 
 
 2 
 2 
 
 3 
 3 
 
 58.68 
 54.93 
 
 \NH 4 ) 2 o as sulnds. 
 
 [ Zinc 
 
 Zn 
 
 
 2 
 
 65.37 
 
 Metals not preeinitated 
 by H 2 S from acid solutions 
 
 f Third Group Seco 
 \ Aluminum 
 
 nd Di^ 
 Ai 
 
 ision : 
 
 3 
 
 27.10 
 
 but precipitated by 
 
 Chromium . . 
 
 Cr 
 
 2 
 
 3 
 
 52.0 
 
 (NH 4 )oS as hydroxids. 
 
 
 
 
 
 
 
 Fourth Group : 
 
 
 
 
 
 Metals not precipitated 
 
 Calcium 
 
 Ca 
 
 
 2 
 
 40.07 
 
 by sulnds, either from acid 
 or alkaline solution, but 
 precipitated by carbonates 
 
 Strontium 
 Barium 
 [ Magnesium. . . . 
 
 Sr 
 Ba 
 Mg 
 
 
 2 
 2 
 2 
 
 87.63 
 137.37 
 24.32 
 
 
 [ Fifth Group : 
 
 
 
 
 
 
 Lithium 
 
 Li 
 
 
 1 
 
 6.94 
 
 Metals not precipitatec 
 by any general reagent. 
 
 j Sodium 
 Potassium 
 
 Na 
 K 
 
 
 1 
 1 
 
 23.0 
 39.10 
 
 
 { Ammonium. . .. 
 
 NH 4 
 
 
 1 
 
 18.04 
 
10 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 16. 
 
 TABLE III. THE ACIDS. 
 INORGANIC HYDRACIDS. 
 
 Name of Acid. Chemical Formula. Name of its Salt. 
 
 Monobasic: Hydrochloric HC1 Chlorid 
 
 ' ' Hydrobromic HBr Bromid 
 
 Hydriodic HI lodid 
 
 Hydrofluoric. , HF Fluorid 
 
 Hydrocyanic HCN Cyanid 
 
 Dibasic: Hydrosulfuric H 2 S Sulfid 
 
 Tribasic: Hydroferricyanic H 3 Fe(CN) 6 Ferricyanid 
 
 Tetrabasic: Hydroferrocyanic H 4 Fe(CN) 6 Ferrocyanid 
 
 INORGANIC OXACIDS. 
 
 Monobasic: Chloric HC1O 3 Chlorate 
 
 1 1 Bromic HBrO 3 Bromate 
 
 ' ' lodic HIO 3 lodate 
 
 " Nitrous HNO, Nitrite 
 
 Nitric HN0 3 Nitrate 
 
 Dibasic: Sulfurous H 2 SO 3 Sulfite 
 
 Sulfuric H SO 4 Sulfate 
 
 Thiosulf uric H 2 S 2 O 3 Thiosulfate 
 
 Carbonic H 2 CO 3 Carbonate 
 
 Chromic H 2 CrO 4 Chromate 
 
 Tribasic: Phosphoric H 3 PO 4 Phosphate 
 
 Arsenpus H 3 AsO 3 Arsenite 
 
 Arsenic H 3 AsO 4 Arsenate 
 
 ORGANIC OXACIDS. 
 
 Monobasic: Formic BCHO 2 Formate 
 
 Acetic HC 2 H 3 O 2 Acetate 
 
 Lactic HC 3 H 5 O 3 Lactate 
 
 Benzoic HC 7 H 5 O 2 Benzoate 
 
 Salicylic HC 7 H 5 O 3 Salicylate 
 
 Valerianic HC 5 H 9 O 2 Valerianate 
 
 Dibasic: Malic H 2 C 4 H 6 O 5 Malate 
 
 Oxalic H 2 C 2 O 4 * Oxalate 
 
 Succinic H 2 C 4 H 4 O 4 Succinate 
 
 " Tartaric H 2 C 4 H 4 O 6 Tartrate 
 
 Tribasic: Citric H 3 C 6 H 5 O 7 Citrate 
 
 " Meconic H 3 C 7 HO 7 Meconate 
 
 17. Importance of Symbols. The symbols in Tables I 
 and II represent not merely the name of the element, but 
 also a definite weight of the latter. Thus the symbol 
 represents not merely oxygen, but it stands for one atom of 
 oxygen or 16 parts by weight; N represents one atom of nitro- 
 
DEFINITIONS AND GENERAL CONSIDERATIONS. 11 
 
 gen or 14.01 parts by weight; and C represents 12 parts by 
 weight of carbon. 
 
 A Formula is an expression representing the composition of 
 a molecule ; it consists of two or more symbols written together, 
 and therefore represents a definite weight, the molecular weight, 
 which is the sum of the atomic weights of the constituent 
 atoms. 
 
 Thus H 2 is the formula which represents water; its molec- 
 ular weight is 18.016, i.e., 2.016 parts by weight of hydrogen 
 and 16 parts by weight of oxygen. NaCl is the formula for 
 sodium chlorid, and represents 58.46 parts by weight of sodium 
 chlorid; 23 for the sodium and 35.46 for the chlorin. KOH 
 is the formula for potassium hydroxid, and represents one atom 
 of potassium, one of oxygen, and one of hydrogen, having the 
 weights 39.1, 16, and 1.008 respectively. Hence KOH repre- 
 sents 56.108 parts by weight of potassium hydroxid. 
 
 When we wish to represent more than one atom, we place a 
 small numeral at the right-hand lower corner of the symbol; 
 thus 2 represents 2 atoms of oxygen, or 32 parts by weight; 
 in the same way K 3 = three atoms of potassium, B 4 =four atoms 
 of boron. 
 
 When we wish to represent more than one molecule, we 
 place a large numeral before the formula. Thus 2KOH repre- 
 sents two molecules of KOH; the 2 multiplies each of the atoms 
 in the molecule. 3H 2 S0 4 represents three molecules of H 2 S0 4 ; 
 thus it means, 6 XH, 3 XS, and 12 XO. The three placed before 
 the molecule multiplies the whole molecule; the smaller nu- 
 merals in this case, 2 and 4, multiply only the atoms which 
 immediately precede them; thus the H is multiplied by 2, and 
 
 the by 4. 
 
 If a group of symbols is inclosed in a parenthesis and a 
 small numeral placed after it, as in (NH^ and (S0 4 ) 3 , the 
 whole group is multiplied by the numeral. 
 
 As symbols always represent atomic weights, so formulas 
 represent molecular weights; thus the molecular weight of 
 
12 QUALITATIVE CHEMICAL ANALYSIS. 
 
 sodium sulphate, Na 2 S0 4 , is: Na 2 (23X2)=46, 8 = 32.07, O 4 
 (16X4) -64, which added together give 142.07. 
 
 Equations are representations, by means of symbols, of 
 chemical reactions. Example: 
 
 Na 2 C0 3 + 2HC1 = 2NaCl + H 2 + C0 2 . 
 
 Sodium Hydrochloric Sodium Water. Carbon 
 
 Carbonate. Acid. Chlorid. Dioxid. 
 
 Na 2 (23X2)=46 2H= 2.016 2Na = 46 2H = 2.016 C = 12 
 C =12 201 = 70.92 201 = 70.92 = 16 2 = 32 
 
 3 (16X3)=48 
 
 106 72.936 116.92 18.016 44 
 
 This equation indicates that sodium carbonate treated with 
 hydrochloric acid will yield sodium chlorid, water, and carbon 
 dioxid. There are one molecule of Na 2 C0 3 and two molecules 
 of HOI reacting, and producing two molecules of NaCl and one 
 molecule each of H 2 and C0 2 . 
 
 Now, since symbols represent definite weights, an equation 
 can be easily reduced to figures. The atomic weights of the 
 elements entering into the foregoing equation are Na=23, 
 = 12, = 16, H = 1.008, and 01 = 35.46. 
 
 Thus we have 106 parts of Na 2 C0 3 reacting with 72.936 parts 
 of HOI and forming 116.92 parts of NaCl, 18.016 parts of H 2 0, 
 and 44 parts of C0 2 . 
 
 In an equation, the sum of the atoms on one side of the 
 sign of equality [ = ] should equal that on the other. 
 
 18. Classification of Compounds. Compounds are classified 
 as bases, acids, and salts. 
 
 Bases are the hydroxids of the metals. Slaked lime is 
 the commonest example of this class. Some of the bases are 
 soluble, others not ; when soluble they have a caustic taste and 
 turn red litmus blue. 
 
 Acids are the salts of hydrogen; these are fully defined in 
 paragrap 1 ! 13 and classified in Table III. When soluble they 
 have a sharp, sour taste and turn blue litmus red. 
 
DEFINITIONS AND GENERAL CONSIDERATIONS. 13 
 
 Salts are acids in which part or all the basic hydrogen 
 has been replaced by a metal; thus, if the hydrogen of sulfuric 
 acid is replaced by potassium, we have formed a salt, called 
 potassium sulfate; if the hydrogen of acetic acid be replaced 
 by potassium, we have a salt called potassium acetate. 
 
 The salts are further classified into normal, acid, basic, and 
 double salts. 
 
 A normal salt is one in which all the basic hydrogen has 
 been replaced by a metal, as in Na2COs, sodium carbonate. 
 
 An acid salt is one in which some of the basic hydrogen still 
 remains, as in NaHCOs, sodium acid carbonate. 
 
 A basic salt is a substitution of a metal in part for the H of 
 an acid, and in part for the half or the whole of the H of water; 
 i.e., a basic salt is a compound partly of the nature of a salt and 
 partly of the nature of a hydroxid or an oxid. 
 
 Double salt is one in which the basic H of an acid is replaced 
 by more than one metal. Example, KNaC-jH^Oe. 
 
 The Names of Acids. All the names of hydracids begin with 
 hydro and end in ic, as hydrochloric, hydroiodic, hydrobromic, 
 etc. 
 
 In the oxacids, the quantity of oxygen present in acids of the 
 same element determines their names, thus: acids containing 
 the least amount of oxygen begin with hypo and end in ous; 
 those containing the next larger quantity of oxygen end in 
 ous, omitting the hypo; those containing the next larger quan- 
 tity of oxygen end in ic. If there is a fourth acid containing 
 still more oxygen than the preceding one, its name begins with 
 per and ends in ic. In this way we derive a table of the 
 nomenclature of the acids. Following is a table of the chlorin 
 oxacids: 
 
 Formula. Name of Acid. 
 
 HC10 Hypochlorous 
 
 HC10 2 Chlorous 
 
 HC10 3 Chloric 
 
 HC10 4 Perchloric 
 
14 QUALITATIVE CHEMICAL ANALYSIS. 
 
 The Names of Salts. The names of salts also indicate their 
 composition, both as regards their constituents and the quanti- 
 ties of these present in them. 
 
 The names of salts generally consist of two words, the first 
 expressing the metal, the second expressing the acid radical; 
 thus, sodium sulfate = Na 2 S0 4 ; zinc chlorid =ZnCl 2 . The above 
 is true only with the normal salts. In the case of acid or basic 
 salts three and more words are required to express their name 
 and composition, as in potassium acid carbonate, KHC0 3 , 
 etc. 
 
 As is seen in the above, the prefixes and suffixes employed in 
 expressing the names of the acids and salts have a very important 
 meaning, which the following further explains : 
 
 The prefix sesqui is used to express a proportion of 1 to 1J, 
 as in Fe 2 3 , iron sesquioxid. Prefix sub, when used, indicates 
 a lower amount of an element than the name would otherwise 
 represent; thus, Cu20, copper suboxid. 
 
 The prefix per or hyper or super (above) indicates the highest 
 of a series of compounds, as contrasted with sub or hypo, indi- 
 cating lowest. Examples: KC10 4 , potassium perchlorate; 
 Fe2Cl 6 , iron perchlond. 
 
 The prefix ortho (straight) is used to distinguish normal acids 
 or salts. Example, H 3 P04, or^ophosphoric acid. 
 
 The prefix pyro (by fire) is used to designate that the body has 
 been produced by heat (fire). Thus 2H 3 P0 4 or H 6 P 2 8 +heat 
 becomes H 4 P 2 7 , pyrophosphoric acid, water (H 2 0) being 
 driven out. CrHeOs, gallic acid, heated, becomes C 6 H 6 3 , 
 pyrogallic acid, C0 2 being driven out. 
 
 The prefix meta is used to designate an altered condition as 
 distinguished from the ortho and pyro (and para) forms. Thus 
 H 4 P 2 7 +heat becomes 2HP0 3 , metaphosphoric acid, water 
 being driven out. 
 
 The prefixes ortho, meta, and para (near to) are used with 
 organic compounds in which some of the constituent radicals 
 are attached in certain relation to each other; these compounds 
 
DEFINITIONS AND GENERAL CONSIDERATIONS. 15 
 
 have the same chemical composition but differ in physical 
 properties. The following examples illustrative of this show a 
 difference in the place of attachment of the OH radicals; the 
 chemical composition C 6 H 4 (OH) 2 being the same in each. 
 
 OH 
 
 QTT 
 
 is 0r//io-dihydroxybenzol, or pyrocatechin. 
 
 is weta-dihydroxybenzol, or resorcin. 
 
 is para-dihydroxybenzol, or hydroquinone. 
 
 OH 
 
 Para also indicates molecular aggregations of certain organic 
 compounds, as C 2 H 4 = aldehyd; and (C 2 H 4 0) 3 or C 6 Hi 2 3 = 
 paraldehyd. 
 
 The prefix hydro indicates binary compounds or acids, as 
 hydrochloric acid, HC1, fo/oYosulfuric acid, H 2 S, etc. 
 
 The prefixes an (without) and de (away from) are used to 
 denote something which has been removed from a body in 
 which it normally exists. Examples: anhydrous, without water 
 or moisture; deodorized, deprived of odor. 
 
 The nomenclature of salts corresponds to that of the acids; 
 thus the name of 
 
 a salt of an hypo . . . ous acid begins with hypo and ends in ite 
 
 ous acid ends in ite 
 
 " " ll lt ic (l " " ate 
 
 ' ' " " a per . . . ic " begins with per and ends in ate. 
 
 The following table of the chlorin oxacids with sodium 
 illustrates this: 
 
 CALIFORNIA COLLEGE 
 
 of PHARMACY 
 
16 QUALITATIVE CHEMICAL ANALYSIS. 
 
 Name of Acid. Name of the Salt. 
 
 Hypochlorous acid forms Sodium Hypochlorite 
 Chlorous " " " Chlorite 
 
 Chloric " " " Chlorate 
 
 Perchloric " " " Perchlorate 
 
 For nomenclature of other salts see Table III. The name 
 of a compound may also be varied in other ways to indicate 
 its composition, as di-sodium phosphate, Na 2 HP04, to indicate 
 that only two atoms of basic hydrogen in phosphoric acid, 
 H 3 P04, have been replaced by the metal. By referring to 
 Table II we note that many elements, as iron, bismuth and 
 arsenic, form two or more classes of compounds corresponding 
 to their varied valences. 
 
 Names of these compounds in which the element has the 
 lower valence end in ous ; those in which it has the higher val- 
 ence end in ic, as ferrous and ferric salts, arsenows and arsem'c 
 salts, etc. 
 
 The names of salts of all the hydracids end in id, as will 
 be observed by referring to Table III; so also do the names 
 of all other binary salts. 
 
 The terms binary and ternary salts designate those composed 
 of only two or of more elements; thus, KC1, KCN, etc., are 
 binary compounds, and KC10 3 , KSCN, etc., are ternary com- 
 pounds. 
 
 An oxid is a compound formed by the union of a metal or 
 non-metal with oxygen. CaO, K 2 0, MgO, C0 2 , and N205. 
 
 An anhydrid is a compound left after removing from an 
 acid all its replaceable hydrogen and enough oxygen to form 
 water. 
 
 Examples. H 2 S0 4 - H 2 = S0 3 =sulfuric anhydrid; 
 
 2H 3 P0 4 - 3H 2 = P 2 5 = phosphoric anhydrid ; 
 H 2 C0 3 H 2 0= C0 2 = carbonic anhydrid. 
 
PART II. 
 
 IDENTIFICATION AND SEPARATION OF INORGANIC 
 BASES AND ACIDS. 
 
 INTRODUCTORY. 
 
 19. Qualitative Analysis has for its object, the resolving of 
 more or less complex substances into simpler ones, without 
 reference to the proportions or quantities of the latter present. 
 
 By qualitative analysis usually we mean the examina- 
 tion of salts, i.e., combinations of bases and acids, the prob- 
 lem involved in such cases being the determination of the 
 particular base and acid present in the given substance. Thus 
 we examine a substance to determine not directly what efo 
 ments are present, but what metals and what acidulous radi- 
 cals the latter usually being groups of elements. For example, 
 in the analysis of barium sulfate we do not search for Ba, S, 
 and separately, but for barium as the base and S0 4 as the 
 acidulous radical. 
 
 In some cases such as ammonium carbonate, (NH 4 ) 2 C0 3 , 
 where neither the positive radical or base (NH 4 ) nor the nega- 
 tive or acidulous radical (C0 3 ) can exist in the free or 
 uncombined state, we detect the former by the evolution 
 of ammonia-gas (NH 3 ), and the latter by the expulsion of 
 carbon dioxid (C0 2 ), from the substance. The word analysis 
 is the true antithesis of the word synthesis; analysis mean- 
 ing splitting up or breaking up of a substance, while synthesis 
 means the building up of a compound from its elements. 
 
 17 
 
18 QUALITATIVE CHEMICAL ANALYSIS. 
 
 Thus if we conduct an electric current into a solution of com- 
 mon salt, we split the compound into its components Na and 
 Cl. This process is truly analytical. If we now bring sodium 
 and chlorin together under suitable conditions, sodium chlorid 
 will be formed in a synthetical way. 
 
 The word analysis, in chemistry, bears a wide meaning. 
 It includes the manifold processes used by chemists in the 
 identification of substances. Thus substances are often recog- 
 nized by some characteristic appearance, like a particular 
 crystalline form, when examined under a microscope, which 
 operation is known as microscopical analysis. Often the pres- 
 ence of certain elements in a substance is determined by exam- 
 ining the light emitted when substances are strongly heated 
 in a non-luminous flame before an optical apparatus known 
 as a spectroscope, in which case the operation is known as spec- 
 troscopic analysis. Again, the substance may be examined in 
 a polariscope as to its effect on light (much employed in oil 
 and sugar analysis). In this last case the operation is called 
 polariscopic analysis. The majority of analytical operations 
 depend on some chemical change or reaction. When this 
 change occurs on strongly heating a substance and observ- 
 ing its peculiar characteristics in the dry way, we call it a 
 dry reaction. Again, when such a change occurs in the sub- 
 stance in the liquid form, by the action upon it of another 
 liquid known as a reagent, we call it a wet reaction. 
 
 20. Reagents, or substances used to bring about chemical 
 changes, may be in either the solid or the liquid state. For 
 convenience in operation they are usually employed as liquids.* 
 
 Reagents are divided into three classes: 
 
 General Reagents, or group reagents, which under certain 
 suitable conditions react with and precipitate a whole group 
 or class of substances of similar character. 
 
 * Students should prepare their own reagents and not be kept in the dark 
 as to their strength; it also gives them an idea of the delicacy of many of the 
 reactions. 
 
INORGANIC BASES AND ACIDS. 19 
 
 Separatory Reagents, by means of which the substance under 
 examination is separated from other members of the same 
 group; and 
 
 Confirmatory or Special Reagents, which are employed be- 
 cause they produce a certain peculiar characteristic reaction 
 with a particular substance under examination, thus identifying 
 it without any further doubt. 
 
 Reagents, says Prof. Newth, are "the tools with which 
 the analyst works, and upon the intelligent and skilful use 
 of them everything depends." 
 
 To the above a word on the impurities in reagents may 
 be added. The student should constantly bear in mind that 
 the substances he is testing for may be present in the reagents 
 as impurities. In all such cases test the reagent directly, and 
 by all means make sure of its purity; it is imperative for two 
 reasons : 
 
 First : It precludes danger of serious errors, and 
 
 Second: It forms a habit of making blank tests with re- 
 agents and thus cultivating observation and logical reason- 
 ing powers. 
 
 In the course of qualitative analysis wet reactions are 
 thought the more important. 
 
 When chemical reaction takes place between two or more 
 substances in solution, and one of the products of the reac- 
 tion is insoluble, it is thrown out of solution or precipitated, 
 and is called a precipitate (abbr., ppt.). 
 
 In these operations the phenomenon of precipitation is 
 taken advantage of. 
 
 In precipitation of a substance the reagent should always be 
 added gradually, and until no further precipitate forms. This 
 can be determined by permitting the precipitate to settle, or, 
 in case of light and flocculent precipitates which settle very 
 slowly, by filtering a little of the liquid and adding to the fil- 
 trate a drop or two of the reagent. 
 
 In this way we guard against adding too much of the reagent, 
 
 COLLEGE 
 
 PHARMACY 
 
20 QUALITATIVE CHEMICAL ANALYSIS. 
 
 which in many cases partly dissolves some of the precipitates 
 a very undesirable thing. 
 
 In washing a precipitate, one should persist until the wash- 
 water will no longer give a test for any substance known to be 
 present in the filtrate, for if the precipitate is not thoroughly 
 washed, the metal will be found present in succeeding groups, 
 which will cause confusion and perhaps error in the analysis. 
 
 Guesswork will not do in these cases; you must be thorough, 
 as on the complete precipitation of the substances and subse- 
 quent thorough washing of the precipitates the success of the 
 analysis depends. 
 
 THE METALS 
 SEPARATION OF GROUPS. 
 
 21. If it were possible to precipitate by a separate reagent 
 each individual metal out of a solution containing several dif- 
 ferent metallic salts, the analysis of such a solution would be 
 a very simple matter. 
 
 Chemical analysis is, however, not so simple, for each 
 reagent will precipitate more than one metal, and therefore 
 in a solution containing a large number of metals the separa- 
 tion must be effected in groups. 
 
 Thus assuming that we have a solution containing twenty- 
 four of the more common metals which we wish to analyze, the 
 procedure must be as follows: 
 
 22. Hydrochloric acid is added to the solution in slight 
 excess. This causes the precipitation of lead, silver, and mercury 
 (if this is in the form of a mercurous salt), as chlorid. (The 
 Metals of Group I.) 
 
 The hydrochloric acid should be added in sufficient quantity to pre- 
 cipitate all the lead, silver, and mercurous mercury (mercurosum) that 
 may be present in the solution. To insure this, the precipitate is allowed 
 to settle, and the clear liquid above it treated with a few drops more of 
 hydrochloric acid. If this fails to produce a precipitate, the acid has been 
 added in sufficient quantity. If, however, a precipitate is produced, more 
 hydrochloric acid must be added. A large excess, however, is to be avoided. 
 
INORGANIC BASES AND ACIDS. 21 
 
 N.B. Bismuth and antimony are precipitated by diluted hydrochloric 
 acid, in the form of oxychlorids. Such a precipitate must not be mistaken 
 for that of the metal 3 of Group I. 
 
 23. Having precipitated the metals of Group I as above 
 described, allow the precipitate to settle, and pass the super- 
 natant liquid through a filter. This solution, which contains 
 the remaining twenty-one metals, is treated with excess, of the 
 Group II reagent, namely, hydrogen sulfid (H 2 S). This causes 
 the separation of seven more metals, namely, mercury in mercuric 
 salts (mercuricum) , copper, bismuth, cadmium, arsenic, anti- 
 mony, and tin, in the form of sulfids. (The metals of Group 1 1.) 
 
 These metals take up the sulfur from the hydrogen sulfid and form in- 
 soluble sulfids. In color the sulfids of mercury, copper, and bismuth so 
 precipitated are black, cadmium and arsenic yellow, antimony orange, 
 and tin brown or yellow. 
 
 The hydrogen sulfid is best used in the form of the pure gas, which 
 should be allowed to bubble through the solution until the latter is thoroughly 
 saturated. A saturated aqueous solution of the gas is sometimes used 
 instead of the gas itself. 
 
 24. Having precipitated the metals of Group II, separate the 
 precipitate by filtration. The filtrate now contains only four- 
 teen metals. To this filtrate is added ammonium chlorid, about 
 J its volume, and ammonium hydroxid in sufficient quantity 
 to render the solution alkaline, then a slight excess of ammonium 
 sulfid. Another separation of seven metals will take place, 
 namely, iron, zinc, aluminum, manganese, chromium, cobalt, and 
 nickel, as sulfids except aluminum and chromium, which sep- 
 arate as hydroxids. (The Metals of Group III.) 
 
 The sulfur of the ammonium sulfid unites with the metals, iron, zinc, 
 manganese cobalt, and nickel forming sulfids of these metals, but chrom- 
 ium and aluminum are precipitated as hydroxids. In color the precipitates 
 produced with iron, cobalt, and nickel are black, with manganese flesh 
 color, with zinc and aluminum white, and with chromium pale greenish. 
 
 25. Having added sufficient of the ammonium sulfid (the 
 Group III reagent) to completely precipitate the metals, the 
 
22 QUALITATIVE CHEMICAL ANALYSIS. 
 
 mixture is again filtered in order to separate the precipi- 
 tate. 
 
 26. If now to the filtrate, in which only seven metals are left, 
 an excess of ammonium carbonate solution be added, the metals 
 barium, calcium, and strontium are precipitated in the form 
 of carbonates (Group 77), leaving in solution magnesium, 
 potassium, sodium, ammonium, and lithium. (Group V.) 
 
 From this solution the magnesium may be precipitated 
 by adding sodium phosphate. 
 
 Since much ammonium has been added in the course of the 
 analysis, a special test must be made for it in the original 
 solution. 
 
 Each group of metals separated as above described, is 
 further separated into its component metals according to the 
 charts, and each metal identified by characteristic tests. 
 
 These tests in most instances cannot be applied satisfac- 
 torily unless upon solutions of single metals. 
 
INORGANIC BASES AND ACIDS. 
 
 23 
 
 27. CHART SHOWING THE EFFECT OF THE GROUP REAGENTS 
 ON THE METALS 
 
 Group I. 
 
 Group II. 
 
 Group III. 
 
 Group IV. 
 
 Group V. 
 
 HC1 
 
 H 2 S 
 
 NH 4 OH 
 
 (NH 4 ) 2 S 
 
 (NH 4 ) 2 CO 3 
 
 No Group 
 
 in slight 
 
 in presence of 
 
 in 
 
 in 
 
 in 
 
 reagent. 
 
 excess. 
 
 HC1. 
 
 presence 
 
 presence 
 
 presence 
 
 
 
 
 of NH 4 C1 
 
 ofNH 4 OH 
 
 ofNH 4 OH 
 
 
 
 
 
 and 
 
 and 
 
 
 
 
 
 NH 4 C1. 
 
 NH 4 C1. 
 
 
 
 
 
 
 
 Na 2 HPO 4 
 
 
 Pb 
 
 Pb 
 
 
 Fe (ous) 
 
 Zn 
 
 Ba 
 
 Mg 
 
 K 
 
 White 
 
 Black ppt. 
 
 
 Greenish 
 
 White 
 
 White 
 
 White 
 
 
 ppt. 
 
 
 
 ppt. 
 
 ppt. 
 
 ppt. 
 
 ppt. 
 
 
 
 Hg" (ic) 
 
 
 Fe (ic) 
 
 
 
 
 
 
 Black ppt. 
 
 
 Brown 
 
 
 
 
 
 
 
 X 
 
 ppt. 
 
 
 
 
 Na 
 
 Ag 
 
 
 w 
 
 
 Mn 
 
 
 
 
 White 
 
 
 fc 
 
 
 Flesh-col- 
 
 
 
 
 ppt. 
 
 
 
 
 ored ppt. 
 
 
 
 
 (curdy) 
 
 
 
 
 
 
 
 
 
 Bi 
 
 rS 
 
 /-\ 
 
 Cr 
 
 
 Sr 
 
 
 
 
 Blackish- 
 
 9 
 
 Greenish 
 
 
 White 
 
 
 
 
 brown 
 
 1 
 
 ppt. 
 
 
 ppt. 
 
 
 
 
 ppt. 
 
 c 
 t 1 
 
 
 
 
 
 
 Hg' (ous) 
 White 
 
 Cu 
 
 
 Al 
 
 
 
 
 Li 
 
 ppt. 
 
 Black ppt. 
 
 
 White 
 ppt. 
 
 Co 
 
 
 
 NIL 
 
 
 
 
 
 Black 
 
 Ca 
 
 
 
 
 Cd 
 
 
 
 ppt. 
 
 White 
 
 
 
 
 Yellow ppt. 
 
 
 
 
 ppt. 
 
 
 
 
 As 
 
 
 
 Ni 
 
 
 
 
 
 Yellow ppt. 
 
 s 
 
 
 Black 
 
 
 
 
 
 
 
 
 ppt. 
 
 
 
 
 
 Sb 
 
 w 
 
 
 
 
 
 
 
 Orange ppt. 
 
 
 
 
 
 
 
 
 
 
 . fl 
 
 
 
 
 
 
 
 Sn (ous) 
 
 <u 
 
 
 
 
 
 
 
 Brown ppt. 
 
 3 
 
 3 
 
 
 
 
 
 
 
 Sn (ic) 
 
 1 
 
 
 
 
 
 
 
 Yellow ppt. , 
 
 
 
 
 
 
 
24 QUALITATIVE CHEMICAL ANALYSIS. 
 
 SPECIAL TESTS FOR METALS OF GROUP I. 
 
 (CHLORID GROUP.) 
 
 Each of these tests should be applied to a fresh portion of 
 the original solution. 
 
 28. Lead. 
 
 (Make test on a solution of Lead Nitrate.) 
 
 1. Precipitated by HCl=a white crystalline precipitate of 
 PbCl 2 soluble in hot water: 
 
 Pb(N0 3 ) 2 +2HCl =PbCl 2 +2HN0 3 . 
 
 Plumbic Chlorid. 
 
 2. The lodid Test: KI gives a crystalline yellow ppt., 
 PbI 2 , soluble in hot water: 
 
 Pb(N0 3 ) 2 +2KI PbI 2 +2KN0 3 . 
 
 Lead lodid. 
 
 3. The Chromate Test: K 2 Cr0 4 gives a bright-yellow ppt., 
 PbO0 4 , soluble in NaOH: 
 
 Pb(N0 3 ) 2 +K 2 Cr0 4 = PbCr0 4 +2KN0 3 . 
 
 Lead Chromate. 
 
 4. The Sulfuric Acid Test: H 2 S0 4 gives a white ppt., 
 PbS0 4 , soluble in NaOH : 
 
 Pb(N0 3 ) 2 +H 2 S0 4 = PbS0 4 +2HN0 3 . 
 
 Lead Sulfate. 
 
 5. The Ammonia Test: NH 4 OH gives a white ppt. (basic salt). 
 3Pb (N0 3 ) 2 +4NH 4 OH = 2PbO Pb (N0 3 ) 2 + 4NH 4 N0 3 +2H 2 0. 
 
COLL 
 
 RMA^ 
 
 INORGANIC BASES AND ACIDS. 25 
 
 29. Silver. 
 
 (Make tests on a solution of Silver Nitrate). 
 6. Precipitated by HC1 = a white ppt. AgCl, soluble in NH 4 OH; 
 reprecipitated by HN0 3 : 
 
 AgN0 3 +HC1 = AgCl +HN0 3 . 
 
 Silver Chlorid 
 
 7. Ammonia Test. NH 4 OH=a brownish-gray ppt., Ag 2 0, 
 soluble in excess: 
 
 2AgN0 3 +2NH 4 OH - Ag 2 +2NH 4 N0 3 +H 2 0, 
 
 Silver Oxid. 
 
 8. Chromate Test. K 2 Cr0 4 = a brick-red ppt., Ag 2 Cr0 4 , 
 soluble in NH 4 OH: 
 
 2AgN0 3 +K 2 Cr0 4 - Ag 2 Cr0 4 +2KN0 3 . 
 
 Silver Chromate. 
 
 9. lodid Test. KI = a pale-yellow ppt., Agl, insoluble in 
 
 AgN0 3 +KI = Agl +KN0 3 . 
 
 Silver lodid. 
 
 30. Mercurous Salts. 
 
 (Make tests on a solution of Mercurous Nitrate.) 
 
 10. Precipitated by HCl = a white ppt., Hg 2 Cl 2 , blackened by 
 NH 4 OH: 
 
 Hg 2 (N0 3 ) 2 + 2HC1 = Hg 2 Cl 2 + 2HN0 3 . 
 
 Mercuroua Chlorid. 
 
26 QUALITATIVE CHEMICAL ANALYSIS. 
 
 11. lodid Test. KI = a greenish-yellow ppt. of Hg 2 l2: 
 
 Hg 2 (N0 3 )2 + 2KI = Hg 2 I 2 + 2KN0 3 . 
 
 Mercurous lodid. 
 
 12. Ammonia Test. NH 4 OH = a black ppt. insoluble in 
 excess : 
 
 Hg 2 (N0 3 ) 2 + 2NH 4 OH = NH 2 Hg 2 N0 3 + NH 4 N0 3 + 2H 2 0. 
 
 Mercurous Ammonium Nitrate. 
 
 13. Chromate Test. K 2 Cr0 4 =red ppt. of Hg 2 Cr0 4 . 
 
 Hg 2 (N0 3 ) 2 + K 2 Cr0 4 = Hg 2 Cr0 4 + 2KN0 3 . 
 
INORGANIC BASES AND ACIDS. 
 
 27 
 
 
 M 
 
 gjj 
 
 8^3 
 
 sS.s 
 
 o 
 
 o 
 o 
 
 5! 
 
 JUa 
 
 ^|oq 
 
 3 8 " 
 
 5 all 
 
 E?.ll = 
 
 fci 
 
 lid 
 
 
 
 I 
 
 SS; 
 
 5 .5 .a 
 
 
 p 
 
 O 
 
 ft ^ 
 
 '3 fl 
 
 'S 
 
28 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 32. CHART FOR THE IDENTIFICATION OF THE METALS OF 
 GROUP I IN A SIMPLE SALT. 
 
 Group. 
 
 Reagent. 
 
 Result. 
 
 Indication. 
 
 Confirmatory Tests which Should 
 be Applied to Original Solution. 
 
 I 
 
 To a por- 
 tion of 
 original 
 solution, 
 add HC1, 
 drop by 
 drop un- 
 til no 
 further 
 ppt . 
 falls. 
 
 White ppt. 
 soluble 
 in hot 
 H 2 O. 
 
 Pb 
 
 Add KI= yellow ppt. 
 Apply tests as under para- 
 graph 28. 
 
 White 
 ppt. sol- 
 uble in 
 NH 4 OH. 
 
 Ag 
 
 Add K 2 CrO 4 = brick-red 
 PPt. 
 Apply tests under para- 
 graph 29. 
 
 White 
 ppt. 
 t u r n ed 
 black by 
 NH 4 OH. 
 
 Hg 
 
 Add KI = greenish-yellow 
 ppt. 
 Apply tests under paragraph 
 30. 
 
 33. In the following chart as in fact in all analyses of solu- 
 tions containing more than one metal the student should 
 remember that he must precipitate all the metals of the group 
 from the original solution by means of the proper group reagent, 
 and then separate the precipitated metals one from the other in 
 the manner described, before any attempt at identity be made. 
 
 He must not test for a particular metal by any particular 
 reagent in the original solution, except in the case of the alkali 
 metals. 
 
 It would, for instance, be quite improper and unsatisfactory 
 to test for silver in the presence of lead and mercury by means of 
 the iodid or the chromate reagents, as these act upon all three 
 metals and give a different colored precipitate with each. 
 
 34- 
 
 SYNOPSIS OF SEPARATION OF GROUP I. 
 
 P.O.S.+HC1 
 
 = ppt. =PbCl 2 +AgCH-H g2 Cl 2 
 
 
 +hot H 2 O 
 
 = dissolvesPbC! 2 
 P pt.=AgCl+Hg 2 Cl 2 
 
 +NH 4 OH 
 
 = dissolves AgCl 
 ppt. black = Hg 2 Cl 2 
 
INORGANIC BASES AND ACIDS. 
 
 29 
 
 35- CHART FOR THE SEPARATION OF GROUP I. 
 
 Group Reagent : Dilute hydrochloric acid. 
 
 To a portion of the original cold solution add dilute HC1 drop by drop 
 as long as a precipitate forms, then add a little more, agitate and filter. 
 Reserve filtrate for Group II and examine the precipitate as below. 
 
 1.* GROUP I. PRECIPITATE. 
 May contain Pb, Ag, or Hg' (ous). 
 
 Wash this precipitate with cold water, till the washings are free from 
 HC1 (when the washings will give no precipitate with AgNO 3 ), and reject 
 the washings. Then pour much hot water on the ppt. and collect the hot 
 solution. 
 
 2. Filtrate may con- 
 tain Pb. 
 
 3. Divide the filtrate 
 into three portions and 
 test as follows: 
 
 1. H 2 SO 4 = white ppt. 
 
 2. Kl yellow ppt. 
 
 3. K 2 CrO 4 = orange ppt. 
 
 i 4. Ppt. on filter paper may contain Ag and 
 Hg(ows). Pour upon it some warm NH 4 OH 
 and collect the fiKrate. 
 
 5. Filtrate may 
 contain Ag. 
 
 Confirm by add- 
 ing HNO 3 = white 
 ppt. 
 
 6. Ppt. on filter paper 
 may contain Hg (ous). -If 
 the ppt. turns black on 
 addition of the NH 4 OH in 
 step 4, it indicates Hg(ows) . 
 Confirm by dissolving in 
 aqua regia (3 parts HC1 
 and 1 part HNO 3 ); dilute 
 with water and add SnCl 2 
 = grayish ppt. 
 
 * The numbers refer to the notes. The student should read the notes 
 as he performs each step, as they explain the reasons for each method used. 
 
 36. 
 
 NOTES ON GROUP I. 
 
 (1) On the addition of HC1 the following chlorids are formed: 
 lead chlorid (PbCl 2 ), silver chlorid (AgCl), and mercurous 
 chloric! (HgCl). These being insoluble are precipitated together 
 with the oxychlorids of antimony (SbOCl) and bismuth (BiOClj. 
 The first three are insoluble in weak acids; the remaining two 
 are soluble in excess of weak acids and water, therefore remain 
 in the filtrate. Lead chlorid is slightly soluble in water, and 
 when present in mere traces only, it passes into Group II, 
 where it precipitates as sulfid. 
 
 CALIFORNIA COLLEGE 
 
 of PHARMACY 
 
30 QUALITATIVE CHEMICAL ANALYSIS. 
 
 It is advisable to use dilute HC1 for the following reasons: 
 
 (a) Strong HC1 precipitates various other salts from, strong 
 solutions. 
 
 (&) AgCl and HgCl are to some extent soluble in strong 
 HC1 ; traces of these might therefore be overlooked. 
 
 (c) The BiOCl and SbOCl are soluble in HC1, and hence 
 pass over into Group II. 
 
 (2) When boiling H 2 is poured over the precipitate, 
 the lead chlorid being soluble passes through the filter and 
 deposits on cooling. 
 
 The presence of lead in the filtrate may be proven by divid- 
 ing it into three portions, and tests applied to each portion. 
 See par. 28. 
 
 (3) When solution of NH 4 OH is poured over the precipi- 
 tate left on filter, the AgCl dissolves, forming argentic amin, 
 AgCl(NH 3 ) 2 . 
 
 (4) The insoluble ppt. left on the filter is the black mer- 
 curous amin, NH 2 Hg2Cl, which is rather unstable and yields 
 some metallic mercury by decomposition. 
 
 The Hg" may also be proven by mixing some of the black 
 precipitate with dry Na 2 C0 3 and heating in a tube, when 
 metallic globules or a mirror of mercury will be formed. 
 
 When aqua regia is poured over the precipitate it forms 
 mercuric chlorid (HgCl 2 ), which is reduced by stannous chlorid 
 (SnCl 2 ) to grayish-white mercurous chlorid (Hg 2 Cl 2 ) or black- 
 ish-gray metallic mercury (Hg). 
 
 (5) The addition of the HN0 3 in the confirmatory test 
 neutralizes the ammonia, and the AgCl is thrown down as a 
 white curdy precipitate. 
 
 SPECIAL TESTS FOR METALS OF GROUP II. 
 (AciD SULFID GROUP.) 
 
 Each test to be made upon a fresh portion of the original 
 solution. 
 
A COLUGE 
 ot HHAHMACX 
 
 INORGANIC BASES AND ACIDS 31 
 
 37. Mercuricum. 
 
 (Make tests on a solution of Mercuric Chlorid.) 
 
 14. Precipitated from acid solution by H 2 S = a reddish-black 
 ppt. of HgS, insoluble in HN0 3 : 
 
 HgCl 2 +H 2 S = HgS+2HCl. 
 
 Mercuric 
 Sulfid. 
 
 15. Sodium Hydroxid Test. NaOH = a yellow ppt. of mer- 
 curic oxid, HgO, insoluble in excess: 
 
 HgCl 2 +2NaOH = HgO +2NaCl +H 2 0. 
 
 Mercuric 
 Oxid. 
 
 16. Potassium Iodid Test. KI=a red ppt. of mercuric iodid, 
 HgI 2 , soluble in excess of KI and HgCl 2 : 
 
 HgCl 2 +2KI = HgI 2 +2KC1. 
 
 Mercuric 
 Iodid. 
 
 17. Ammonia Test. NH 4 OH = a white ppt. of mercuric 
 ammonium chlorid, NH 2 HgCl: 
 
 HgCl 2 +2NH 4 OH = NH 2 HgCl +NH 4 C1 +2H 2 0. 
 
 Mercuric Am- 
 monium Chlorid. 
 
 18. Chromate Test. K 2 O0 4 =a reddish-yellow ppt. of mer- 
 curic chromate HgCr0 4 , soluble in HNOs. 
 
 HgCl 2 + K 2 Cr0 4 = HgCr0 4 + 2KC1. 
 
32 QUALITATIVE CHEMICAL ANALYSIS. 
 
 38. Bismuth. 
 
 (Make tests on a solution of Bismuth Nitrate.) 
 
 19. H 2 S in acid solution = a brown ppt. of Bi 2 S 3 , insoluble 
 in (NH 4 ) 2 S: 
 
 2Bi(N0 3 ) 3 + 3H 2 S = Bi 2 S 3 + 6HN0 3 . 
 
 Bismuth Sulfid. 
 
 20. Potassium lodid Test. KI = a greenish-brown ppt. of 
 BiI 3 , soluble in excess: 
 
 Bi(N0 3 ) 3 +3KI = BiI 3 + 3KN0 3 . 
 
 Bismuth lodid. 
 
 21. ChromateTest. K 2 Cr0 4 =a yellow ppt. of Bi 2 (Cr0 4 ) 3 : 
 
 Bismuth Chromate. 
 
 22. Water Test. Acidify with HC1, evaporate to a small bulk 
 in test tube, and then pour into a large volume of water. A 
 milkiness indicates bismuth: 
 
 BiCl 3 + H 2 = BiOCl + 2HC1. 
 
 39- Copper. 
 
 (Make tests on a solution of Copper Sulphate.) 
 
 23. Precipitated from acid solutions by H 2 S = a brownish- 
 black ppt. of CuS, soluble in HN0 3 : 
 
 CuS0 4 + H 2 S = CuS + H 2 S0 4 . 
 
 Copper Sulfid. 
 
 24. Ammonia Test. NH 4 OH = a blue ppt. soluble in excess 
 to a dark-blue liquid: 
 
 CuS0 4 +2NH 4 OH = Cu(OH) 2 + (NH 4 ) 2 S0 4 
 and 
 
 CuS0 4 +4NH 4 OH = Cu(NH 4 ) 2 (NH 2 ) 2 S0 4 +4H 2 0. 
 
 Ammomo-cupric Sulfate. 
 
INORGANIC BASES AND ACIDS. 33 
 
 25. Sodium Hydroxid Test. NaOH = a blue ppt., becoming 
 black, CuO, on boiling. 
 
 CuS0 4 + 2NaOH = Cu(OH) 2 + Na 2 S0 4 
 
 Copper Hydroxid. 
 
 and 
 
 Cu(OH) 2 +heat=CuO+H 2 0. 
 
 26. Ferrocyanid Test. K 4 Fe(CN) 6 =a brown ppt. of 
 Cu 2 Fe(CN) 6 , insoluble in dilute acids: 
 
 2CuS0 4 + K 4 Fe (CN) 6 = Cu 2 Fe (CN) 6 + 2K 2 S0 4 . 
 
 Copper Ferrocyanid. 
 
 27. Chromate Test. K 2 Cr0 4 = a reddish-brown ppt. of CuCr0 4 , 
 soluble in NH 4 OH to a green solution. 
 
 CuS0 4 + K 2 Cr0 4 = CuCr0 4 + K 2 S0 4 . 
 
 Copper Chromate. 
 
 40. Cadmium. 
 
 (Make tests on a solution of Cadmium Chlorid.) 
 
 28. Precipitated from acid solution by H 2 S= yellow ppt. 
 CdS insoluble in (NH 4 ) 2 S but soluble in HN0 3 . This ppt. will 
 form in the presence of potassium cyanid (distinction from copper) : 
 
 CdCl 2 +H 2 S = CdS+2HCl. 
 
 Cadmium 
 Sulfid. 
 
 29. Ammonia Test. NH 4 OH = a white ppt. of Cd(OH) 2 , 
 soluble in excess: 
 
 CdCl 2 + 2NH 4 OH = Cd(OH)2 + 2NH 4 C1. 
 
 Cadmium 
 Hydroxid. 
 
 30. Sodium-hydroxid Test.N&OH = a white ppt. of Cd(OH) 2 , 
 insoluble in excess : 
 
 CdCl 2 + 2NaOH = Cd (OH) 2 + 2NaCl. 
 
 31. Apply sodium-carbonate test. A brown coating of CdO; 
 no metallic bead. 
 
34 QUALITATIVE CHEMICAL ANALYSIS. 
 
 41. Arsenic. 
 
 (Make tests on a solution of Arsenic Chlorid.) 
 
 32. Precipitated from acid solutions by H 2 S = a yellow ppt. 
 of As 2 S3 : 
 
 As 2 5 + 5H 2 S = As 2 S 3 + 5H 2 + S 2 . 
 
 Arsenous 
 Sulfid. 
 
 Upon boiling and passing an excess of H 2 S through the 
 solution, As 2 S 5 is pptd. 
 
 33. Ammonio-Silver-nitrate Test. AgN0 3 in NH 4 OH solu- 
 tion = a reddish-brown ppt. of AgsAs0 4 . 
 
 H3As0 4 + 3AgN0 3 = A g3 As0 4 + 3HN0 3 . 
 
 This is the differentiating test from arsenosum, which com- 
 pare. 
 
 42. Arsenous. 
 
 (Make tests on a solution of Arsenous Chlorid.) 
 
 34. Precipitated from acid solutions by H 2 S = a yellow ppt. 
 of As 2 S 3 , soluble in (NH 4 ) 2 S, and reprecipitated by HC1: 
 
 2As 2 3 + 6H 2 = 4H 3 As0 3 
 and 
 
 4H 3 As0 3 + 6H 2 S = 2As 2 S 3 + 12H 2 0. 
 
 Arsenous Sulfid. 
 
 35. Copper-sulphate Test. In neutral solutions CuS0 4 =a 
 pale-green ppt. of CuHAs0 3 (Scheele's green), soluble in NH 4 OH: 
 
 H 3 As0 3 + CuS0 4 + 2NH 4 OH = CuHAs0 3 + (NH 4 ) 2 S0 4 + 2H 2 0. 
 
 Copper Arsenite. 
 
 36. Ammonio-Silver-nitrate Test. AgN0 3 in NH 4 OH solu- 
 tion = yellow ppt. Ag 3 As0 3 (silver arsenite): 
 
 H-jAsOs + 3AgN0 3 = A g3 As0 3 + 3HN0 3 . 
 
 37. Charcoal Test. Heated on charcoal, arsenic gives a white 
 incrustation and a garlicky odor. 
 
INORGANIC BASES AND ACIDS. 35 
 
 38. Apply both Marsh's and Fleitmann's tests. 
 
 Marsh's Arsenic Test. Generate hydrogen with dilute 
 H2S04 and metallic zinc in a bottle furnished with a jet and 
 funnel- tube. After the gas has been given off in sufficient 
 qu'antity to expel all the air contained in the bottle, the gas 
 is ignited. 
 
 In order to minimize the danger of explosion, it is advisable, 
 before igniting the gas, to place an empty test-tube over the 
 mouth of the jet, and when the gas has been given off for about 
 five minutes, ignite the gas in the test-tube, and use this to ignite 
 the gas issuing from the jet. Notice that the flame is yellow, 
 due to the sodium in the glass. Now introduce the arsenical 
 solution through the funnel tube, a little at a time. 
 
 The yellow flame is at once changed to a bluish flame char- 
 acteristic of arsenic, and which emits a garlicky odor. If a 
 piece of cold porcelain is held in this flame, a brownish-black 
 spot of metallic arsenic is deposited upon it. (This is called an 
 arsenic-spot.) The zinc and sulfuric acid used for generating 
 the hydrogen must both be free from arsenic. 
 
 Marsh's test is based on the formation of arsine gas, AsH 3 , 
 the product of the action of nascent hydrogen upon arsenic 
 in an acid medium: 
 
 6Zn + 6H 2 S0 4 + As 2 3 = 2AsH 3 + 6ZnS0 4 + 3H 2 0. 
 
 Marsh's test, further, is used to differentiate between arsenic 
 and antimony in a solution; for instance, antimony produces 
 the same kind of spot as arsenic, but the arsenic spots dissolve 
 readily when treated with a few drops of a hypochlorite or 
 euchlorin solution, while the antimony spots are not affected. 
 
 39. Fkitmann's Test for Arsenic. Place a fragment of metallic 
 zinc or aluminum in a test-tube with some KOH solution and 
 add a small quantity of the arsenical solution. 
 
 Heat the mixture and place over the mouth of the tube a 
 cap of poper moistened with a solution of AgN0 3 . The arsine 
 which is evolved acts uDon the silver nitrate, reducing it to 
 
36 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 metallic silver, which is shown by the development of a dark 
 stain on the paper. 
 
 The advantage of this test lies in the fact that stibine, SbH 3 , 
 is not evolved, as is the caso in Marsh's test, and hence only 
 arsenic reacts in the manner described : 
 
 Zn+2KOH = K 2 Zn0 2 +H 2 ; 
 
 Potassium 
 Zincate. 
 
 H 3 As0 3 + 3H 2 = Asli 3 + 3H 2 ; 
 
 Arsine. 
 
 AsH 3 +6AgN0 3 -f 3H 2 = 3Ag 2 +H 3 AsO 3 +6HN0 3 . 
 
 Metallic 
 Silver. 
 
 40. U. S. P. Arsenic Test. The U. S. P. and N. F.fix a permis- 
 sible limit of arsenic in chemicals and employ a modification of 
 Gutzeit's test measuring the stain produced on mercuric bromid 
 paper and comparing this with a standard stain prepared under 
 exact conditions of the test. (See U. S. P. IX, page 584.) 
 
 41. In testing bismuth and antimony stilts for arsenic, apply 
 Bettendorf s test for arsenic. (See U. S. T. IX, page 586.) 
 
 42. Reinch's Test for Arsenic and Antimony. Acidify a por- 
 tion of ths original solution with HC1 and introduce a strip of 
 bright shiny copper foil and boL for a few minutes. 
 
 Arsenic. 
 
 Antimony. 
 
 A gray film is deposited on the coppe: 1 
 foil. Wash the foil in water, and dn 
 it between filter papers. Heat in a 
 long, perfectly dry, test-tube. A 
 wide band of crystals of ^4s 2 3 if 
 deposited on the cooler portion of 
 the tube. These crystals, when 
 viewed by a hand lens, or under the 
 microscope, are found to be eight- 
 sided. They are soluble in water 
 (distinction from Sb), and when H 2 Q 
 is passed into the acidulated solu- 
 tion, a yellow precipitate results. 
 
 A black film is deposited on the copper. 
 Wash the foil in water, and dry it 
 between filter papers. Heat in a 
 long, perfectly dry, test-tube. A 
 band of amorphous Sbz0 3 is de- 
 posited on the tube near the copper. 
 This deposit is insoluble in water, 
 but soluble in a solution of Potassium 
 Bitartrate, and if this pcluiion is 
 treated with P 2 ^ g?s, it gives an 
 orange precipitate, characteristic of 
 Sb. 
 
INORGANIC BASES AND ACIDS. 37 
 
 43. Antimony. 
 
 (Make tests on a solution of Antimony Chlorid.) 
 
 43. Precipitated from acid solutions by H 2 S = an orange ppt. of 
 80283, soluble in (NH 4 ) 2 S, and reprecipitated by HC1. The ppt. 
 is not soluble in (NH 4 ) 2 C03 solution (distinction from arsenic) : 
 
 2SbCl 3 +3H 2 S =Sb 2 S 3 +6HC1. 
 
 Antimonic 
 Sulfid. 
 
 44 Copper Test. Metallic copper in acid solutions of anti- 
 mony receives a grayish deposit of antimony; when this is 
 heated in a test-tube a white ring of Sb 2 3 forms in the tube, 
 near the copper : 
 
 Cu 5 +Sb 4 +30 2 = Cu 5 +2Sb 2 3 . 
 
 Metallic 
 Copper. 
 
 45. Water Test. Slightly acid solutions of SbCl 3 poured in 
 water = a white ppt. of (SbOCl) 2 + Sb 2 3 , soluble in tartaric acid: 
 
 4SbCl 3 + 5H 2 = (SbOCl) 2 +Sb 2 3 + 10HC1. 
 
 Powder of Algaroth. 
 
 46. Apply Marsh's Test. Antimony stain is insoluble in 
 hypochlorite solution. 
 
 44. Stannic Salts. 
 
 (Make tests on a solution of Stannic Chlorid.) 
 
 47. H 2 S precipitates from acid solutions SnS 2 = a yellow ppt. 
 slowly soluble in (NH 4 ) 2 S, and reprecipitated by HC1: 
 
 SnCl 4 + 2H 2 S = SnS 2 + 4HC1. 
 
 Stannic 
 Sulfid. 
 
38 QUALITATIVE CHEMICAL ANALYSIS. 
 
 48. Sodium-hydroxid 7^. NaOH = white ppt. Sn(OH) 4 : 
 
 SnCl 4 +4NaOH = Sn(OH) 4 +4NaCl. 
 
 Stannic 
 Hydroxid. 
 
 49. Molybdenum Test. (NH 4 ) 2 Mo0 4 =no blue coloration 
 (distinction from stannous). 
 
 45. Stannous Salts 
 
 (Make tests on a solution of Stannous Chlorid.) 
 
 50. Precipitated by H 2 S from acid solution as SnS = a brown 
 ppt. slowly soluble in (NH 4 ) 2 S; reprecipitated by HCl = a yellow 
 ppt. of SnS 2 : 
 
 SnCl 2 +H 2 S = 
 
 51. Sodium-hydroxid Test. NaOH = a white ppt. of Sn(OH) 2; 
 soluble in excess of reagent : 
 
 SnCl 2 + 2NaOH = Sn(OH) 2 + 2NaCl; 
 Sn(OH) 2 + 2NaOH = Na 2 Sn0 2 + 2H 2 0. 
 
 Sodium 
 
 Stannite. 
 
 52. Mercuric Test. HgCl 2 produces in solutions of stannous 
 salts a white ppt. of Hg 2 Cl 2 which darkens on boiling, being 
 reduced to Hg: 
 
 SnCl 2 + HgCl 2 = SnCl 4 + Hg. 
 
 53. Molybdenum Test. (NH 4 ) 2 Mo0 4 =a blue ppt. (dis- 
 tinguished from stannic.) 
 
INORGANIC BASES AND ACIDS. 
 
 39 
 
 46. CHART FOR THE "COMPARATIVE" OBSERVATION OF THE 
 REACTIONS OF THE METALS OF GROUP II. 
 
 DIVISION A. SULFIDS INSOLUBLE IN (NH 4 ) 2 S 
 
 Reagents. 
 
 Pb. 
 
 Hg(ic). 
 
 Bi. 
 
 Cu. 
 
 Cd. 
 
 H 2 S in 
 pres- 
 
 Black ppt. 
 PbS. Solu- 
 
 Reddish 
 black ppt. 
 
 Brown ppt. 
 
 Bi 2 S 3 . 
 
 Black ppt. 
 CuS. Sol- 
 
 Yellow ppt. 
 CdS. Solu- 
 
 ence of 
 
 ble in hot, 
 
 HgS. Insol- 
 
 Soluble in 
 
 uble i n 
 
 b 1 e in 
 
 HC1. 
 
 dilute 
 
 b 1 e in 
 
 HN0 3 . 
 
 HNO 3 . 
 
 HNO 3 . 
 
 
 HNO 3 . 
 
 HNO 3 . 
 
 
 
 
 NaOH 
 
 White ppt. 
 Pb(OH) 2 . 
 
 Yellow ppt. 
 HgO. In- 
 
 White ppt. 
 Bi(OH),. 
 
 Blue ppt. 
 Cu(OH) 2 . 
 
 White ppt. 
 Cd(OH) 2 . 
 
 
 Soluble in 
 
 soluble in 
 
 Soluble in 
 
 Becomes 
 
 Insoluble 
 
 
 excess. 
 
 excess. 
 
 HNO 3 . 
 
 black on 
 
 in excess. 
 
 
 
 
 
 boiling. 
 
 
 NH 4 OH 
 
 White ppt. 
 Insoluble in 
 
 White ppt. 
 HgNHaCl. 
 
 White ppt. 
 Bi(OH) 3 . 
 
 Blue ppt. 
 Cu(OH) 2 . 
 
 White ppt. 
 Cd(OH) 2 . 
 
 
 excess. 
 
 Soluble in 
 
 Insoluble 
 
 Soluble in 
 
 Soluble in 
 
 
 
 HC1. 
 
 in excess. 
 
 excess to a 
 
 excess. 
 
 
 
 
 
 blue solu- 
 
 
 
 
 
 
 tion. 
 
 
 KI 
 
 Crystalline 
 yellow ppt. 
 
 Red ppt. 
 HgI 2 . Sol- 
 
 Brown ppt. 
 BiI 3 . Sol- 
 
 Dirty-white 
 ppt. CuI 2 
 
 
 
 Soluble in 
 
 uble in ex- 
 
 uble in ex- 
 
 and free 
 
 
 
 boiling 
 
 cess of KI 
 
 cess. 
 
 iodine. 
 
 
 
 water. 
 
 and HgCl 2 . 
 
 
 
 
 K,CrO 4 . 
 
 Yellow ppt. 
 PbCrO 4 . 
 
 Reddish 
 yellow ppt. 
 HgCr0 4 . 
 
 Yellow ppt. 
 Bi 2 O(CrO 4 ) 2 
 Soluble in 
 
 Reddish- 
 brown ppt. 
 CuCrO 4 . 
 
 Yellow ppt. 
 CdCrO 4 . 
 Soluble in 
 
 
 
 Soluble in 
 
 HNO 3 . In- 
 
 Soluble in 
 
 acids. 
 
 
 
 HNO 3 . 
 
 soluble in 
 
 NH 4 OHto 
 
 
 
 
 
 KOH. 
 
 a green 
 
 
 
 
 
 
 solution. 
 
 
 K 4 Fe- 
 (CN).. 
 
 White ppt. 
 
 Pb 2 Fe(CN) 6 . 
 
 White ppt. 
 becomin g 
 blue on 
 
 Pale yellow 
 ppt. Sol- 
 uble in 
 
 Brown ppt. 
 Cu 2 Fe(CN) 6 . 
 Insoluble 
 
 Almost 
 white ppt. 
 Cd 2 Fe(CN). 
 
 
 
 long stand- 
 
 HC1. 
 
 in dilute 
 
 Soluble in 
 
 
 
 ing. 
 
 
 acids. 
 
 HC1. 
 
40 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 46a. CHART FOR THE "COMPARATIVE" OBSERVATION 
 THE REACTIONS OF THE METALS OF GROUP II 
 DIVISION B. SULFIDS SOLUBLE IN (NH 4 ) 2 S 
 
 OF 
 
 Reagents. 
 
 As. 
 
 Sb. 
 
 Sn. 
 
 H 2 S in 
 
 presence 
 of HC1. 
 
 ous. 
 
 ic. 
 
 Orange ppt. 
 Sb 2 S 3 . Sol- 
 uble in 
 HC1. 
 
 ous. 
 
 ic. 
 
 Yellow ppt. 
 As 2 S 3 . In- 
 soluble in 
 HC1. 
 
 Yellow ppt. 
 As 2 S 3 . In- 
 soluble in 
 HC1. 
 
 Brown ppt. 
 SnS. Sol- 
 uble in 
 boiling 
 HC1. 
 
 Yellow ppt. 
 SnS 2 . Sol- 
 uble in 
 boiling 
 HC1. 
 
 NaOH 
 
 
 
 White ppt. 
 Soluble in 
 excess. 
 
 White ppt. 
 Sn(OH) 2 . 
 Soluble in 
 excess. 
 
 White ppt. 
 Sn(OH) 2 . 
 Soluble in 
 excess. 
 
 NH 4 OH 
 
 
 
 White ppt. 
 Insoluble 
 in excess. 
 
 White ppt. 
 Sn(OH) 2 . 
 Darkens 
 on boiling 
 in excess. 
 
 White ppt. 
 Sn(OH) 4 . 
 Slightly 
 soluble in 
 excess. 
 
 NH 4 OH 
 and 
 AgN0 3 . 
 
 Yellow ppt. 
 Ag 3 AsO 3 . 
 
 Brown ppt. 
 Ag 3 AsO 4 . 
 
 
 
 
 NH 4 OH 
 and 
 CuSO 4 . 
 
 Yellowish- 
 green ppt. 
 CuHAsO 3 . 
 
 Pale green 
 ppt. 
 CuHAsO 4 . 
 
 
 
 
 H 2 O 
 acidu- 
 lated. 
 
 
 
 White ppt. 
 (SbOCl) 2 
 +Sb 2 3 . 
 
 
 
 (NH 4 ) 2 
 MoO 4 . 
 
 
 
 
 Blue color- 
 ation. 
 
 No blue 
 coloration. 
 
 HgCl 2 . 
 
 Marsh's 
 Test. 
 
 
 
 
 White ppt. 
 Hg 2 Cl 2 
 darkens 
 on boiling. 
 
 
 Dark stain of As (metal- 
 lic). Soluble in NaCIO 
 solution. 
 
 Black stain 
 of metallic 
 Sb. Insol- 
 uble in 
 NaCIO. 
 
 
 
 Fleit- 
 mann's 
 Test. 
 
 Black stain of Ag (metal- 
 lic) on paper moistened 
 with AgNO 3 . 
 
 No black 
 stain o f 
 Ag. 
 
 
 
CALIFORNIA COL 
 PHARMACY 
 
 INORGANIC BASES AND ACIDS. 
 
 41 
 
 47- CHART FOR THE IDENTIFICATION OF THE METALS OF 
 GROUP H IN A SIMPLE SALT 
 
 Group. 
 
 Reagent. 
 
 Result. 
 
 
 Indication 
 
 Confirmatory Tests which should 
 be Applied to Original Solution. 
 
 II 
 
 If no ppt. 
 with HC1 or 
 if ppt. is 
 
 Black 
 ppt. 
 
 
 Pb 
 
 Add K 2 CrO 4 = Yellow ppt. 
 Apply tests under paragraph 
 
 28. 
 
 
 an excess of 
 the reagent, 
 pass H 2 S 
 
 Black 
 ppt. 
 
 X 
 
 9 
 
 Hg" 
 
 Add KI = red ppt. soluble hi 
 excess. Apply tests under 
 paragraph 37. 
 
 
 the acidi- 
 fied .8 1 U - 
 tion. 
 
 Dark 
 brown 
 ppt. 
 
 
 
 ..a 
 ^ 
 
 Q 
 
 Bi 
 
 Add KI = greenish-brown ppt 
 Apply tests under para- 
 graph 38. 
 
 
 
 Black 
 ppt. 
 
 '3 
 
 1 
 
 
 
 Cu 
 
 Add NH 4 OH=a light blue 
 ppt. Soluble in excess. 
 Apply tests under para- 
 graph 39. 
 
 
 
 Yellow 
 ppt. 
 
 
 Cd 
 
 Add NH 4 OH=a white ppt. 
 Soluble in excess. Apply 
 tests under paragraph 40. 
 
 
 
 Yellow * 
 ppt. 
 
 ^ 
 
 As 
 
 Ppt. soluble in (NH 4 ) 2 S, re- 
 precipitated by HC1. Ap- 
 ply tests under paragraphs 
 41 and 42. 
 
 
 
 Orange 
 ppt. 
 
 w 
 fc 
 
 a 
 
 Sb 
 
 Ppt. soluble in (NH 4 ) 2 S, re- 
 precipitated by HC1. Apply 
 tests under paragraph 43. 
 
 
 
 Brown 
 ppt. 
 
 
 | 
 ~o 
 
 02 
 
 Sn 
 
 Add NaOH = white ppt.; 
 boil, ppt. is insoluble. Ap- 
 ply tests under paragraph 44. 
 
 
 
 Yellow 
 ppt. 
 
 
 Sn 
 
 Add NaOH = white ppt.; 
 boil, ppt. dissolves. Apply 
 tests under paragraph 45. 
 
42 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 48. SYNOPSIS OF THE SEPARATION OF THE METALS 
 
 OF GROUP II. 
 
 To the fil- 
 trate o f 
 Group I, 
 or to a 
 portion of 
 the origi- 
 nal solu- 
 tion acidi- 
 ified with 
 HC1, add 
 H 2 S gas 
 in excess 
 = ppt. 
 
 Ppt.= Pb Hg Bi Cu Cd As Sb Sn 
 + (NH 4 ) 2 S, which dissolves As Sb Sn 
 
 DIVISION A 
 Ppt.= Pb Hg Bi Cu Cd 
 
 DIVISION B 
 
 Solution = As Sb 
 
 Sn 
 
 +HNO 3 , which eliminates Hg 
 
 +dil. HCl+strong HC1 
 precipitates As 
 
 Solution = Pb Bi Cu Cd 
 
 Q/rlnfi/vn QK 
 
 Sn 
 
 +H,SO 4 precipitates Pb 
 
 ooiution OD 
 
 Boil, add Cu turn- 
 ings +HgCl 2 precipitates 
 
 Sn 
 
 Solution = Bi Cu Cd 
 
 +NH 4 OH in excess precipi- 
 tates Bi 
 
 Solution = Sb 
 
 Solution = Cu Cd 
 
 
 
 +HNO 3 and divide into two 
 portions. 
 
 Portion 1 -f NH 4 OH =blue 
 solution = Cu 
 
 Portion 2+NH 4 OH+HCl 
 
 H- H 2 S gas precipitates Cd 
 
 
 49. CHART FOR SEPARATION OF GROUP II. 
 
 Pass H 2 S gas into the warmed filtrate of Group I, until it 
 smells strongly of the gas, after shaking. Heat to boiling, pass 
 some more H 2 S into the solution, allow the precipitate to sub- 
 side, and filter. Test a small portion of the filtrate, diluted with 
 water, by passing more H 2 S through it, to see if the precipita- 
 tion is complete. Wash the precipitate with boiling hot water, 
 until free from acid, collect all the precipitate on a filter paper, 
 and reserve the filtrate and washings, for Group III. The pre- 
 cipitate may contain Cu, Pb, Hg, Bi, Cd, As, Sb, Sn. 
 
 Puncture the filter paper, and completely wash the precipitate 
 into a clean porcelain crucible, with a few drops of NH 4 OH and 
 an excess of (NH 4 ) 2 S and filter. 
 
INORGANIC BASES AND ACIDS. 
 
 43 
 
 DIVISION A. 
 
 Precipitate. 
 
 10. May contain Cu, Pb, Hg, Bi, Cd. 
 over the ppt., and filter. 
 
 Wash, pour dilute boiling HNO 3 
 
 11. Precipitate. 
 
 Hg. 
 
 Dissolve in aqua regia by aid of 
 heat. Evaporate to dry ness, di- 
 lute with H 2 O, and add KI: red 
 ppt. = Hg. 
 
 12. Filtrate. 
 Cu, Pb, Bi, Cd. 
 Add dil. H 2 SO 4 , boil 
 well and filter. 
 
 13. Precipitate. 
 
 Pb. 
 
 Dissolve the ppt. in NH 4 C 2 H 3 O 2 , 
 made by adding HC 2 H 3 O 2 in ex- 
 cess to NH 4 OH, divide into two 
 portions, and add to 
 P. 1, KI=yellow ppt.=Pb. 
 P 2, K 2 CrO 4 = orange ppt. = Pb. 
 
 14. Filtrate. 
 Cu, Bi, Cd. 
 Dilute with H 2 O, 
 add excess of NH 4 OH, 
 and filter. 
 
 15. Precipitate. 
 
 Bi. 
 
 Puncture filter papar, and wash 
 into a clean test-tube, with a small 
 quantity of warm dil. HC1, evap- 
 orate to a low bulk, and pour into 
 a large volume of cold water: 
 White ppt. = Bi. 
 
 16. Filtrate. 
 
 Cu, Cd. 
 
 A blue solution in- 
 dicates Cu. Add a 
 little HNO 3 . Divide 
 in two portions. 
 
 Portion 1 Add NH 4 OH: blue 
 = Cu or, add to acidified solution, 
 someK 4 Fe(CN) 6 : brown ppt.=Cu. 
 
 DIVISION B. 
 
 Filtrate. 
 
 7. May contain As, Sb, Sn. Add dilute HC1, filter and w. sh. Diss Ive 
 the ppt. in strong HC1, boil gently, and filter. 
 
 8. Precipitate. 
 
 As. 
 
 Apply Marsh's test. 
 A metallic stain = As. 
 
 9. Filtrate. 
 Sb and Sn. 
 Divide into two portions. 
 
 Portion 1. 
 
 B .ilwith copper turn- 
 ings and add HgCl 2 : 
 white or grayish ppt. 
 =Sn. 
 
 Portion 2. 
 
 Apply Marsh's test. If a metallic stain 
 ir* sol. in N..C1O solution is produced : =Sb. 
 
44 QUALITATIVE CHEMICAL ANALYSIS. 
 
 50. OBSERVATIONS ON GROUP II. 
 
 The separation of the members of this group requires very 
 careful manipulation to insure success. 
 
 The precipitate may contain any or all of the following 
 metals and possess characteristic colors, thus: Black or brown- 
 ish black: CuS, PbS, HgS, Bi 2 S 3 , SnS. Yellow: CdS, As 2 S 3 , 
 As 2 S 5 , SnS 2 . Orange: Sb 2 S 3 , Sb 2 S 5 . When H 2 S is first 
 passed into solutions containing lead and mercuric mercury 
 they give colored precipitates due to formation of double 
 salts, thus: HgCl 2 Hg. At first it is white, then it turns red, 
 brown, and finally black under the continuous action of H 2 S, 
 owing to the formation of HgS. Lead salts under like condi- 
 tions give red precipitates gradually changing to brown, then 
 to black, owing the conversion to PbS. 
 
 In addition to the above-mentioned sulfids of this group 
 a white precipitate of sulfur is formed, especially if the original 
 solution is very acid or when it contains a ferric salt, chromic 
 or nitric acid, or a chlorate. These substances being strong 
 oxidizing agents will be reduced by the H 2 S, precipitating 
 sulfur, which is easily distinguished from CdS and As 2 S 3 by 
 its lighter color and density. 
 
 Ferric salts will be reduced to ferrous salts: 
 
 2FeCl 3 +H 2 S = 2FeCl 2 +2HC1 +S. 
 Chromic acid will be reduced to chromic chlorid: 
 2H 2 Cr0 4 +3H 2 S +6HCl = Cr 2 Cl 6 +S 3 +8H 2 
 Nitric acid will be reduced to nitric oxid: 
 2HN0 3 +3H 2 S=2NO +S 3 +4H 2 0. 
 
 As said above, it is almost useless to pass H 2 S into very 
 acid solutions, especially those containing HN0 3 or aqua 
 regia. If these acids have been used in dissolving the original, 
 the solution so formed should be first evaporated to dryness 
 
INORGANIC BASES AND ACIDS. 45 
 
 the residue dissolved in a little water with the aid of a few 
 drops of HC1, before passing H 2 S into it. It is, however, 
 essential that the solution be slightly acid; this is necessary 
 to prevent the precipitation of Zn, Co, and Ni. 
 
 Complete precipitation of the second group often seems 
 tedious, but it should under no circumstances be scamped, 
 if accurate and definite results are to be obtained. 
 
 To attain this end it is necessary, first, to use a sufficient 
 quantity of H 2 S; second, to test a portion of the solution by 
 filtration, dilution, and repeated precipitation until the satura- 
 tion be complete. 
 
 The metals precipitate much more quickly from a hot than a 
 cold solution, especially arsenicum; its yellow precipitate forms 
 very slowly, thus: 2H 3 As04+5H 2 S = As 2 S 5 +8H 2 0; and to 
 facilitate its precipitation the solution should be well heated 
 from time to time. 
 
 Besides the above reason, the sulfids thus precipitated from 
 hot, weakly acid solutions and allowed to stand may be filtered 
 much more easily, for they exhibit to a marked degree the 
 property of becoming " colloidal" and consequently passing 
 through the filter-paper upon washing. If water saturated 
 with H 2 S or very dilute acetic acid be used for washing the 
 precipitate, this tendency is checked. 
 
 51. NOTES ON GROUP II. 
 
 7. The object of adding a little NH 4 OH before the addi- 
 tion of (NH 4 ) 2 S is to neutralize the acid present, thus preventing 
 the precipitation of sulfur. The precipitate should be digested, 
 not boiled: boiling precipitates some As, Sb, Sn. These sulfids 
 unite with the (NH4) 2 S, with the formation of salts of the 
 sulfo-acids, thus: 
 
 + 3(NH 4 ) 2 S x =2(NH 4 ) 3 AsS 3 ; 
 
 SnS + (NH 4 ) 2 S,= (NH 4 ) 2 SnS 2 . 
 
 CALIFORNIA COLLEGE 
 f PHARMACY 
 
46 QUALITATIVE CHEMICAL ANALYSIS. 
 
 The (NH 4 ) 2 S solution should be warmed with diluted HC1 (the 
 strong acid dissolves Sb 2 S 3 ). This reprecipitates all the sulfids 
 which must be filtered off and washed from the soluble ammonium 
 compounds. This reprecipitation is due to the instability of 
 the free acids (formed by the HC1) corresponding to the sulfo- 
 acid ammonium compounds above mentioned. On adding 
 strong HC1 and boiling, Sb and Sn dissolve as chlorids, while 
 the yellow arsenic sulfid remains undissolved. The boiling is 
 necessary to drive off the H 2 S. 
 
 8. The black spot formed in Marsh's test is soluble in solu- 
 tions of chlorinated soda or calcium. If part of the solution 
 is treated with CS 2 , and this solution allowed to evaporate 
 spontaneously, free S is separated. 
 
 9. The acid solution on being boiled with metallic copper 
 (preferably turnings), reduces the stannic chlorid to stannous 
 according to the reaction SnCU + Cu = SnCl 2 + CuCl 2 . The 
 SnCl 2 reduces mercuric chlorid (HgCl 2 ) to the mercurous 
 chlorid (Hg 2 Cl 2 ) or gray metallic Hg, according to the quantity 
 of SnCl 2 present. 
 
 10. The precipitate should be well washed to insure absence 
 of the metals of Group III, as the (NH4) 2 S will precipitate the 
 metals of the aluminum and iron groups. 
 
 11. Mercuric sulfid (HgS) is insoluble in boiling dilute 
 HNOs, but, owing to the presence of other sulfids, the treat- 
 ment with HNOs will cause evolution of H 2 S and formation of 
 nitrates and free sulfur, thus: 
 
 3H 2 S +2HN0 3 = S 3 +2NO +4H 2 0. 
 
 The free sulfur thus formed occludes a portion of the sulfids 
 other than HgS, and protects them from action of the HNOs. 
 Therefore the black residue thus formed which is insoluble in 
 HN0 3 should always be further tested before rejecting it. 
 
 HgS dissolved in aqua regia forms HgCl 2 ; this should be 
 evaporated to dryness to get rid of the chlorin, which would 
 liberate free iodin on the addition of KI. 
 
INORGANIC BASES AND ACIDS. 47 
 
 When the chlorin has all been driven off ; add a few drops of 
 water to dissolve the HgCl 2 , transfer to a test-tube, and allow 
 1 drop of KI T.S. to slowly run down the side of the test- tube, till 
 both solutions meet: A red precipitate forming, indicates Hg. 
 The KI T.S. is added in this manner, because the red iodid of 
 mercury which is formed is soluble in an excess of both KI and 
 HgCl 2 . Hg may further be identified by adding a few drops of 
 solution stannous chlorid (SnCl 2 ), when a grayish- white precip- 
 itate will form. Or, the precipitated HgS may be fused with 
 potassium cyanid (KCN) and sodium carbonate (Na 2 C0 3 ) in a 
 dry tube, when Hg will sublime a little above the fused mass. 
 
 12. The sulfids of Cu, Pb, Bi, Cd, dissolve in the nitric acid, 
 forming corresponding nitrates. Evaporate this nitrate solu- 
 tion to about one-fourth the original bulk and add sufficient 
 dilute H 2 S04 to displace the nitric acid and form corresponding 
 sulf ates. Continue evaporation until white H 2 S0 4 fumes appear. 
 This is a sign that all the HNOs is dissipated, which is important 
 for the reason that lead nitrate might remain in solution and 
 interfere in the detection of cadmium. 
 
 Cool the solution of sulfates, and dilute with water. The 
 sulfates of bismuth, copper, and cadmium go in solution and 
 may be readily filtered off from the insoluble PbS04. 
 
 13. Lead sulf ate dissolves readily in ammonium acetate, 
 forming a double salt. Divide this solution into two portions; to 
 one add KI; lead iodid will form : PbS0 4 +2KI = PbI 2 +K 2 S0 4 . 
 To the other portion add K 2 Cr0 4 ; lead chromate will form 
 according to the reaction PbS0 4 +K 2 Cr0 4 = PbCr0 4 +K 2 S0 4 . 
 Lead iodid forms a yellow, and the chromate an orange-colored, 
 precipitate. Either of the reagents may be applied directly to 
 the PbS0 4 on the filter. 
 
 14. The nitrate must be slightly diluted with water before 
 addition of NH 4 OH. The Cu and Cd dissolve in the ammonium 
 hydroxid to form soluble ammonium compounds, while the Bi 
 is precipitated as hydroxid, Bi(OH)3. 
 
 15. Filter off the Bi(OH) 3 and dissolve it on the filter by 
 
48 QUALITATIVE CHEMICAL ANALYSIS. 
 
 pouring warm dilute HC1 over the precipitate, returning the 
 filtrate until all the precipitate has passed into solution. The 
 solution contains BiCl 3 , and on evaporating it to a small bulk 
 to free it from excess of the HC1 and pouring it into a large 
 volume of water, a white, cloudy precipitate of bismuth oxy_ 
 chlorid (BiOCl) is produced. The evaporation to a small bulk 
 above directed is for the purpose of increasing the delicacy of 
 t le test, as the less HC1 used for dissolving the Li(OH) 3 the 
 more positive does this reaction become. 
 
 16. If the solution be of a blue cclcr, it indicates the pres- 
 ence of copper, the color being due to the formation of a new 
 compound, ammonio-sulfate of copper. Add to this solution a 
 few drops of HN0 3 , and divide, into two portions, a and b. 
 To portion a add NH 4 OH; a blue color = copper. To portion b 
 add NH 4 OH, acidulate with HC1, and pass H 2 S through the solu- 
 tion; a yellow precipitate indicates cadmium sulfid, CdS. 
 
 SPECIAL TESTS FOR METALS OF GROUP III. 
 
 (ALKALI SULFID GROUP.) 
 To be applied to separate portions of the solution. 
 
 52. Ferric Salts. 
 
 (Make tests on a solution of Ferric Chlorid.) 
 
 54. (NH^S precipitates from alkaline solutions (FeS-J-S), a 
 black ppt.; the FeS is soluble in HC1: 
 
 2FeCl 3 + 3 (NH 4 ) 2 S = 2FeS + S + 6NH 4 C1. 
 
 55. K4Fe(CN) Q Test. K 4 Fe(CN) 6 gives a deep blue ppt. of 
 of Fe 7 (CN)i 8 or Fe 4 (Fe(CN) 6 ) 3 insoluble in acids: 
 
 4FeCl 3 + 3K 4 Fe(CN) 6 = Fe 4 Fe(CN) 6 ) 3 + 12KC1. 
 
 Ferric 
 Ferrocyanid. 
 
INORGANIC BASES AND ACIDS. 49 
 
 56. K 3 Fe(CN) Q Test. K 3 Fe(CN) 6 gives a brown solution: 
 
 2FeCl 3 + 2K 3 Fe(CN) 6 = Fe 2 (Fe(CN) 6 ) 2 + 6KC1. 
 
 57. Hydroxid Test. Both NaOH and NH 4 OH= brown ppt., 
 insoluble in excess : 
 
 FeCl 3 +3NH 4 OH = Fe(OH)3+3NH 4 CL 
 
 Ferric 
 Hydroxid. 
 
 58. Sulphocyanid Test.~KCNS = blood-red coloration: 
 
 FeCl 3 + 3KS(CN) = Fe(GNS) 3 + 3KC1. 
 
 Ferric 
 Sulphocyanid. 
 
 53. Ferrous Salts. 
 
 (Make tests on a solution of Ferrous Sulfate.) 
 
 59. (NH 4 ) 2 S precipitates from alkaline solutions FeS soluble 
 in HC1 and quickly oxidized in the solution to FeS0 4 : 
 
 FeCl 2 + (NH 4 ) 2 S=FeS + 2NH 4 Cl. 
 
 Ferrous 
 Sulfid. 
 
 60. Ferrocyanid Test. K 4 Fe(CN) 6 = white ppt. (distinction 
 from ferric), rapidly becoming blue: 
 
 2FeCl 2 + 2K 4 Fe(CN) 6 = 2FeK 2 Fe(CN) 6 +4KCl. 
 
 61. Ferricyanid Tes. K 3 Fe(CN) 6 = deep-blue ppt. insoluble 
 in acids : 
 
 3FeCl 2 + 2K 3 Fe(CN) 6 = Fe 3 Fe 2 (CN)i 2 + 6KC1. 
 
 Ferrous 
 Ferricyanid. 
 
 62. Sulfocyanid Test. No red coloration (distinction from 
 ferric). 
 
 63. Ammonia Test. NH 4 OH= greenish ppt.: 
 
 FeCl 2 + 2NH 4 OH = Fe(OH) 2 + 2NH 4 C1. 
 
 Ferrous 
 Hydrate. 
 
50 QUALITATIVE CHEMICAL ANALYSIS. 
 
 64. Hydroxid Testf. NaOH= white ppt. rapidly becoming 
 green, then brown : 
 
 FeCl 2 +2NaOH=Fe(OH) 2 + 2NaCl. 
 
 Ferrous 
 Hydrate. 
 
 54. Aluminum. 
 
 (Make tests on a solution of Aluminum Sulfate.) 
 
 65. (NH 4 ) 2 S precipitates from alkaline solutions A1 2 (OH) 6 
 insoluble in excess: 
 
 Aluminum 
 Hydroxid. 
 
 66. Phosphate Test. Na 2 HP0 4 +NH 4 OH + HC 2 H 3 2 = a 
 white ppt. of A1P0 4 insoluble in hot HC 2 H 3 2 , but soluble in HC1 : 
 
 A1 2 (S0 4 ) 3 + 2H 3 P0 4 = 2A1P0 4 + 3H 2 S0 4 . 
 
 Aluminum 
 Phosphate. 
 
 67. Hydroxid Test. Both NH 4 OH and NaOH give a gelat- 
 inous white ppt. soluble in excess, with the former only slightly 
 soluble: 
 
 A1 2 (S0 4 ) 3 4- 6NaOH = AJ, (OH) 6 + 3Na 2 S0 4 . 
 
 Aluminum 
 Hydroxid. 
 
 68. Cobalt Test. Co(N0 3 ) 2 added to a portion, heated on 
 charcoal gives an infusible blue mass. 
 
 55. Chromium. 
 
 (Make tests on a solution of Chromium Sulfate.) 
 
 69. (NH 4 ) 2 S precipitates from alkaline solutions Cr 2 (OH) 6 =a 
 green ppt. soluble in diluted HC1: 
 
 Cr 2 (S0 4 ) 3 +3(NH 4 ) 2 S + 6H 2 = Cr2(OH) 6 +3(NH 4 ) 2 S0 4 +3H 2 S. 
 
 Chromium 
 Hydroxid. 
 
 70. Sodium-hypochlorite Test. Chlorinated soda solution 
 (NaClO + NaCl) boiled with an alkaline chromium salt gives a 
 yellow solution of sodium chromate, (Na 2 Cr0 4 ). 
 
INORGANIC BASES AND ACIDS. 51 
 
 71. Sodium-hydroxid Test. NaOH = a bluish-green ppt. of 
 Cr 2 (OH)e soluble in excess, and reprecipitated on boiling: 
 
 Cr 2 (S0 4 ) 3 + 6NaOH = Cr 2 (OH) 6 +3Na 2 S0 4 . 
 
 Chromium 
 Hydroxid. 
 
 72. Ammonia Test.NR^OU = reaction similar to NaOH. 
 
 73. Borax-bead Test. The bead is emerald-green in color. 
 
 56. Zinc. 
 
 (Make tests on a solution of Zinc Sulfate.) 
 
 74. Precipitated in presence of NH 4 C1 from alkaline solutions 
 by (NH 4 ) 2 S as ZnS = a white ppt. soluble in HC1: 
 
 ZnS0 4 + (NH 4 ) 2 S = ZnS + (NH 4 ) 2 S0 4 . 
 
 Zinc 
 Sulfid. 
 
 75. Cobalt Test. Heat a portion of the solution on char- 
 coal with a drop or two of Co(N0 3 ) 2 solution = a green mass 
 which is infusible. 
 
 76. Ferrocyanid Test. K 4 Fe(CN)e gives a white gelatinous 
 ppt. of Zn 2 Fe(CN) 6 insoluble in diluted acids: 
 
 2ZnS0 4 +K 4 Fe(CN) 6 = Zn 2 Fe(CN) 6 +2K 2 S0 4 . 
 
 77. Ammonia Test. NH 4 OH = white ppt. soluble in excess: 
 
 ZnS0 4 + 2NH 4 OH=Zn(OH) 2 + (NH 4 ) 2 S0 4 . 
 
 Zinc 
 Hydrate. 
 
 78. Carbonate Test. NaC0 3 = a white ppt. soluble in NH 4 C1 
 andinNH 4 OH: 
 
 ZnS0 4 + Na 2 C0 3 = ZnC0 3 + Na 2 S0 4 . 
 
 57. Manganese. 
 
 (Make tests on a solution of Manganese Sulfate.) 
 
 79. Precipitated from alkaline solutions by (NH 4 ) 2 S as MnS, 
 a flesh-colored ppt. soluble in diluted HC1 or HC 2 H 3 2 : 
 
 MnS0 4 + 2(NH 4 )2S = MnS + 2(NH 4 ) 2 S0 4 . 
 
 Manganese 
 Sulfid. 
 
52 QUALITATIVE CHEMICAL ANALYSIS. 
 
 80. Lead Test. Pb0 2 heated with some of the substance and 
 HNOs (until free from nitrous fumes) and poured into H 2 
 gives a purple solution of permanganate: 
 
 2MnS0 4 + 6HN0 3 + 5Pb0 2 
 
 = 2HMn0 4 + 2PbS0 4 + 3Pb(N0 3 ) 2 + 2H 2 0. 
 
 Permanganic 
 Acid. 
 
 81. Alkaline-Hydroxid Test. NaOH or KOH = a white ppt. of 
 Mn(OH) 2 , which becomes brown upon heating: 
 
 MnS0 4 + 2NaOH = Mn(OH) 2 + Na 2 S0 4 . 
 
 Manganese 
 Hydroxid. 
 
 82. Ammonia TesZ. NH 4 OH= white ppt. soluble inNH 4 Cl: 
 
 MnS0 4 +2NH 4 OH = Mn(OH) 2 + (NH 4 ) 2 S0 4 . 
 
 Manganese 
 Hydrate. 
 
 83. Carbonate Test. Na 2 C0 3 = nearly white ppt.: 
 MnS0 4 + Na 2 C0 3 + 2 = Na 2 Mn0 4 + Na 2 S0 4 + C0 2 . 
 
 84. Carbonate Test. Heated on a platinum wire with some 
 Na 2 C0 3 gives a green mass. 
 
 85. Borax-bead Test. Bead hi flame is purple-colored. 
 
 58. Cobalt. 
 
 (Make tests on a solution of Cobalt Nitrate.) 
 
 86. In alkaline solutions gives a black ppt. of CoS with 
 (NH 4 ) 2 S: 
 
 Co(N0 3 ) 2 + (NH 4 ) 2 S = CoS + 2NH 4 N0 3 . 
 
 Cobllt 
 Sulfid. 
 
 87. Ammonia Test. NH 4 OH=a blue ppt. of Co(OH) 2 soluble 
 in excess to a brown solution, and reprecipitated by NaOH : 
 
 Co(N0 3 ) 2 + 2NH 4 OH = Co(OH) 2 + 2NH 4 N0 3 . 
 
 Cobalt 
 Hydroxid. 
 
INORGANIC BASES AND ACIDS. 53 
 
 88. Borax-bead Test gives a blue bead. 
 
 89. Cyanid 7^. KCN = a brown ppt. of Co(CN) 2 soluble in 
 excess on boiling and not precipitated by chlorinated soda 
 solution (distinction from nickel) : 
 
 Co(N0 3 ) 2 + 2KCN = Co(CN) 2 + 2KN0 3 , 
 then 
 
 Co(CN) 2 + 2KCN=K(CN) 2 -fCo(CN) 2 . 
 
 90. Sodium Hydroxid Test. NaOH = a blue ppt. of Co(OH) 2 , 
 changed to red on boiling: 
 
 Co(N0 3 ) 2 + 2NaOH = Co(OH) 2 + 2NaN0 3 . 
 
 Cobalt 
 Hydrate. 
 
 59. Nickel. 
 
 (Make tests on a solution of Nickel Sulfate.) 
 
 91. Precipitated from alkaline solutions by (NH^S =a black 
 ppt. of NiS, nearly insoluble in dil. HC1: 
 
 NiS0 4 + (NH 4 ) 2 S = NiS + (NH 4 ) 2 S0 4 . 
 
 Nickel 
 Sulfid. 
 
 92. Sodium-Hydroxid Test. NaOH = a green ppt. insoluble 
 in excess not changed by boiling : 
 
 NiS0 4 + 2NaOH = Ni(OH) 2 + Na 2 S0 4 . 
 
 Nickel 
 Hydroxid. 
 
 93. Ammonia Test. NH 4 OH gives a precipitate similar to 92 
 but soluble in excess of the reagent, forming a violet-colored 
 solution : 
 
 NiS0 4 +2NH 4 OH = Ni(OH) 2 + (NH 4 ) 2 S0 4 . 
 
 94. Cyanid Test. KCN = a pale green ppt. soluble in ex- 
 cess. When boiled with chlorinated soda solution = a black ppt. : 
 
 NiS0 4 +2KCN = Ni(CN) 2 +K 2 S0 4 . 
 
 95. Borax-bead Test. Purplish brown: hot; pinkish brown: 
 cold. 
 
54 
 
 SB 
 
 O 
 
 W 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 e.fl 
 
 H 
 
 
 '.2 
 
 &s 
 
 .a- 
 
 Q} ^i 
 
 rfl - 
 
 lli 
 
 ^ 
 
 ^ d 
 
 a'^ 
 
 llll 
 
 ^ 8 
 
 *1- 
 
 " 03 CO 
 
 ^ ^-S 
 
 ^ S-Q . 
 
 & QJ 
 
 Prg 
 
 as 
 
 Greenish 
 white p p 
 Insoluble i 
 HCI. 
 
 K 
 
 . 
 
 fl . 
 e 
 2-2 
 
 ^ ' H 
 
 d'g-- 1 
 
 
 
 d 
 
 
 ^^2 CL< O 
 
 ' 
 
 - 03 
 
 C i co 
 
 Si* 
 
 ^j > co d 
 
 Qr-t O * 
 
 S 8 
 

 INORGANIC BASES AND ACIDS. 
 
 55 
 
 2 
 
 ^ a, ^ <D . 
 03 ^ g ^ g 
 
 G 3 W)= 
 
 o.S II B 
 
 oJ 
 
 WE 
 
 O o 
 
 ^_ 
 
 ff! 
 
 i. A >> 
 
 O . 
 
 1^8351 
 
 Jlll 
 
 isr 
 
 liiri 
 
 rH t> ^3 
 
 T3 g 
 
 T3U 
 
 O >! 
 
56 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 6l. CHART FOR THE IDENTIFICATION OF THE METALS OF 
 GROUP III IN A SIMPLE SALT. 
 
 Group. 
 
 Reagent. 
 
 Result. 
 
 Indication. 
 
 Confirmatory Tests which should be 
 Applied to Original Solution. 
 
 HI , 
 
 If no ppt. 
 withH 2 S, 
 add to a 
 fresh por- 
 tion of the 
 original so- 
 tion, first, 
 NH 4 C1, 
 then 
 NH 4 OH, 
 and 
 (NH 4 ) 2 S. 
 Warm, and 
 filter. 
 
 Black 
 ppt. 
 
 Fe(ic) 
 
 Ppt. soluble in HC1. Add 
 
 K 4 Fe(CN)e = heavy blue ppt., in- 
 soluble in acids. Apply tests 
 under paragraph 52. 
 
 Black 
 ppt. 
 
 Fe(ous) 
 
 Ppt. soluble in HC1. Add 
 K 4 Fe(CN) 6 = white ppt. rapidly 
 turning blue. Apply tests under 
 paragraph 53. 
 
 White 
 ppt. 
 
 Al* 
 
 Ppt. soluble in HC1. Add KOH 
 = white ppt., soluble in excess, 
 reprecipitated by NH 4 C1. Apply 
 tests under paragraph 54. 
 
 Green 
 
 ppt. 
 
 Cr 
 
 Ppt. soluble in dil. HC1. Add 
 KOH = green ppt., soluble in 
 excess, reprecipitated by boiling. 
 Apply tests under paragraph 55. 
 
 White 
 ppt. 
 
 Zn* 
 
 Ppt. soluble in HC1. Add 
 K 4 Fe(CN) 6 = white ppt. Apply 
 tests under paragraph 56. 
 
 Flesh- 
 colored 
 ppt. 
 
 Mn 
 
 Ppt. soluble in dil. HC1. Add 
 KOH = white ppt.; shake; turns 
 brown. Apply tests under par- 
 agraph 57. 
 
 Black 
 ppt. 
 
 Co 
 
 Ppt. insoluble in dil. HC1. Add 
 NH 4 OH = a blue ppt. soluble 
 in excess to a brown solution. 
 Apply tests under paragraph 58. 
 
 Black 
 
 ppt. 
 
 Ni 
 
 Ppt. almost insoluble in dil. HC1. 
 Add K 3 Fe (CN) 6 = yellow ppt. 
 Apply tests under paragraph 59. 
 
 * If the ppt. in Group III is white in color and does not answer tests for Al or Zn, it 
 may contain insoluble phosphates, metals, or oxalates, or all of these. Confirm by dissolving 
 some of the original substance in cone. HNOs and pouring this into sol. of ammonium 
 molybdate. 
 
 Yellow precipitate or coloration on boiling indicates insoluble phosphate; in which case 
 treat as described under paragraph 86. 
 
INORGANIC BASES AND ACIDS. 
 
 57 
 
 62. CHART FOR A "SHORT METHOD" OF SEPARATING METALS 
 OF GROUP III IN A SIMPLE SALT. 
 
 
 Fe (ic). 
 
 Fe (ous). 
 
 Al. 
 
 Cr. 
 
 NH 4 C1 + 
 NH 4 OH 
 
 Reddish ppt. 
 
 Greenish ppt. 
 
 White ppt. 
 
 Bluish-green 
 ppt. 
 
 + (NH 4 ) 2 S 
 
 Turned black. 
 
 Turned black. 
 
 No. further 
 effect. 
 
 No further 
 effect. 
 
 
 Zn. 
 
 Mn. 
 
 Co. 
 
 Ni. 
 
 NH 4 C1 + 
 NH 4 OH 
 
 No effect. 
 
 No effect. 
 
 No effect. 
 
 No effect. 
 
 + (NH 4 ) 2 S 
 
 White ppt. 
 
 Flesh-colored 
 ppt. 
 
 Black ppt. 
 
 Black ppt. 
 
 63. SYNOPSIS OF THE SEPARATION OF METALS OF GROUP III. 
 
 To a portion of the original solution add HNOs, then NH 4 C1 in excess, 
 then NH 4 OH. 
 
 DIVISION A. 
 Precipitate. 
 Ppt.= Fe* Al Cr 
 
 DIVISION B 
 
 Filtrate. 
 Solution = Co Ni Zn Mn 
 
 +NaOH+H 2 O 2 pre- 
 cipitates Fe 
 
 +cold dilute HC1 
 precipitates Co Ni 
 
 Solution = 
 
 Al Cr 
 
 Solution = Zn Mn 
 
 Divide solution into two portions: 
 
 Precipitate = 
 
 Co Ni 
 
 Solution = 
 Zn Mn 
 
 Portion 1 
 AddHCl = NH 4 OH 
 
 = white ppt. = Al 
 
 Portion 2 
 Add HC 2 H 3 O 2 + 
 AgNO 3 =red 
 ppt. =Cr 
 
 +aqua regia + 
 KOH precipitates 
 Co. 
 
 Boil, cool +NaOH 
 dissolves Zn 
 
 Solution = Mn 
 
 
 * The Fe is in the ferric state, having been 
 oxidized by the HNOs. To determine the 
 original state of the iron, place a portion of 
 the original solution into two test tubes. To 
 one, add KSCN: a red coloration indicates 
 ferric iron; to the other, add KsFe(CN)6: 
 a dark blue color or ppt. indicates ferrous 
 iron. 
 
 Ppt = Ni 
 
 
58 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 boil well, 
 
 a grill 
 
 B^-frs 
 
 g sjlj* 
 
 ^rfS^ri . 
 g -11 &o 
 
 ^ trt *-" M M "^ 55 
 
 ^a?,i 
 
 m 
 
 fro 
 
 As 
 
 trate 
 en. 
 to 
 t 
 
 64. 
 
 Hi 
 
 
 S o 
 
 so < 
 
 il 
 
 a s 
 
 s- 2 
 
 
 
 
 M 
 
 
 
 "* ' o 
 
 ^ 
 
 c? 
 
 '> 
 
 151 
 
 .9 
 
 " 
 
 r ^s 02 
 
 ,s<9 
 
 Q-g 
 
 18. Evaporate fil 
 original solution is tak 
 the evaporation down t on 
 Here also account mu 
 glycerin, etc., be present ( 
 should be determined (see 
 19. Add a few drops of 
 
 . 
 
 a 
 
 o^o 
 
 fsSl 
 
 sS 
 
 O rt 
 
 0)^3 
 
 1 1 
 
 Mai, 
 
 
 o3 o ^ PL, 
 
 
 
 
 
INORGANIC BASES AND ACIDS. 59 
 
 65. OBSERVATIONS ON GROUP III. 
 
 18. The object of evaporating the filtrate from Group II 
 is to dissipate the H 2 S and thus prevent the formation of 
 (NH 4 ) 2 S, which in turn would precipitate the iron, cobalt, 
 and nickel, etc. 
 
 Attention here is called to organic substances mentioned 
 in No. 18, paragraph 64. 
 
 The precipitation of iron, aluminum, and chromium as 
 hydroxids can only be accomplished in the absence of organic 
 acids and other organic substances, like sugar or glycerin, con- 
 taining several of the hydroxyl groups. Therefore, if these be 
 detected in the preliminary tests, evaporate the H 2 S nitrate 
 to dryness, heat the residue with a few drops of strong HN0 3 
 (thus decomposing organic substances), dissolve the residue 
 in HC1, and proceed in the usual way. 
 
 19. Should organic substances be absent, boil the solution 
 with HNOs to oxidize the ferrous salts to the ferric state (thus 
 insuring the complete precipitation of iron by ammonia). Excess 
 of HNOs should be avoided. 
 
 The NH 4 OH (which should be added until the solution 
 smells strongly of NH 3 ) precipitates Fe(OH) 3 , A1(OH) 3 , and 
 Cr(OH)s, with a trace of manganese. Zinc, manganese, cobalt, 
 and nickel, which are also precipitated, form soluble hydroxids 
 which dissolve in the excess of NH 4 OH, and are found in the 
 filtrate. 
 
 Although the manganese is soluble in the excess of NH 4 OH, 
 during the heating and subsequent filtration employed in the 
 separation of the Al and Cr, it absorbs oxygen, and from man- 
 ganous becomes oxidized to mangano-manganic oxid (Mi^Os), 
 which, being insoluble in NH 4 OH, is precipitated together 
 with the Fe, Al, and Cr. The object of adding NH 4 C1 before 
 the group reagent NH 4 OH is to prevent the precipita- 
 tion of Mg(OH)2- It forms a soluble double compound, 
 MgCl 2 .2NH 4 Cl. The solution of NH 4 C1 also facilitates the 
 
60 QUALITATIVE CHEMICAL ANALYSIS. 
 
 complete solution of Co, Ni, Zn, and Mn in the excess of NH 4 OH. 
 To completely precipitate the Al and Cr, the mixture must be 
 boiled. 
 
 66. NOTES ON GROUP III. 
 
 22. Aluminate of potassium (KA10 2 ) is colorless; chromate 
 of potassium (K 2 Cr0 4 ) is yellow; manganate of potassium 
 (K 2 Mn0 4 ) is green, but after boiling in water it becomes pink. 
 
 23. The portion of the solution reserved for the detection of 
 Cr will be yellow from the presence of K 2 Cr04, indicating Cr. 
 
 The object of acidifying the solution with acetic acid is to 
 convert the carbonates into acetates; if this were not done, 
 brown argentic oxid and white plumbic carbonate would be 
 precipitated. 
 
 24. Neutralization is done with HC1, which at the same 
 time forms aluminum chlorid, and from which NH 4 OH throws 
 out aluminum hydroxid as a gelatinous precipitate, A1(OH) 3 , 
 insoluble in excess. 
 
 25. The metals are precipitated as sulfids, their identity 
 being indicated by the color of the precipitate, thus : MnS, flesh- 
 colored; ZnS, white; CoS and NiS, black. Excess of (NH 4 ) 2 S 
 should be carefully avoided, as it dissolves some of the NiS 
 (in which case the filtrate is brownish black). A black filtrate 
 is evaporated and the precipitate in the form of black NiS is 
 reclaimed. Cold, diluted HC1, should be used, as both the Ni 
 and Co are insoluble in it, but are soluble in concentrated HC1. 
 
 26. If the precipitate is not black, Co and Ni need not be 
 sought for. 
 
 31. An excess of HN0 3 and of Pb0 2 must be added, in order 
 to insure complete oxidation to the permanganate state. 
 
 32. When dried and fused the hydroxids lose water and 
 are converted into oxids, Fe 2 3 , A1 2 3 , and Cr 2 3 . When 
 treated with water and filtered, the Fe 2 3 remains as an insoluble 
 reddish-brown powder on the filter. The A1 2 3 combines 
 with the alkaline fusing mixture to form a soluble potassium 
 
INORGANIC BASES AND ACIDS. 61 
 
 aluminate thus: A1 2 3 +K 2 C0 3 =2KA10 2 +C0 2 . The Cr 2 3 
 likewise unites with the fusing mixture in the presence of oxi- 
 dizers, according to the following reaction: Cr 2 03+03 = 2CrOs; 
 then 2Cr0 3 +2K 2 C0 3 = 2K 2 Cr 2 4 +2C0 2 . The oxidizer in this 
 case is KNOs; KClOs acts similarly. 
 
 When the ppt. is fused, the Mn is oxidized to green potas- 
 sium manganate (K 2 Mn0 4 ); this being soluble in the water 
 interferes with detection of the Al and Cr. This green solu- 
 tion is therefore treated with alcohol, drop by drop, until the 
 green color is discharged. The alcohol is reduced to aldehyd, 
 which in turn reduces the manganese to mangano -manganic 
 oxid (Mn 2 3 ), which then precipitates and should be filtered 
 out before testing for Al and Cr. 
 
 SPECIAL TESTS FOR METALS OF GROUP IV. 
 
 (CARBONATE GROUP.) 
 To be applied to separate portions of the solution. 
 
 67. Barium. 
 
 (Make tests on Barium Chlorid solution.) 
 
 96. Precipitated from alkaline solutions (previously heated) 
 by (NH 4 ) 2 C0 3 = BaC0 3 ; soluble in acids (except H 2 S0 4 ): 
 
 BaCl 2 + (NH 4 ) 2 C0 3 + 2NH 4 C1 = BaC0 3 +4NH 4 C1. 
 
 Barium 
 Carbonate. 
 
 97. Sulfuric Test. H 2 S0 4 =a white ppt. BaS0 4 insoluble 
 in acids: 
 
 BaCl 2 + H 2 S0 4 = BaS0 4 + 2HC1. 
 
 Barium 
 Suifate. 
 
 98. Suifate Test.K 2 SO or CaS0 4 = a white ppt. of BaS0 4 
 insoluble in acids: 
 
 BaCl 2 + K 2 S0 4 = BaS0 4 + 2KC1. 
 
 Barium 
 
 Suifate. 
 
 CALIFORNIA COLLEGE 
 
 of PHARMACY 
 
62 QUALITATIVE CHEMICAL ANALYSIS. 
 
 99. Chromate Test. K 2 Cr0 4 =a yellow ppt. of BaCr0 4 
 insoluble in HC 2 H 3 2 : 
 
 BaCl 2 + K 2 Cr0 4 = BaCr0 4 + 2KC1. 
 
 Barium 
 Chromate. 
 
 100. Oxalate Test. (NH 4 ) 2 C 2 4 =a white ppt. soluble in 
 HC 2 H 3 2 : 
 
 BaCl 2 + (NH 4 ) 2 C 2 4 = BaC 2 4 + 2NH 4 C1. 
 
 Barium 
 Oxalate. 
 
 101. Flame Test. Barium salts heated with HC1 on a plat- 
 inum wire = a green flame. 
 
 68. Strontium. 
 
 (Make tests on a solution of Strontium Nitrate.) 
 
 102. Precipitated from hot alkaline solutions by (NH 4 ) 2 COa 
 = a white ppt. soluble in acids: 
 
 Sr(N0 3 ) 2 + (NH 4 ) 2 C0 3 = SrC0 3 + 2NH 4 N0 3 . 
 
 Strontium 
 Carbonate. 
 
 103. Chromate Test. K 2 Cr 2 7 = no precipitate except in 
 very concentrated solutions when it becomes yellow: 
 
 Sr (N0 3 ) 2 + K 2 Cr0 4 = SrCr0 4 + 2KN0 3 . 
 
 Strontium 
 Chromate. 
 
 104. Sulfate Test. K 2 S0 4 or CaS0 4 =a white ppt. of SrS0 4 
 (which forms very slowly, and is more soluble than BaS0 4 ) : 
 
 Sr(N0 3 ) 2 + CaS0 4 = SrS0 4 + Ca(N0 3 ) 2 . 
 
 105. Flame Test. Strontium salts heated with HC1 on a 
 platinum wire = a crimson-red flame. 
 
INORGANIC BASES AND ACIDS. 63 
 
 69. Calcium. 
 
 (Make tests on a solution of Calcium Chlorid.) 
 
 106. Precipitated from hot alkaline solutions by (NH 4 ) 2 C03 
 = a white ppt. of CaCOs soluble in acids: 
 
 CaCl 2 + (NH 4 ) 2 C0 3 = CaC0 3 + 2NH 4 C1. 
 
 ' Calcium 
 Carbonate. 
 
 107. Oxalate Test. (NH 4 ) 2 C 2 4 = a white ppt. of CaC 2 4 
 nearly insoluble in HC 2 H 3 2 : 
 
 CaCl 2 + (NH 4 ) 2 C 2 4 = CaC 2 4 + 2NH 4 C1. 
 
 Calcium 
 Oxalate. 
 
 108. Sulfate Test. K 2 S0 4 in concentrated solutions = a white 
 ppt. of CaS0 4 : 
 
 CaCl 2 +K 2 S0 4 = CaS0 4 +2KCl. 
 
 Calcium 
 Sulfate. 
 
 109. Flame Test. Calcium salts heated on a platinum wire 
 with HC1= orange-red flame. 
 
 COLL 
 
64 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 P5 
 
 tf 
 
 O 
 
 I 
 S 
 
 a 
 
 o 
 
 O 
 
 S . 
 
 .al-J. 
 
 3 --3 
 
 p'S 
 
 O 
 
 l 
 
 
 O.g^QJ 
 
 0,0 
 
 8C 
 
 1 
 
 O,OO 
 
 -T ra 
 
 6 
 

 -MA 
 
 INORGANIC BASES AND ACIDS. 
 
 65 
 
 71- CHART FOR THE IDENTIFICATION OF THE METALS OF 
 GROUP IV IN A SIMPLE SALT. 
 
 Group. 
 
 Reagent. 
 
 Result. 
 
 Indication. 
 
 Confirmatory Tests to be Applied to 
 Original Solution. 
 
 IV 
 
 If reagents 
 of Group 
 III give no 
 ppt., add 
 (NH 4 ) 2 CO 3 , 
 warm and 
 filter. 
 
 White 
 ppt. 
 
 Ba 
 
 Ppt. soluble in HC1. Add 
 K 2 CrO 4 = yellow ppt. Apply 
 tests under paragraph 67. 
 
 White 
 ppt. 
 
 Sr 
 
 Ppt. soluble in HNO 3 . Add 
 K 2 CrO 4 = no ppt. Add solution 
 of CaSO 4 , shake = white ppt. 
 Apply tests under paragraph 68. 
 
 White 
 ppt. 
 
 Ca 
 
 Ppt. soluble in acids. Add 
 K 2 CrO 4 = no ppt. x Add solu- 
 tion CaSO 4 , shake = no ppt. 
 Add (NH 4 ) 2 C 2 O 4 = white ppt. 
 Apply tests under paragraph 69. 
 
 72. 
 
 SYNOPSIS OF THE SEPARATION OF GROUP IV. 
 
 To a portion of the original solution (made alkaline with NH 4 C1+NH 4 OH) 
 
 add (NH 4 ) 2 CO 3 , warm, and allow to settle. 
 
 Precipitate 
 
 Ba Sr Ca 
 
 +HC 2 H 3 O 2 dissolves 
 Solution 
 
 Ba Sr Ca 
 Ba Sr Ca 
 
 +K 2 CrO 4 precipitates 
 
 Ba 
 
 Solution 
 
 Sr Ca 
 
 +dilute H 2 SO 4 (1:50) precipitates 
 
 Sr 
 
 Solution 
 
 Ca 
 
66 
 
 QUALITATIVE CHEMICAL ANALYSIS 
 
 73- 
 
 CHART FOR THE SEPARATION OF GROUP IV. 
 
 33. To the alkaline filtrate from Group III, add some solution (NH 4 ) 2 Cp 3 , 
 warm, and allow to rest for a few minutes; if a ppt. occurs, it may contain 
 
 Ba, Sr, Ca. 
 
 Filter and reserve the filtrate for Group V. 
 
 34. Collect and wash the precipitate, and reject the washings. Add 
 acetic acid and then add some solution of K 2 CrO 4 ; if a ppt. occurs, filter. 
 
 35. Precipitate = Ba. 
 
 tYellow. ppt. 
 Dissolve ppt. in HC1 
 and apply flame test. 
 Green-colored flame 
 = Ba. 
 
 36. Filtrate. 
 May contain Sr, Ca. 
 
 Add some dilute H 2 S0 4 (1:50), shake well, 
 and filter. 
 
 37. Precipitate. 
 
 May be Sr. 
 Moisten ppt. with 
 HC1, and apply flame 
 test. Crimson flame = 
 Sr. 
 
 38. Filtrate. 
 May be Ca. 
 
 Neutralize with NH 4 OH, 
 add (NH 4 ) 2 C 2 O 4 = white ppt. 
 = Ca. 
 
 74- 
 
 OBSERVATIONS ON GROUP IV. 
 
 33. The metals of this group are precipitated as carbonates, 
 thus: BaC0 3 , SrC0 3 , CaC0 3 . Magnesium carbonate is not pre- 
 cipitated here on account of its being present as a double 
 magnesium-ammonium soluble compound (MgCl2.2NH 4 Cl.) 
 
 The solution with the precipitated carbonates should only 
 be warmed, not boiled. If the mixture be boiled, the precipi- 
 tated carbonates are decomposed into chlorids through the 
 presence of the magnesium-ammonium compound, and may later 
 be mistaken for magnesium when Na 2 HP0 4 is added for the 
 detection of that metal. 
 
 The above-mentioned decomposition into chlorids is ex- 
 plained by the following two reactions: 
 
 (1) CaCl 2 + (NH 4 ) 2 C0 3 - CaC0 3 +2NH 4 C1. 
 
 (2) CaC0 3 +2NH 4 C1 = CaCl 2 + (NH 4 ) 2 C0 3 . 
 
INORGANIC BASES AND ACIDS. 67 
 
 75. NOTES ON GROUP IV. 
 
 34. When the precipitated carbonates are treated with 
 acetic acid, acetates of the metals are formed with the evolu- 
 tion of C0 2 . 
 
 When neutral potassium chromate is added, barium is 
 separated as yellow barium chromate (BaCr0 4 ). 
 
 36. The exact separation of the calcium and strontium is 
 tedious. The following simple method based on the solubilities 
 in water of SrS0 4 (1 in 7000) and CaS0 4 (1 in 400) is usually 
 employed: To a small portion of the filtrate add some satu- 
 rated solution of CaS0 4 and set the mixture aside for some 
 time. If strontium be present, SrS0 4 (a white ppt.) will be 
 obtained. To another portion add some very dilute H 2 S0 4 
 (1 in 50) and set aside for complete deposition of SrS0 4 (this 
 will contain some CaSO). 
 
 37. Apply the flame test for the strontium (crimson flame). 
 
 38. If the least trace of calcium be present in the filtrate, 
 a white precipitate of calcium oxalate insoluble hi water and 
 acetic acid is obtained on the addition of ammonium oxalate. 
 
 SPECIAL TESTS FOR METALS OF GROUP V. 
 To be applied to separate portions of the solution. 
 
 76. Magnesium. 
 
 (Make tests on a solution of Magnesium Sulfate.) 
 
 110. Precipitated from its alkaline ammonium-chlorid solu- 
 tion by Na 2 HP0 4 as MgNH 4 P0 4 =a white ppt., from concen- 
 trated solutions, and a crystalline ppt. from dilute solutions: 
 
 MgS0 4 + NH 4 OH + Na 2 HP0 4 =MgNH 4 P0 4 -f Na 2 S0 4 + H 2 0. 
 
 Ammonio-magnesium 
 Phosphate. 
 
 111. Alkaline-hydroxid Test. Both NaOH and NH 4 OH=a 
 white ppt. of Mg(OH) 2 soluble in NH 4 C1: 
 
 MgS0 4 + 2NaOH = Mg(OH) 2 + Na 2 S0 4 . 
 
68 QUALITATIVE CHEMICAL ANALYSIS. 
 
 112. Charcoal Test. Heated on charcoal with a drop or two 
 of Co(N0 3 ) 2 solution, leaves a pinkish mass. 
 
 113. Carbonate Test. Sodium carbonate produces a white 
 ppt. of basic magnesium carbonate, soluble in NH 4 C1: 
 
 4MgS0 4 + 4Na 2 C0 3 + H 2 = Mg 4 (OH) 2 (C0 3 ) 3 +4Na 2 S0 4 + C0 2 . 
 
 114. Calcium Hydrate Test. Ca(OH) 2 = a white ppt. insol- 
 uble in excess. Soluble in ammonium salts : 
 
 MgS0 4 +Ca(OH) 2 = Mg(OH) 2 
 
 77. Potassium. 
 
 (Make tests on a solution of Potassium Nitrate.) 
 
 115. Alkaline-tartrate Test. NaHC 4 H 4 6 =a white crystal- 
 line ppt. of KHC 4 H 4 Oe (in concentrated solutions only). This is 
 a distinguishing test between potassium and sodium, the latter 
 not giving a ppt. with alkaline tartrate: 
 
 KN0 3 + NaHC4H 4 6 = KHC 4 H 4 6 + NaN0 3 . 
 
 Potassium-hydrogen 
 Tartrate.; 
 
 116. Platinum-chkrid TesZ. PtCl 4 =a yellow ppt. of K 2 PtCl 6 
 soluble in excess of water (distinction from Na) : 
 
 2KCl+PtCl=K 2 PtCl 6 . 
 
 Double Potassio- 
 platinic Chlorid. 
 
 117. Sodium-Cobaltic-nitrite Test. NaN0 2 -Co(N0 2 ) 2 in pres- 
 ence of HC 2 H 3 2 = a yellow crystalline ppt. 
 
 118. Flame Test. Potassium salts heated with HC1 on a 
 platinum wire = a violet coloration when viewed through a 
 blue glass. 
 
INORGANIC BASES AND ACIDS. 69 
 
 78. Sodium. 
 
 (Make tests on a solution of Sodium Chlorid.) 
 
 119. Alkaline-tartrate Test. NaHC 4 H 4 6 = no precipitate 
 (distinction from potassium) . 
 
 120. Platinum-chlond Test. PtCl4=no precipitate with 
 sodium salt (distinction from potassium). 
 
 121. Antimony Test. K 2 Sb 2 Oe=a white crystalline ppt. of 
 Na 2 Sb 2 6 (metantimonate) in neutral solutions only and on 
 vigorous shaking: 
 
 2NaCl + K 2 Sb 2 6 = Na^baOe + 2KC1. 
 
 122. Flame Test. Sodium salts with HC1 heated on platinum 
 wire give intense yellow coloration to the flame (invisible through 
 blue glass). 
 
 79. Lithium. 
 
 (Make tests on a solution of Lithium Chlorid.) 
 
 123. Phosphate Test. Na 2 HP0 4 in boiling solutions = a white 
 ppt. of Li 3 P0 4 : 
 
 3LiCl + Na 2 HP0 4 = Li 3 P0 4 + 2NaCl + HC1. 
 
 Lithium 
 Phosphate. 
 
 124. Carbonate Test. Na 2 C0 3 in concentrated solutions = 
 Li 2 C0 3 : 
 
 2LiCl + Na 2 C0 3 = Li 2 C0 3 + 2NaCl. 
 
 Lithium 
 Carbonate. 
 
 125. Flame Test. Lithium salts heated with HC1 on a plati- 
 num wire = a bright-red flame. 
 
70 QUALITATIVE CHEMICAL ANALYSIS. 
 
 80. Ammonium. 
 
 (Make tests on a solution of Ammonium Chlorid.) 
 126. Alkaline-tartrate Tes. NaHC 4 H 4 6 = white ppt.: 
 
 NH 4 C1 + NaHC 4 H 4 06= NH 4 HC4H40 6 + NaCl. 
 
 Ammonium 
 Acid Tartrate. 
 
 127. Platinic-chlorid Test. PtCl 4 = a yellow ppt. of 
 (NH 4 ) 2 PtCl 6 (in concentrated solutions) : 
 
 2NH 4 Cl+PtCl 4 = (NH 4 ) 2 PtCl 6 . 
 
 Double Ammonio- 
 platininc Chlorid. 
 
 128. Hydroxid Test. Either NaOH or Ca(OH) 2 heated with 
 some of the solution gives off NH 3 (detected by the odor). 
 This vapor turns red litmus paper blue : 
 
 NH 4 C1 + KOH = NH 3 + KC1 + H 2 0. 
 
 Hold a glass rod moistened with HC1 over the mouth of the 
 test-tube: white fumes of NH 4 C1 are formed: 
 
 NH 3 +HC1=NH 4 C1. 
 
 129. Nessler's Test. Nessler's reagent (made from HgCl 2 + KI 
 till ppt. dissolves, then NaOH in excess) gives a yellow or brown- 
 ish ppt. of NHg 2 I (di-mercuric ammonium iodid). 
 
 NH 3 + 2HgI 2 + 3NaOH = NHg 2 I + 3NaI + 3H 2 0. 
 
INORGANIC BASES AND ACIDS. 
 
 71 
 
 8l. CHART FOR THE "COMPARATIVE" OBSERVATION OF 
 REACTIONS OF METALS OF GROUP V. 
 
 
 NaOH. 
 
 NH4OH. 
 
 NasCOa. 
 
 Na2HPO 4 . 
 
 j NaHC 4 H 4 O. 
 
 Mg 
 
 White ppt. 
 Soluble in 
 NH 4 C1. 
 
 White ppt. 
 Soluble in 
 NH 4 C1. 
 
 White ppt. 
 Soluble in 
 NH 4 C1. 
 
 White ppt. 
 in concen- 
 trated sols. 
 Crystalline 
 ppt. in dil. 
 sols. 
 
 
 K 
 
 
 
 
 
 White crys- 
 talline ppt. 
 in concen- 
 trated sol. 
 
 Na 
 
 
 
 
 
 No white crys- 
 talline ppt. 
 
 Li 
 
 
 
 White ppt. 
 in concen- 
 centrated 
 solutions. 
 
 White ppt. 
 on boiling. 
 
 
 NH 4 
 
 NH 3 gas 
 given off on 
 heating. 
 
 
 NH 3 gas 
 given off on 
 heating. 
 
 
 White ppt. 
 
 
 PtCU. 
 
 NaN0 2 
 Co(NO 2 ) 2 
 
 Sb. 
 
 Ca(OH) 2 . 
 
 Flame. 
 
 Mg 
 
 
 Heated on 
 charcoal 
 with cobalt- 
 ic-nitrite 
 solution = 
 pink mass. 
 
 
 White ppt. 
 Insoluble in 
 excess. Sol- 
 u ble in 
 NH 4 C1. 
 
 
 K 
 
 Yellow ppt. 
 soluble i n 
 excess o f 
 water. 
 
 Yellow crys- 
 talline ppt. 
 in presence 
 ofHC 2 H 3 O 2 . 
 
 
 
 Violet color 
 through 
 blue glass. 
 
 Na 
 
 No ppt. 
 
 
 White crys- 
 talline ppt. 
 in neutral 
 sols, on 
 shaking. 
 
 
 Yellow. 
 
 Li 
 
 
 
 
 
 Bright red 
 flame. 
 
 NH 4 
 
 Yellow ppt. 
 in concen- 
 trated solu- 
 tions. 
 
 
 NESSLER'S TEST. 
 Brownish or yellow ppt. 
 
 
72 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 82. CHART FOR THE IDENTIFICATION OF THE METALS OF 
 GROUP V IN A SIMPLE SALT. 
 
 Group. 
 
 Reagent. 
 
 Result. 
 
 Indication. 
 
 Confirmatory Tests which should be 
 Applied to Original Solution. ' 
 
 V 
 
 If reagent of 
 Group IV 
 gives n o 
 ppt., add 
 Na 2 HPO 4 . 
 
 White 
 ppt. 
 
 Mg 
 
 Add (NH 4 ) 2 CO 3 and boil = white 
 ppt'. Apply tests under par- 
 agraph 76. 
 
 KHC<H 4 6 
 (in alcohol) 
 
 White 
 ppt. 
 
 K 
 
 Add HC 2 H 3 O 2 + sodium-cobaltic- 
 nitrite = yellow ppt. Apply tests 
 under paragraph 77. 
 
 Na 2 Sb 2 O 6 
 
 White 
 crystal- 
 1 i n e 
 ppt. on 
 shaking 
 
 Na 
 
 Apply flame test = intense yellow. 
 Apply tests under paragraph 78. 
 
 Na 2 HPO 4 
 
 White 
 ppt. 
 
 Li 
 
 Apply flame test = crimson flame. 
 Apply tests under paragraph 79. 
 
 KOH 
 
 Odor of 
 NH 3 . 
 
 NH 4 
 
 Add Nessler's reagent = brownish 
 ppt. Apply tests under para- 
 graph 80. 
 
 83. 
 
 SYNOPSIS OF SEPARATION OF GROUP V. 
 
 Divide portion of the original solution or the filtrate from Group IV 
 into two portions. 
 
 PORTION 1 
 Contains NH 4 Li Na 
 
 K Mg 
 
 PORTION 2 
 To a portion of original 
 solution, add KOH or 
 NaOH = odor of NH 3 . 
 Hold a glass rod moist- 
 ened with HC1 near 
 escaping fumes = white 
 clouds of NH 4 C1 indi- 
 cate NH 4 . 
 
 Add NH 4 OH+Na 2 HPO 4 
 precipitates 
 
 Mg 
 
 Solution contains NH 4 Li 
 
 Na K 
 
 Evaporate to dryness, 1 Intense yellow 
 
 Na 
 
 add a few drops of 1 
 HCl,2milsH 2 Oand [ NH < 
 apply flame test. J Finally red 
 
 Li K 
 Li 
 
 NH 4 
 
 K 
 
 Add sodium-cobaltic-nitrite 
 precipitates 
 
 K 
 
 Solution contains NH 4 
 
INORGANIC BASES AND ACIDS. 73 
 
 84. CHART FOR THE SEPARATION OF GROUP V. 
 
 39. To a portion of the original solution or to the filtrate from Group 
 IV, add NH 4 OH and Na 2 HPO 4 and filter. 
 
 40. Precipitate. 
 
 May be Mg. 
 Dissolve in HNO 3 
 and add excess of 
 Ca(OH) 2 : a white ppt. 
 -Mg. 
 
 45. The original so- 
 lution must be tested 
 forNH 4 . AddKOH + 
 heat: odor of NH 3 = 
 NH 4 . 
 
 41. Filtrate. 
 May contain 
 
 Li, Na, K, NH 4 . 
 Evaporate to dry- 
 ness, add a few drops 
 of HC1, 2 mils of water 
 and apply flame test. 
 
 43. Na. 
 Flame = 
 intense yel- 
 low. 
 
 44. K. 
 
 Add sodium cobaltic- 
 nitrite T. S. = yellow 
 ppt. =K. Apply flame 
 test: violet (through 
 blue glass) = K. 
 
 85. 
 
 OBSERVATIONS AND NOTES ON GROUP V. 
 
 The filtrate from Group IV contains only the salts of Mg, K, 
 Na, Li, and NH 4 . 
 
 39. The object of adding NH 4 OH before the Na 2 HP0 4 
 is to render the ppt. less soluble in water. 
 
 40. If magnesium be present, it is indicated by a crystalline 
 precipitate of ammonio-magnesium phosphate (MgNEUPC^). 
 
 This precipitate appears only on standing. Any non- 
 crystalline precipitate is calcium which may have escaped 
 from the previous group. 
 
 43. The platinum wire should be held in the flame for a 
 minute or two, as the intense yellow flame of sodium may 
 obscure the red of the lithium. 
 
 44. The lithium and sodium having been tested for by the 
 
74 QUALITATIVE CHEMICAL ANALYSIS. 
 
 flame test, and as they do not react with sodium-cobaltic-nitrite, 
 we may disregard them entirely when testing for K. 
 
 45. The NH 4 having been dissipated by evaporation, it must 
 be tested for, in the original solution. In any case, NH 4 must 
 be tested for in a portion of the original solution, as NH 4 OH was 
 added, in the course of separations, quite frequently, and might 
 be detected in this solution, whereas, the original solution might 
 not contain any NH 4 . 
 
 86. CHART FOR THE SEPARATION OF INSOLUBLE 
 PHOSPHATES. 
 
 46. If the precipitate in Group III contains phosphates, 
 proved by ammonium molybdate test (made by dissolving some 
 original substance in strong HNOs, boil, and pour into a solution 
 of ammonium molybdate and boil. Yellow coloration or pre- 
 cipitate indicates insoluble phosphates), dissolve the precipitate 
 in a very small quantity of HC1, add some NaC 2 H 3 2 and then 
 some solution FeCl 3 . Boil for five minutes and filter. (The 
 ppt. contains the insoluble phosphates of iron, chromium, and 
 aluminum.) 
 
 The filtrate is tested for the ordinary metals of the third and 
 fourth groups in the usual manner. 
 
 Fuse the ppt. well with KNOs and Na 2 COs, treat with boil- 
 ing water and filter. Test a portion of the filtrate f or Cr with 
 a solution of AgNOaf a red ppt. = Cr. The remainder of the fil- 
 trate is next acidified with HC1, and an excess of NH 4 OH added; 
 a white flocculent ppt.=Al. The residue on the filter is dis- 
 solved with a few drops of hot aqua regia, diluted with water, 
 and added to some KSCN solution; a blood-red coloration 
 = Fe. 
 
 47. If the original substance is insoluble and was found 
 to contain phosphates, employ the folio whig chart: 
 
INORGANIC ACIDS AND BASES. 
 
 75 
 
 Boil some of the substance with a very small quantity of HC1, add cold 
 NaOH in excess, filter. The residue will contain the iron and other insoluble 
 phosphates. Digest with cold acetic acid and filter. 
 
 Precipitate. 
 
 FePO 4 . 
 Reddish-white ppt. 
 
 Filtrate. 
 Phosphates of Al, Cr, Co, Ni, Zn, Mn, Ba, Sr, 
 
 Ca, Mg. 
 
 Add FeCls, drop by drop, until a pale-reddish 
 tint is obtained. Heat for some time and filter 
 while hot. 
 
 Filtrate. 
 
 Members of Group III and IV 
 to be proved in the ordinary 
 way. 
 
 NOTE. The important insoluble (in water and acids) substances which 
 iray be found in the insoluble residues are: C, S, BaSO 4 , SrSO 4 , CaSO 4 , PbSO 4 , 
 PbCl 2 , AgCl, CaF 2 , silica and silicates, and native oxids of Al, Cr, Fe, and Sn. 
 Special tests should be applied to identify these. 
 
 87. Borax Bead Test. Borax, Na 2 B 4 7 , when ignited on a 
 loop of a platinum wire forms a bead, known as borax bead, 
 which when dipped in certain compounds or their solutions 
 yields a colored ghiss useful for the detection of many of the 
 metallic compounds, thus: 
 
 In the Oxidizing Flame. 
 
 In the Reducing Flame. 
 
 Indicates 
 
 Hot. 
 
 Cold. 
 
 Hot. 
 
 Cold. 
 
 Green 
 Blue 
 Green 
 Red 
 Amethyst 
 Purple-brown 
 
 Blue 
 
 Blue 
 Green 
 Bottle-green 
 Colorless 
 Reddish brown 
 
 Red 
 
 Cu 
 Co 
 Cr 
 Fe 
 Mn 
 Ni 
 
 
 Yellowish 
 Pink-brown 
 
 
 
 Yellow 
 
 88. PREPARATION OF A SOLUTION FOR ANALYSIS 
 IN THE WET WAY. 
 
 The molecules of reacting substances are brought into 
 closer contact when they are in solution than otherwise, and 
 
76 QUALITATIVE CHEMICAL ANALYSIS. 
 
 hence in this state the reaction between them takes place more 
 readily; in fact most substances will not react at all except 
 in the presence of a solvent or in a fused state. It is therefore 
 important to bring the substance (if it be a solid) into solution. 
 For analytical purposes all substances may be divided into 
 four classes, as follows: 
 
 1. Substances soluble in water. 
 
 2. Substances insoluble in water but soluble in an acid. 
 
 3. Substances insoluble in an acid but soluble in a mixture 
 of acids. 
 
 4. Substances decomposed by fusing with carbonates. 
 Complex substances may contain compounds belonging to 
 
 each of the above four classes. A small portion is heated 
 with some water in a test-tube and filtered; the filtrate is now 
 tested for compounds which may have gone into solution. 
 The residue is next treated with an acid, the excess of the 
 acid evaporated off, the substance diluted" with water and 
 filtered, and the filtrate tested for substances that may have 
 been dissolved, etc. The order most frequently followed is: 
 1st, water ; 2d, hydrochloric acid, dilute ; 3d, HC1 concentrated ; 
 4th, nitric acid, dilute; 5th, HN0 3 concentrated; 6th, nitro- 
 hydrochloric acid; 7th, sulfuric acid. 
 
 In using acids as solvents care must be taken not to use them 
 in excess; if, however, an excess has been used, evaporate the 
 solution under a hood to drive off the excess of acid. If the 
 acid is the proper solvent, very little of it will dissolve a large 
 quantity of the substance. 
 
 If, after going through the above-mentioned list of acid sol- 
 vents, the substance still remains insoluble, it may consist of 
 BaS0 4 , PbS0 4 , C, S, oxids of tin, silica and silicates, fluorids ; 
 alumina and aluminates, Sb 2 03 and Sb 2 0s, chrome iron ore, 
 some metaphosphates, arsenates, silver chlorid, etc. Fuse a 
 small portion of the powder with about five times its bulk of a 
 fusion mixture (Na 2 C0 3 +KN0 3 ) in a small crucible (preferably 
 platinum), extract the fused mass with water, and filter. Dis- 
 
* 
 
 INORGANIC BASES AND ACIDS. 77 
 
 solve what remains on the filter in HC1; if this does not effect 
 solution, try HN0 3 . 
 
 NOTE 1. If the preliminary examination shows absence of 
 Pb, boil the powder with NaOH solution, thus avoiding the 
 more difficult and tedious fusion. 
 
 The action of the fusion mixture in the above operation 
 is, generally speaking, to convert the base into an oxid or a 
 carbonate, the acid of the substance combining with the Na 
 and K as a corresponding salt. 
 
 NOTE 2. It should be remembered that the excess of any 
 acid solvents must be removed before proceeding to examine for 
 metals of the second group; strong acids (a) decompose H 2 S 
 into its elements and (6) prevent the precipitation of some of 
 the metals. 
 
 Above all it should be borne in mind that: 
 
 (1) If the substance is solid, it must be finely powdered 
 before effecting solution. 
 
 (2) That each solvent should be tried first cold, and then, 
 if required, hot. 
 
 (3) The solution for analysis should be neutral or just 
 slightly acid. If alkaline, neutralize with HNOs, any pre- 
 cipitate produced being filtered off and examined separately. 
 
 (4) Since cyanids, ferrocyanids, cobalt icyanids, etc., greatly 
 interfere with the ordinary processes of analysis, it is best 
 to destroy them before proceeding, by evaporating some of 
 the solution to dryness with H 2 S0 4 , whereby all the metals 
 will be obtained as sulfates. 
 
 (5) If the substance is a hard metal or alloy, treat it as 
 under " Alloys and Hard Metals." (Paragraph 89.) 
 
 (6) In making a solution, as above described, by the use of 
 acids, a clue to the identity of the substance is frequently obtained. 
 
 (7) Having obtained a solution, test it successively, for 
 metals of Groups I, II, III, IV and V, or by the table under 
 paragraph 93, and finally for the acidulous radical as described 
 under Acids under paragraph 94. 
 
78 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 89. 
 
 ALLOYS AND HARD METALS. 
 
 Procedure. Cut the alloy into very small pieces, or file off 2 grams of it, 
 or hammer it out flat so as to expose the largest possible surface to the 
 action of the acid. Heat about 2 grams of the thus-prepared substance with 
 about 40 c.c. of strong HNO 3 in a capsule, evaporate to small bulk to remove 
 excess of acid, dilute with H 2 O, and filter. 
 
 i : i 
 
 Precipitate. 
 
 SnO 2 and Sb 2 p 6 (as hydroxids or as arsenates). 
 [Also possibly Bi as arsenate or phosphate, and Au 
 
 and Pt 4 .] 
 
 Digest with zinc and dilute HC1. Test the 
 evolved gases for arsine by the AgNOs test. Resi- 
 due on the zinc may consist of the remaining 
 metals. Boil for some time with strong HC1 under 
 hood, and filter. 
 
 Filtrate. 
 
 Apply the usual 
 group reagents and 
 identify the metals 
 in the groups. 
 
 Precipitate. 
 Sb [Bi, Au, Pt.] 
 Digest with yellow 
 (NH 4 ) 2 S; Sb dissolves 
 as sulfo-salt. Evaporate 
 solution to d r y n e s s. 
 Orange-red residue = anti- 
 mony. 
 
 Filtrate. 
 SnCl 2 . 
 
 Add HgCl 2 . White 
 ppt., turning gray 
 on heating = tin. 
 
 QO. CHART FOR THE " COMPARATIVE " OBSERVATION OF THE 
 REACTIONS OF THE METALS WITH THREE COMMONLY 
 USED REAGENTS. 
 
 GROUP I. 
 
 Reagent. 
 
 NaOH. 
 
 NH4OH. 
 
 Na 2 C0 3 . 
 
 LEAD, Pb 
 
 White ppt. Soluble 
 in excess. 
 
 White ppt. Insol- 
 soluble in excess. 
 
 White ppt. (White 
 lead.) 
 
 SILVER, Ag 
 
 Brown ppt. Sol- 
 uble in NH 4 OH. 
 
 Brown ppt. Sol- 
 uble in excess. 
 
 White ppt. Soluble 
 in NH 4 OH. 
 
 MERCURY 
 (<nui) Hg. 
 
 Black ppt. Insol- 
 uble in NH 4 OH. 
 
 Black ppt. Insol- 
 uble in excess. 
 
 Yellow ppt. turn- 
 ing black. 
 
 GROUP II. 
 
 MERCURY (ic) 
 Hg. 
 
 Yellow ppt. In- 
 soluble in excess. 
 
 White ppt. Soluble 
 in HC1. 
 
 Reddish-brown 
 ppt. 
 
 BISMUTH, Bi 
 
 White ppt. Soluble 
 in HNO 3 . 
 
 White ppt. Insol- 
 ble in excess. 
 
 White ppt. 
 
INORGANIC BASES AND ACIDS. 
 
 79 
 
 CHART FOR THE "COMPARATIVE" OBSERVATION OF THE 
 REACTIONS OF THE METALS WITH THREE COMMONLY 
 USED REAGENTS (Continued). 
 
 GROUP II (Continued). 
 
 Reagent. 
 
 NaOH. 
 
 NEUOH. 
 
 NaaCOs. 
 
 COPPER, Cu. 
 
 Blue ppt. Becom- 
 ing black on boil- 
 ing. 
 
 Blue ppt. Soluble 
 in excess, to a 
 blue solution. 
 
 Bluish ppt. Black 
 on boiling. 
 
 CADMIUM, Cd 
 
 White ppt. Insol- 
 uble in excess. 
 
 White ppt. Soluble 
 in excess. 
 
 White ppt. 
 
 ARSENIC (cms) 
 As. 
 
 
 
 
 ARSENIC (ic) 
 
 As. 
 
 
 
 
 ANTIMONY, 
 Sb. 
 
 White ppt. Soluble 
 in excess. 
 
 White ppt. Insol- 
 uble in excess. 
 
 White ppt. Soluble 
 in excess. 
 
 TIN, (Stan- 
 nous), Sn. 
 
 White ppt. Soluble 
 in excess. 
 
 White ppt. Dark- 
 ens on boiling in 
 excess. 
 
 White ppt. Insol- 
 uble in excess. 
 
 TIN (Stan- 
 nic), Sn. 
 
 White ppt. Soluble 
 in excess. 
 
 White ppt. Slight- 
 ly soluble in excess. 
 
 White ppt. Insol- 
 uble in excess. 
 
 GROUP III. 
 
 IRON (Fer- 
 rous), Fe. 
 
 White ppt. Becom- 
 ing green, then 
 brown. 
 
 Greenish ppt. 
 
 White ppt. Soluble 
 in excess. Be- 
 comes brown. 
 
 IRON (Fer- 
 ric), Fe. 
 
 Brown ppt. In- 
 soluble in excess. 
 
 Reddish ppt. In- 
 soluble in excess. 
 
 Reddish-brown ppt. 
 
 ALUMINUM, 
 Al. 
 
 White ppt. Soluble 
 in excess. 
 
 White ppt. Slight- 
 ly soluble in excess 
 
 White ppt. Slight- 
 ly soluble in excess. 
 
 CHROMIUM. 
 Cr. 
 
 Bluish-green ppt. 
 Soluble in ex- 
 cess. 
 
 Bluish-green ppt. 
 Soluble in excess. 
 
 Green ppt. Slightly 
 soluble in excess. 
 
 COBALT, Co. 
 
 Blue ppt. Insol- 
 u b 1 e in excess. 
 Changed to red on 
 boiling. 
 
 Blue ppt. Soluble 
 in excess to a 
 brown solution. 
 
 Pink ppt. Soluble 
 in NH 4 OH. 
 
 NICKEL, Ni. 
 
 Green ppt. Insol- 
 uble in excess. 
 
 Green ppt. Soluble 
 in excess to a violet 
 solution. 
 
 Green ppt. Soluble 
 in NHiCl and in 
 NH 4 OH. 
 
 CALIFORNIA COLLEGE 
 of PHARMACY 
 
80 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 CHART FOR THE "COMPARATIVE" OBSERVATION OF THE 
 REACTIONS OF THE METALS WITH THREE COMMONLY 
 USED REAGENTS. (Continued). 
 
 GROUP III (Continued). 
 
 , Reagent. 
 
 NaOH. 
 
 NH4OH. 
 
 Na 2 CO 3 . 
 
 ZINC, Zn. 
 
 
 White ppt. Soluble 
 in excess. 
 
 White ppt. Soluble 
 in NH 4 C1 and in 
 NH 4 OH. 
 
 MANGANESE, 
 Mn. 
 
 White ppt. becomes 
 brown on heating. 
 
 White ppt. Soluble 
 in NH 4 C1. 
 
 Nearly white ppt. 
 
 GROUP IV. 
 
 BARIUM, Ba. 
 
 White ppt. in con- 
 centrated solution. 
 
 
 White ppt. Soluble 
 in acids. 
 
 STRONTIUM, 
 Sr. 
 
 White ppt. in con- 
 centrated solution. 
 
 
 White ppt. soluble 
 in acids. 
 
 CALCIUM, Ca. 
 
 White ppt. Spar- 
 ingly soluble. 
 
 
 W T hite ppt. soluble 
 in acids. 
 
 GROUP V. 
 
 MAGNESIUM, 
 Mg. 
 
 White ppt. Soluble 
 in acids. Soluble 
 in NH 4 C1. 
 
 White ppt. Soluble 
 in NH 4 C1. 
 
 White ppt. Soluble 
 in NH 4 C1. 
 
 POTASSIUM, 
 K. 
 
 
 
 
 SODIUM, Na. 
 
 
 
 
 LITHIUM, Li. 
 
 
 
 White ppt. in con- 
 centrated solution. 
 
 AMMONIUM, 
 NH 4 . 
 
 Free NH 3 on boiling. 
 
 
 Free NH 3 on boiling. 
 
INORGANIC BASES AND ACIDS. 
 
 81 
 
 
 
 a 
 
 
 1 
 
 
 1 
 
 03 
 
 
 
 
 
 
 
 1 
 
 
 4? 
 
 PH 
 
 & 
 
 
 
 
 
 
 
 - 
 
 
 v - 
 
 03 
 
 \D 
 
 
 
 
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 6 
 
 
 C~ o 
 
 
 w 5 
 
 4? 
 
 W . 
 
 
 
 
 1 
 
 3 
 
 
 am .-H 
 
 
 
 
 \D 
 
 
 
 
 o 
 
 J 
 
 
 
 
 
 jcT 
 
 v 
 
 ?Tl 
 
 
 
 
 E 
 
 HH 
 
 
 ^ 
 
 
 S 
 
 w 
 
 bB 
 
 
 
 
 I 
 
 
 
 ^ 
 
 
 g 
 
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 ^ 
 
 
 
 
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 0) 
 
 
 03 w 
 
 OQ 
 
 M 
 
 o 
 
 
 
 
 j 
 
 
 
 CD 
 
 
 i^-j p^ 
 
 T3 
 
 
 
 
 
 T^ 
 
 
 
 J'? 
 
 
 'E 3 N 
 
 ' 
 
 OQ v 
 
 
 
 
 5 
 
 
 
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 QQ 
 
 
 r2o 
 
 u 
 
 2 
 
 CQ 
 
 HH 
 
 
 
 
 1 
 
 HH 
 
 '3 
 
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 a 
 
 s ., 
 
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 o 
 
 
 which are 
 lute HNO 3 . 
 
 1 
 
 Q 
 
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 ^ 
 
 
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 G cj 25 
 
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 "d^ 
 
 
 cS^ 
 
 
 
 -J- t i 
 
 
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 3 
 
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 g'S 
 
 8 
 
 s.a 
 
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 11 
 
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 c - 
 
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 llj 
 
 
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 S.g 
 
 o 
 
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 S P 
 
 Ji 55 
 
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 CO CO 
 
 J^ 
 
 Id 
 
 d 
 
 bib Q^ 
 
 
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 ii 
 
 
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 ll 
 
 
 
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 pel 
 
 I 
 
 1 
 
 g 
 
 1=31 
 
 O 
 
 
 tpj 
 
 J 
 
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 At" 
 
 
 P^os 
 
 ? 
 
 
 
 
 
 
 W .Os 
 
 
 i* 
 
 
 *5 
 
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 1 
 
 
 
 
 
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 & 
 
 if 
 
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 ^ 
 
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 1 
 
 ^ C CD 
 
 ^ 1 
 
 5 
 
 M-l 
 
 
 
 
 
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 DQ 
 
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 OQ 5: o 
 
 s "O 
 
 A*2 
 
 
 
 
 
 5^3 
 
 fl 
 
 ^ 
 
 Soluble 
 
 5 ^ o3 
 o - w 
 
 ^l^ 
 
 1 
 
 Most nitrates 
 trates except 
 
 Most chlorids. 
 
 Most bromids. 
 
 J 
 
 1 
 
 All chlorates. 
 
 Alkaline and all 
 fids. MgS an 
 ly soluble. 
 
 Alkaline phosp 
 
 <-. 
 
 0)23 
 111 
 
 
 
 
 
 
 | 
 
 
 
 
 ;' 
 
 
 Q 
 
 s 
 
 
 
 j 
 
 
 
 
 
 
 CD 
 
 
 
 of 
 
 
 ' 
 
 
 
 
 w 
 
 
 1 
 
 1 
 
 
 a 
 
 i 
 
 OQ* 
 
 OQ' 
 
 5 
 
 a 
 
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 OQ' 
 
 "i 
 
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 | 
 
 
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 2 
 
 s 
 
 02 
 
 & 
 
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82 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 
 o 
 
 g 
 
 02 
 
 
 
 
 r^i 
 
 CC C3 
 
 ^! 6 
 
 % 
 
 ~ - 
 
 i 
 
 5 -| 
 
 os ^ spQ^o a . 
 
 ^iig-liij|i 
 
 6!l^4f3ds|4 
 
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 111 I 
 
 o 
 
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INORGANIC BASES AND ACIDS. 
 
 83 
 
 93. CHART FOR THE DETECTION AND SEPARATION OF A 
 MIXTURE OF THE METALS OF THE FIVE GROUPS. 
 
 Add HC1 in excess and filter. Reserve filtrate for Group II. 
 Wash the ppt. thoroughly, reject the washings, pour boiling 
 water over the ppt., and collect the filtrate. 
 
 Precipitate = Ag Hg (ous) . 
 Pour warmed (not hot) NH 4 OH over 
 the ppt. and collect the nitrate. 
 
 1 
 
 
 1 
 
 Filtrate = Ag. 
 Add HN0 3 = 
 white ppt. 
 Ag. 
 
 Ppt. =Hg(ows). 
 Turns black. 
 Dissolve in aqua 
 regia, dil. with 
 H 2 O and add 
 SnCl 2 = gray ppt. 
 Hg(ows). 
 
 
 
 Filtrate. 
 Divide in two 
 portions. For. 1. 
 add K 2 CrO 4 = yel- 
 low ppt. Por. 2. 
 Add KI = yellow 
 
 ppt ' p b . 
 
 (Continued on page 84.) 
 
 CALIFORNIA COL 
 
84 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 H 
 
 SP 
 
 R 
 
 C 
 
 a 
 
 
 
INORGANIC BASES AND ACIDS. 
 
 85 
 
 OF A M 
 
 (Continue 
 
 
 
 Is 
 
 O <& 
 
 So 
 
 n 
 
 v 
 *i 
 
 11 
 s 
 
 OS 
 
 Is 
 
 <i 
 
 d 
 a" . 
 
 & 
 
 flt_ 
 
 CS3 O 
 
 ^TS i^w o 
 
 ex 
 
 .Cr.Al 
 nto a beakei 
 20 minutes 
 
 > o O 
 ^ ^ 
 
 i| 
 
 O O^ 
 
 f f^ .?* 
 
 "** HH 
 
 So 
 
 a 
 
 g (D 
 II 
 
 
 2 
 
 .s 
 
 Is j i 
 
 ac 
 
 ao 
 
 1388 
 
 2 
 
86 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 CHART FOR THE DETECTION AND SEPARATION OF A MIX- 
 TURE OF THE METALS OF THE FIVE GROUPS (Concluded). 
 
 Filtrate from Group III. 
 Add (NH 4 ) 2 CO 3 , warm gently, allow to rest for a few minutes, then filter. 
 Reserve filtrate for Group V. 
 Ppt. Wash thoroughly, and reject the washings. 
 Puncture the filter paper and wash ppt. into a test-tube, add HC 2 H 3 O 2 
 and K 2 CrO 4 and filter. 
 
 1 
 
 
 1 
 
 Ppt. = yellow = Ba. 
 Dissolve in HC1 
 and apply flame test 
 = green flame. 
 Ba. 
 
 
 Filtrate = Sr, Ca. 
 Add dil. H 2 SO 4 (1:50), shake well, and filter. 
 
 1 
 
 
 1 
 
 Ppt. -Sr. 
 
 Moisten with HC1 
 and apply flame test = 
 crimson flame. 
 
 Sr. 
 
 Filtrate = Ca. 
 Neutralize with 
 NH 4 OH, add 
 
 (NH 4 ) 2 C 2 4 
 = white ppt. 
 
 
 
 Filtrate from Group IV. 
 Add NH 4 OH and Na 2 HPO 4 , and filter. 
 
 Ppt. = Mg. 
 
 Dissolve in HNO 3 , 
 
 add excess of 
 
 Ca(OH) 2 = white ppt. 
 
 Mg. 
 
 Filtrate, Li, Na, K, NH 4 . 
 
 Evaporate to dryness. Add a few drops of 
 HC1, 2 mils of water, and apply flame test. 
 
 Solution = K, NH 4 . 
 Add sodium cobaltic-nitrite 
 = yellow ppt. 
 
 To a portion of original solu- 
 tion add KOH and warm = an 
 odor of ammonia. 
 NH 4 . 
 
INORGANIC BASES AND ACIDS. 87 
 
 94. THE ACIDS. 
 
 Acids do not admit of being separated in groups and the 
 members of each group again separated, as in the systematic 
 examination of the metals. It is customary, however, to group 
 the acids hi accordance with their behavior when treated with 
 certain reagents, which may serve to indicate the presence or 
 absence of entire groups of acids. 
 
 Some of these acids will give reactions with the reagent of two 
 or more groups, and hence may be found listed under each one of 
 these groups, but in the text the acid is found listed under the 
 group with whose group reagent the acid will give its most 
 important or best-known reaction. 
 
 GROUP A. THE VOLATILE ACID OR EFFERVESCING GROUP. 
 
 This group includes acids which are volatilized or decom- 
 posed when their salts are acted upon by a dilute mineral acid. 
 
 They are: Carbonic (H 2 C0 3 ), hydrosulfuric (H 2 S), nitrous 
 (HN0 2 ), sulfurous (H 2 S0 3 ) thiosulfuric (H 2 S 2 3 ), hypochlorous 
 (HC10), and hydrocyanic (HCN). 
 GROUP B. THE BARIUM GROUP. 
 
 This group includes acids which are precipitated by BaCl 2 . 
 Two members of this group are precipitated by BaCl 2 in 
 the presence of HC1, namely, sulfuric (H 2 S0 4 ) and hydro- 
 fluorsilicic (H 2 SiF 6 ). The others are precipitated by the 
 same reagent from neutral solutions only. They are: 
 Carbonic, sulfurous, thiosulfuric, phosphoric (H 3 P0 4 ), 
 boric (H 3 B0 3 ), oxalic (H 2 C 2 4 ), hydrofluoric (HF), 
 silicic (H 2 Si0 2 ), arsenic (HsAsCh), arsenous (H-jAsOs), 
 and chromic (H 2 Cr04). 
 GROUP C. THE SILVER GROUP. 
 
 This group includes acids which are precipitated by AgNOs 
 from solutions acidulated with HN0 3 , but which are not 
 precipitated by BaCl 2 . 
 
 They are: Hydrochloric (HC1), hydrobromic (HBr), hydriodic 
 (HI), hydrocyanic (HCN), hydrosulfuric, sulfocyanic 
 
88 QUALITATIVE CHEMICAL ANALYSIS. 
 
 (HCNS), hydroferrocyanic (H 4 Fe(CN) 6 ), and hydro- 
 ferricyanic (H 3 Fe(CN) 6 ). 
 GROUP D. THE OXIDIZING GROUP. 
 
 This group includes acids which are oxidizing agents, and 
 liberate oxygen when decomposed. 
 
 They are: Nitric (HN0 3 ), nitrous, chloric (HC10 3 ), acetic, per- 
 manganic (HMn0 4 ), bromic, iodic, and hypophosphoric. 
 GROUP E. THE ORGANIC ACIDS. 
 
 The acids of this group with the exception of oxalic and 
 formic char on heating. 
 
 They are divided into three divisions: 
 
 Div. I. Ferric chlorid: acetic, tannic, gallic, pyrogallic, 
 phenol (carbolic), phenolsulphonic, salicylic and benzoic. 
 Div. 2. CaC^: tartaric and citric. 
 Div. 3. Acids not listed under other groups. 
 
 95. SYSTEMATIC ANALYSIS FOR THE ACID. 
 
 Before proceeding with the analysis for the acids, it is 
 important to ascertain what metals are present, because this 
 will aid materially in the rapid detection of the acid. 
 
 A knowledge of the metal present enables the analyst to 
 avoid making needless tests for acids that cannot possibly be 
 present. For instance, if the substance under analysis is 
 soluble in water, and lead is known to be present, it will be 
 needless to look for acids whose lead salts are insoluble, namely, 
 sulfuric, carbonic, hydrosulfuric, oxalic, chromic, phosphoric, 
 etc. On the other hand, the analysis may be rapidly and 
 satisfactorily completed by searching for such acids only as 
 will form soluble salts with the metal present, in the above 
 case acetic, nitric, etc. Again, if the original substance is 
 soluble in water and barium is known to be present, it will 
 be a waste of time and energy to look for acids of Group B. 
 If silver is present in a soluble salt the acids included in Group 
 C cannot possibly be present. 
 

 INORGANIC BASES AND ACIDS. 
 
 89 
 
 If in a preliminary examination, the substance chars on 
 heating to redness, organic matter is present and organic acids 
 should be looked for. But if it does not char, it will be unnec- 
 essary to enter into the testing for organic acids, because none 
 can possibly be present, except oxalic or formic. 
 
 Thus it is readily seen that with a knowledge of the metal 
 contents of the substance under examination, the identification 
 of the acid present is facilitated, and the number of the latter 
 to be looked for is comparatively few. 
 
 96. GROUP A. VOLATILE ACID GROUP. 
 
 STEP I. Preliminary Examination of the Dry Substance. 
 
 Heat in a test-tube a portion of the dry substance, or the residue 
 by evaporation with three times its bulk of strong sulfuric 
 acid and observe effect. 
 
 Result observed. 
 
 Colored vapors are evolved. 
 Violet (coloring starch paste blue) 
 
 Reddish (coloring starch paste yellow) 
 
 Greenish-yellow (detonation with 
 odor of chlorin, and bleaching 
 litmus). 
 
 Yellow (odor of chlorin). 
 
 Brownish-yellow (irritating). 
 
 Colorless gases ensue. 
 Odor of vinegar (HC 2 H 3 O 2 ). 
 Odor of rotten eggs (H 2 S). 
 Odor of burning sulphur (SO 2 ) 
 
 (bleaching litmus). 
 Odor of burnt sugar and blackening. 
 Odor of peach kernels (HCN). 
 Odorless gas burning with a blue 
 
 flame (CO). 
 Odorless gas turning lime water turbid 
 
 (CO,). 
 Odorless gas (oxygen). 
 
 Gas evolved etches glass, test best 
 
 performed in a lead dish. 
 Hydrochloric acid gas is evolved, 
 
 forms white clouds with ammonia. 
 
 Indication. 
 
 / lodate. 
 I lodid. 
 / Bromate. 
 \ Bromid. 
 Chlorate. 
 
 Hypochlorite. 
 f Nitrite. 
 
 \ Nitrate (in presence 
 [ agents). 
 
 of reducing 
 
 Acetate. 
 
 Sulfid. 
 
 Sulfite, thiosulfate or reducing agents 
 
 acting on sulfuric acid. 
 Tartrate, citrate or organic matter, 
 yanid. 
 Oxalate, ferro- and ferricyanid and 
 
 sulfocyanate. 
 Carbonate, oxalate and cyanate. 
 
 Chromate, dichromate manganate, 
 
 permanganate, bromate and iodate. 
 Fluorid and fluorsilicate. 
 
 Jhlorid. 
 
9(J QUALITATIVE CHEMICAL ANALYSIS. 
 
 Caution. When strong sulfuric acid is added to certain 
 compounds such as chlorates, iodates, etc., an explosion is 
 apt to occur, hence the acid should be applied with great care, 
 one drop should be first added and the effect noted. 
 
 If step I gives a decided indication as to the identity of 
 the acid, the confirmatory tests should be applied. If the 
 acid is not found, proceed by the following steps. 
 
 The tests described in the text are applied to salts of the alkali 
 metals only, for in such combination only can reliable results be 
 obtained in all cases. 
 
 A strong acid reaction (blue litmus turning red) indicates 
 that the acid is in the free state. 
 
 If the acid is not combined with an alkali it is a general 
 rule to convert the salt into a salt of sodium by boiling with 
 NaOH. 
 
 The ppt., if any, should be separated by filtration and 
 the filtrate tested. 
 
 (a) If the salt is soluble in water and neutral or alkaline 
 in reaction, the boiling with NaOH is generally not needed. 
 
 (6) If the substance is insoluble in water but soluble in 
 acids, boil a portion of the solid with a strong solution of 
 sodium carbonate, filter, and use the filtrate. 
 
 (c) If the substance is insoluble, treat as described for 
 the preparation of the solution for analysis of insoluble sub- 
 stances, using the filtrate, which is neutralized with NH 4 OH. 
 
 (d) In those cases where the metal present is one whose 
 hydroxid is soluble, and which cannot in consequence be 
 removed by treatment with NaOH, it is necessary to use, 
 instead of the latter, Na 2 G0 3 , boil, and neutralize with 
 HN0 3 . 
 
INORGANIC BASES AND ACIDS. 91 
 
 CHARACTERISTIC TESTS FOR INDIVIDUAL ACIDS. 
 
 The following characteristic tests are to be made preferably 
 upon salts of the acids with alkali metals. 
 
 CHARACTERISTIC TESTS FOR THE ACIDS OF GROUP A. 
 97. CARBONIC ACID, CARBONATES AND BICARBONATES. 
 
 Carbonic Acid (H 2 C03) is not known in the free state, as 
 it splits up into CO 2 and H20. Carbonic anhydrid C0 2 is a 
 colorless, odorless gas which, 'when passed into a solution of 
 Ca(OH) 2 or Ba(OH) 2 produces a white precipitate of CaCOs 
 or BaCOs respectively. When brought into contact with blue 
 litmus paper, it turns the latter wine-red, but the blue is restored 
 upon heating, the C0 2 being driven off. 
 
 Carbonate. 1. Treated with a dilute acid, violent effer- 
 vescence takes place, carbonic anhydrid being evolved, which 
 produces turbidity in a drop of Ba(OH) 2 solution held on a 
 glass rod near the mouth of the test-tube : 
 
 Na 2 C0 3 + 2HC1 = 2NaCl + H 2 + C0 2 . 
 C0 2 + Ba(OH) 2 = BaC0 3 + H 2 0. 
 
 2. Treated with AgNOz T.S. gives a gray ppt. soluble in 
 acids. 
 
 3. Treated with HgCl 2 T.S. produces a reddish-brown ppt. 
 
 4. Treated with a cold solution of Magnesium Sulfate 
 produces a white ppt. 
 
 Bicarbonates. 5. Treated with a dilute acid behaves like 
 carbonate (1). 
 
 6. Treated with HgCl 2 T.S. gives a white ppt. 
 
 7. Treated with a cold solution of MgSO does not give a 
 white ppt. 
 
 9 8. HYDROSULFURIC ACID AND SULFIDS. 
 
 8. Hydrosulfuric acid (H 2 S) (sulfuretted hydrogen) is a color- 
 less gas having an odor of rotten eggs. It is inflammable, S0 2 
 being produced by its combustion. 
 
92 QUALITATIVE CHEMICAL ANALYSIS. 
 
 9. Paper moistened with lead acetate solution is blackened 
 when held in the gas. This is due to the formation of PbS. 
 
 10. Sulfids. Treated with dilute hydrochloric acid evolve 
 H 2 S, which may be recognized by the tests described above. 
 Usually the odor of H 2 S is a sufficient test. 
 
 11. Treated with AgN0 3 T.S. =a black precipitate of Ag 2 S. 
 
 12. Treated with sodium-nitro-ferricyanid in an alkaline 
 solution = a purplish-red color. 
 
 13.. Insoluble sulfids, upon which the foregoing tests cannot 
 be applied, should be fused with a little NaOH on a porcelain 
 crucible cover; if the fused mass is placed on a bright silver 
 coin and moistened with water, a black stain will be produced 
 (Ag 2 S). 
 
 99. SULFUROUS ACID AND SULFITES. 
 
 Sulfurous acid (H 2 SOs) may be looked upon as a solution 
 of S0 2 in water. It is recognized by its odor of burning sulfur. 
 
 14. Treated with BaCh T.S. in slight excess gives a white ppt. 
 of BaS0 4 due to the inevitable presence of sulfuric acid. This 
 ppt. is removed by filtration and a small quantity of chlorin 
 water or hydrogen dioxid added, whereupon a copious ppt. of 
 BaS0 4 is formed. This is due to the oxidation of H 2 S03 to 
 H 2 S0 4 . 
 
 15. Treated with zinc and dilute hydrochloric acid it 
 evolves H 2 S, which blackens lead acetate paper : 
 
 H 2 S0 3 + 3Zn + 6HC1 = 3ZnCl 2 + H 2 S + 3H 2 0. 
 
 16. Sulfites. Treated with # 2 $0 4 evolves $0 2 , recognized' 
 by its odor of burning sulfur : 
 
 Na 2 S0 3 + H 2 S0 4 = Na 2 S0 4 + S0 2 + H 2 0. 
 
 17. Treated with BaCl 2 T.S. or CaCk T.S. gives a white ppt. 
 soluble in dilute HC1. 
 
 18. Heated with a small piece of zinc and a few drops of 
 # 2 $0 4 , H 2 S will be evolved, which blackens lead acetate paper- 
 
 19. With AgNOs sulfites produce a white ppt. which on 
 being heated darkens and deposits metallic silver. 
 
INORGANIC BASES AND ACIDS. 93 
 
 ioo. THIOSULFATES. 
 
 Thiosulfuric acid cannot be isolated because it splits up 
 into S0 2 , S, and H 2 0. The chief salt of this acid is sodium 
 thiosulfate (Na 2 S 2 3 ) which is used extensively in photog- 
 raphy for " fixing " because of its property of dissolving the 
 silver halids. 
 
 ^0. Dilute HC1 added to a solution of a thiosulfate produces 
 a slowly-forming precipitate of sulfur and an evolution of 
 S0 2 : 
 
 Na 2 S 2 3 +2HCl = 2NaCl +H 2 +S0 2 +S. 
 
 The precipitation of sulfur in this reaction distinguishes 
 thiosulfates from sulfites. 
 
 21. Silver Nitrate T.S. added in slight excess produces a 
 white precipitate of silver thiosulfate; this precipitate does not 
 form if the thiosulfate is in excess, and furthermore redissolves 
 if an excess of sodium thiosulfate is added : 
 
 2AgN0 3 +Na 2 S 2 3 = Ag 2 S 2 3 +2NaN0 3 
 Ag 2 S 2 3 +Na 2 S 2 3 = 2NaAgS 2 3 . 
 
 The precipitate of silver thiosulfate is very unstable, and 
 decomposes almost as soon, as it is formed, becoming yellow, 
 brown, and lastly black, through formation of Ag 2 S : 
 
 Ag 2 S 2 3 + H 2 = Ag 2 S + H 2 S0 4 . 
 
 22. Ferric Chlorid T.S. produces a reddish-violet color which 
 gradually disappears : 
 
 2FeCl 3 + 2Na 2 S 2 3 = 2FeCl 2 + 2NaCl + Na 2 S 4 6 . 
 
 23. Barium Chlorid T.S. produces a white precipitate. Cal- 
 cium chlorid forms no precipitate (distinction from sulfite) : 
 
 BaCl 2 + Na 2 S 2 3 = BaS 2 3 + 2NaCl. 
 
94 QUALITATIVE CHEMICAL ANALYSIS. 
 
 ioi. HYDROCYANIC ACID AND CYANIDS. 
 
 24. CYANIDS. Sulfuric Acid added to an alkali cyanid gives 
 odor of bitter almonds (HCN).* 
 
 25. Silver Nitrate T.S. added in excess to hydrocyanic acid 
 or a cyanid produces a curdy white precipitate of silver cyanid, 
 which is soluble in ammonia water, and in concentrated hot 
 nitric acid, but not in dilute nitric acid. It is also soluble in 
 sodium thiosulfate. 
 
 26. Scheele's Iron Test. The hydrocyanic acid or the cyanid 
 is made strongly alkaline by the addition of potassium hydroxid; 
 to this is added a little ferrous sulfate and ferric chlorid, the 
 mixture is then gently heated and finally acidified with hydro- 
 chloric acid. A precipitate of ferric ferrocyanid (Prussian 
 Blue) is formed. The reactions are as follows: 
 
 (a) HCN+KOH = KCN+H 2 0. 
 
 (6) FeS0 4 +2KOH = Fe(OH) 2 +K 2 S0 4 . 
 
 (c) Fe(OH) 2 +KCN=Fe(CN) 2 + 2KOH. 
 
 (d) Fe(CN) 2 +4KCN=K 4 Fe(CN) 6 . 
 
 (e) 3K 4 Fe(CN) 6 +2Fe 2 Cl 6 = Fe 4 (Fe(CN) 6 )3+12KCl. 
 
 27. The Sulfocyanate Test. To the cyanid add a few drops 
 of yellow ammonium sulfid solution and evaporate the mixture 
 to dryness at a gentle heat. The residue, which consists of 
 ammonium sulfocyanate, is treated with one or two drops of 
 dilute hydrochloric acid to destroy any undecomposed sulfid 
 present. A drop of ferric chlorid solution is now added and a 
 blood-red color (Fe 2 (SCN) 6 ) is produced. 
 
 The reactions are as follows: 
 
 (a) 2HCN + (NH 4 ) 2 S + S 2 = 2NH 4 SCN + H 2 S. 
 (6) 6NH 4 SCN+2FeCl 3 = F 
 
 * (Caution: The gas so evolved should be very cautiously sniffed, it being 
 highly poisonous.) 
 
INORGANIC BASES AND ACIDS. 
 
 95 
 
 
 
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 Special Tests. 
 
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 color. Acidify with di- 
 lute H 2 SO 4 bleaches lit- 
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 CIO 
 
 CALIFORNIA COLLEGE 
 
 of PHARMACY 
 
96 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 103. 
 
 HYPOCHLORITES. (R'CIO.) 
 
 28. Acetic Acid or Dilute Sulfuric Acid, added to a solution 
 of a hypochlorite, causes evolution of chlorin, recognized by 
 its odor and by giving a blue color upon trie subsequent addition 
 of potassium iodid and starch solution. 
 
 29. Indigo or Litmus Solutions treated with a solution of a 
 hypochlorite, and acidified with dilute sulfuric acid are decolor- 
 ized. 
 
 104. 
 
 GROUP B. BARIUM CHLORIC GROUP. 
 
 STEP II. To a portion of the aqueous solution acidulated 
 with hydrochloric acid, add a little barium chlorid T.S. 
 
 A , .. . .. r . .. f sulfate, or 
 
 A white precipitate indicates I , . 7 . 
 
 [ Fluorsihcate. 
 
 STEP III. To another portion of a neutral aqueous solution 
 add barium chlorid T.S., and observe effect. 
 
 Result. 
 
 Indication. 
 
 A white ppt. sol. in acetic and all 
 stronger acids. 
 
 A white ppt. sol. in acids. 
 
 A white ppt. which chars when heated 
 
 on platinum foil. 
 A white ppt. which effervesces 
 
 violently when treated with dilute 
 
 HC1. 
 A white ppt. which when treated with 
 
 dU. HC1 evolves SO 2 . 
 
 A white ppt. insol. in dil. HC1. 
 
 A white ppt. sol. in excess of reagent, 
 
 in acids, and in NH 4 C1. 
 A yellow ppt. sol. in HC1. 
 
 f Phosphate. 
 V Oxalate. 
 / Silicate. 
 1 Fluorid. 
 / Tartrate. 
 \ Citrate. 
 Carbonate. 
 
 / Sulfite. 
 
 1 Thiosulfate. 
 
 I Sulfate. 
 
 1 Fluorsilicate. 
 
 Borate. 
 
 Chromate. 
 
INORGANIC BASES AND ACIDS. 97 
 
 CHARACTERISTIC TESTS FOR ACIDS OF GROUP B. 
 105. SULFURIC ACID AND SULFATES. 
 
 30. SULFURIC ACID (H 2 S0 4 ) a heavy, oily, colorless liquid. 
 Upon adding water to the acid considerable heat is produced. 
 
 31. Charring Test. A piece of paper or wood placed in strong 
 sulfuric acid is charred, or if the dilute acid is evaporated in 
 contact with a little white sugar the latter is charred. This 
 charring is due to the abstraction of the elements of water. 
 
 32. Precipitation Tests. Dilute sulfuric acid gives a white 
 precipitate with barium and lead salts. 
 
 33. SULFATES. Sulfates are soluble in water with the excep- 
 tion of basic sulfates and those of barium, strontium, and lead. 
 Silver sulfate and calcium sulfate are only slightly soluble. 
 
 34. Barium Chlorid Test. BaCl 2 added to a solution of a 
 sulfate precipitates white BaS0 4 insoluble in dilute acids even 
 on boiling. The sulfate solution should be acidified with dilute 
 hydrochloric acid before the barium chlorid is added: 
 
 K 2 1 S0 4 + BaCl 2 = BaS0 4 + 2KC1. 
 
 106. HYDROFLUORSILICIC ACID (H 2 SiF 6 ) AND 
 
 FLUORSILICATES. 
 
 35. FLUORSILICATES. Barium Chlorid gives with fluor- 
 silicates a white precipitate, which is insoluble in hydrochloric 
 
 acid: 
 
 H 2 SiF 6 + BaCl 2 = BaSiF 6 + 2HC1. 
 
 36. Potassium Chlorid gives a gelatinous precipitate of 
 K 2 SiF 6 : 
 
 H 2 SiF 6 + 2KC1 = K 2 SiF 6 + 2H|C1. 
 
 107. PHOSPHORIC ACID AND PHOSPHATES. 
 
 37. ORTHO-PHOSPHORIC ACID (H 3 P0 4 ). This is a strong 
 acid liquid, which when heated is converted into pyro- and 
 finally weta-phosphoric acid, which remains as a vitreous residue. 
 
98 QUALITATIVE CHEMICAL ANALYSIS. 
 
 38. The Magnesia Test. A small portion of the acid is 
 supersaturated with ammonia water, and some magnesia mix- 
 ture added. A white crystalline precipitate of ammonio-mag- 
 nesium phosphate is formed (NH 4 MgP0 4 + 6H 2 0). 
 
 39. The Silver Nitrate Test. The precipitate obtained in 
 the magnesia test is washed and dissolved in dilute acetic 
 acid. To this solution some silver nitrate T.S. is added and 
 a yellow precipitate of silver phosphate Ag 3 P0 4 results. 
 
 40. PHOSPHATES. The alkali phosphates are soluble in 
 water; most of the other phosphates are insoluble. They are, 
 however, soluble in dilute acids from which they are reprecip- 
 itated upon neutralizing with an alkali. 
 
 41. The Barium Test. Barium chlorid gives with a phos- 
 phate a white precipitate, which is soluble in acetic acid and 
 in all stronger acids. The white precipitate produced by 
 barium chlorid with a sulfate is insoluble in acids. That pro- 
 duced with an oxalate by the same reagent is soluble in acetic 
 acid and the mineral acids : 
 
 Na 2 HP0 4 + BaCl 2 = BaHP0 4 + 2NaCl. 
 
 42. The Silver Test. Silver nitrate gives a yellow precip- 
 itate of silver phosphate which is soluble both in nitric acid 
 and ammonium hydroxid : 
 
 Na 2 HP0 4 + 3AgN0 3 = Ag 3 P0 4 + 2NaN0 3 + HN0 3 . 
 
 43. The Magnesia Test. Magnesia mixture gives a white 
 crystalline precipitate (NH 4 MgP0 4 + 6H 2 0) soluble in dilute 
 acids : 
 
 Na 2 HP0 4 +MgCl 2 +NH 4 OH = NH 4 MgP0 4 +2NaCl +H 2 0. 
 
 44. The Molybdate Test. Ammonium molybdate 
 (NH 4 ) 2 Mo0 4 dissolved in nitric acid, gives with phosphates a 
 canary-yellow precipitate of ammonium phosphomolybdate 
 readily soluble in alkalies. (NH 4 ) 3 P0 4 , 12Mo0 3 . 
 
INORGANIC BASES AND ACIDS. 99 
 
 108. META- AND PYRO-PHOSPHORIC ACIDS. 
 
 45. META-PHOSPHOKIC ACID (HP0 3 ). A glassy solid, con- 
 verted by boiling water into ortho-phosphoric acid. 
 
 46. Ammonio-silver Nitrate produces a white precipitate 
 (AgP0 3 ) in neutralized solutions only. Soluble in nitric acid 
 and in ammonia water, also soluble in an excess of an alkali 
 meta-phosphate (difference from pyro-phosphoric acid and its 
 salts). 
 
 47. Albumen is coagulated (difference from pyro-phosphoric 
 acid). 
 
 48. Magnesia mixture gives no precipitate with meta-phos- 
 phates. 
 
 49. PYRO-PHOSPHORIC ACID (H 4 P 2 7 ). A glass-like solid, 
 converted by boiling water into ortho-phosphoric acid. 
 
 50. Ammonio-silver Nitrate. Same reaction as above except 
 that the precipitate is not soluble in excess of alkali pyro- or 
 meta-phosphate. The precipitate is Ag 4 P 2 7 . 
 
 51 . Albumen is not coagulated. 
 
 52. Ammonium Molybdate gives no precipitate with pyro- 
 phosphates until after long standing. 
 
 109. BORIC ACID AND BORATES. 
 
 BORIC ACID (HaBOs) occurs either in crystals or in fine 
 white powder. When heated to 100 C. orthoboric acid loses 
 water forming meta-boric acid (HB02). When heated to 160 
 C. it fuses to a glassy mass of tetra-boric acid (pyro-boric acid) 
 (H 2 B 4 7 ). 
 
 53. Its solution in alcohol or glycerine burns with a flame 
 enveloped with a green mantle. 
 
 54. An aqueous solution of boric acid (1-50) reddens blue 
 litmus, and turns yellow turmeric paper brownish-red after 
 drying even when the solution has been acidulated with hydro- 
 chloric acid. This brownish-red color is changed to bluish- 
 black by ammonia water. 
 
100 QUALITATIVE CHEMICAL ANALYSIS. 
 
 BORATES. Sodium tetra-borate (Borax) is the most common 
 and hence concerns us most. Only the alkali borates are soluble 
 in water. 
 
 55. Barium Chlorid produces a white ppt. soluble in acids. 
 
 56. The Turmeric Paper Test. A piece of turmeric paper is 
 moistened with a solution of a borate slightly acidified with 
 hydrochloric and the paper then dried; the paper becomes 
 brownish-red in color. If the paper is now moistened with 
 ammonium or sodium hydroxid the color changes to bluish- 
 black. 
 
 57. The Flaine Test. If a drop of a solution of borax in 
 glycerin be held in a Bunsen flame a transient bright green 
 color will appear. 
 
 58. The Gylcerin Test. An aqueous solution of borax colors 
 red litmus blue, if glycerin be added to this solution, boric 
 acid is liberated and blue litmus is turned red. 
 
 no. OXALIC ACID AND OXALATES. 
 
 OXALIC ACID (H 2 C 2 4 ) colorless crystals. 
 
 59. This acid added to an acidulated solution of potassium 
 permanganate completely discharges the color of the latter. 
 
 60. This acid added to a solution of copper sulfate sets free 
 sulfuric acid. 
 
 61. It gives all the reactions of oxalates. 
 
 62. OXALATES. Concentrated Sulfuric Acid, when added to 
 an oxalate in the dry state, decomposes- it with the evolution 
 ofC0 2 andCO: 
 
 H 2 C 2 4 + H 2 S0 4 = H 2 + H 2 S0 4 + CO + C0 2 . 
 If the unmixed gases are passed through lime water, the 
 C0 2 will be absorbed, forming a precipitate of CaCOs and the 
 escaping CO may be ignited, and recognized by its blue flame. 
 
 63. Calcium Chlorid Test. Calcium chlorid gives a white 
 crystalline precipitate of calcium oxalate soluble in hydro- 
 chloric acid, but not soluble in acetic acid : 
 
 K 2 C 2 4 + CaCl 2 = CaC 2 4 + 2KC1. 
 
* COLLtGt 
 t PHARMACY 
 
 INORGANIC BASES AND ACIDS. 101 
 
 64. Barium Chlorid Test. BaCl 2 gives a white ppt. of 
 barium oxalate, soluble in hydrochloric acid but not soluble in 
 acetic acid. 
 
 65. The Permanganate Test. Potassium permanganate solu- 
 tion added to a hot solution of an oxalate acidulated with sulfuric 
 acid is decolorized: 
 
 5H 2 C 2 4 + 3H 2 S0 4 + 2KMn0 4 
 
 = K 2 S0 4 + 2MnS0 4 + 8H 2 + 10C0 2 . 
 
 in. HYDROFLUORIC ACID AND FLUORIDS. 
 
 HYDROFLUORIC ACID (HF). Very corrosive. It acts upon 
 and etches glass. 
 
 FLUORIDS. (Practice upon fluor spar (CaF 2 ).) 
 
 66. The Etching Test. The salt is powdered, and intro- 
 duced into a platinum or leaded dish with a little sulfuric 
 acid. The dish is covered with a piece of glass previously 
 coated on one side with wax, through which some characters 
 are scratched with the point of a pin. The waxed side of the 
 glass is placed over the dish so that the liberated HF comes 
 in contact with it, and the dish gently heated, being careful, 
 however, not to melt the wax. After some time the glass is 
 removed, the wax wiped or melted off, and the characters 
 scratched on the waxed surface will be found engraved upon 
 the glass : 
 
 (a) CaF 2 + H 2 S0 4 = CaS0 4 + 2HF. 
 
 (6) 28HF + Na 2 Si 3 7 CaSi 3 7 = 2NaF + CaF 2 + 6SiF 4 + 14H 2 0. 
 
 Glass. 
 
 112. SILICA AND SILICATES. 
 
 67. SILICA (Si0 2 ) is the anhydrid of silicic acid (H 4 Si0 4 ). 
 It is infusible, insoluble in water and in all acids except HF. 
 When silica is heated with sulfuric acid and calcium fluorid 
 in a leaden or platinum vessel, and a drop of water in the loop 
 
102 QUALITATIVE CHEMICAL ANALYSIS. 
 
 of a platinum wire held in the escaping gas, the water will become 
 turbid, due to the formation of gelatinous silicic acid. 
 
 (a) 4HF + Si0 2 = SiF 4 + 2H 2 0. 
 
 (6) 3SiF 4 +4H 2 = 2H 2 SiF 6 +H 4 Si0 4 . 
 
 SILICATES. These salts are insoluble in water except the 
 alkali silicates. They are decomposed by gaseous hydrofluoric 
 acid or a mixture of sulfuric acid and calcium fluorid. 
 
 68. Hydrochloric Acid (HC1) added to a solution of an 
 alkali silicate produces a gelatinous precipitate (scarcely visible) 
 of H 4 Si0 4 - 
 
 69. Ammonium Chlorid does the same. 
 
 113. ARSENIC ACID (H 3 As0 4 ) AND ARSENATES. 
 
 70. ARSENATES behave in every respect exactly like phos- 
 phates except in the following reaction. 
 
 71. Silver Nitrate, added to a neutral solution of an arsenate, 
 produces a reddish-brown precipitate of silver arsenate (Ag 3 As0 4 ) : 
 
 Na 3 As0 4 +3AgN0 3 = Ag 3 As0 4 +3NaN0 3 . 
 
 Phosphates and also arsenites treated in this manner pro- 
 duce yellow precipitates. 
 
 72. Magnesia Mixture added to a neutral or ammoniac al 
 solution of an arsenate produces a white crystalline precipitate of 
 ammonio-magnesium arsenate (NH 4 MgAs0 4 ) (distinction from 
 arsenites) : 
 
 K 3 As0 4 +MgCl 2 +NH 4 C1 = NH 4 MgAs0 4 +3KC1. 
 
 73. Potassium lodid added to an acid solution of an arsenate 
 will reduce it with a separation of iodin : 
 
 H 3 As0 4 +2HI = H 3 As0 3 +H 2 +I 2 . 
 
 This test will detect arsenic acid in the presence of arsenous 
 acid, but is useful only in the absence of oxidizing agents, as 
 chromates, nitrites, manganates and ferric salts. 
 
INORGANIC BASES AND ACIDS. 103 
 
 114. ARSENOUS ACID (HsAs0 3 ) AND ARSENITES. 
 
 74. Hydrogen Sulfid added to a solution of an arsenite 
 acidulated with hydrochloric acid produces a copious yellow 
 precipitate of As 2 S 3 : 
 
 2H 3 As0 3 +3H 2 S= As 2 S 3 + 6H 2 0. 
 
 If the solution is neutral instead of acid, H 2 S does not 
 precipitate the sulfide, but colors the solution yellow, due 
 to the formation of colloidal As 2 S 3 . 
 
 75. Silver Nitrate added to a neutral solution of an arsenite 
 precipitates yellow silver arsenite, Ag 3 As0 3 (distinction from 
 arsenate) : 
 
 K 3 As0 3 +3AgN0 3 = Ag 3 As0 3 +3KN0 3 . 
 
 76. Magnesia Mixture does not precipitate arsenites (dif- 
 ference from arsenates). 
 
 77. lodin added to a solution of an arsenite made alkaline 
 with NaHCOs, is decolorized and oxidizes the arsenite to 
 arsenate: 
 
 As 2 3 + 1 4 + 2H 2 = 4HI + As 2 5 . 
 
 Other tests for arsenic and arsenous compounds will be 
 found under tests for metals of Group II. 
 
 n 5 . CHROMIC ACID AND CHROMATES. 
 
 78. CHROMIC ACID (H 2 Cr0 4 ) cannot be isolated, but its 
 anhydrid, Cr0 3 , is well known. If a solution of this anhydrid 
 be treated with dilute hydrogen dioxid and a little ether added 
 and shaken up with it, the perchromic acid formed will separate 
 from the water and enter the ether, forming an intense blue 
 solution. This test is exceedingly delicate and may be applied 
 to chromates after slight acidulation with sulfuric acid. It 
 will detect 1 part of K 2 Cr0 4 in 40,000 parts of water, and 
 may be used also as a very delicate test for H 2 2 . 
 
104 QUALITATIVE CHEMICAL ANALYSIS. 
 
 79. CHROMATES. Alkali chromates and chromates of mag- 
 nesium and calcium are soluble in water. Most other chromates 
 are insoluble. 
 
 Soluble chromates in solution are yellow in color, and when 
 treated with an acid turn orange, due to formation of dichromate. 
 
 Soluble dichromates in solution, when treated with an 
 alkali hydroxid, turn yellow. 
 
 80. Barium Chlorid added to a solution of a chromate 
 precipitates- yellowish-white barium chromate (BaCr0 4 ) which 
 is soluble in hydrochloric acid : 
 
 K 2 Cr0 4 + BaCl 2 = BaCr0 4 + 2KC1. 
 
 With potassium dichromate only partial precipitation results, 
 because of the formation of hydrochloric acid : 
 
 K 2 Cr 2 7 +2BaCl 2 +H 2 = 2BaCr0 4 +2KC1 +2HC1. 
 
 The addition of alkali acetate will, however, prevent the 
 solvent action of HC1 on the precipitate, and insure a more 
 complete separation. 
 
 81. Lead Acetate added to a neutral or acetic acid solution 
 or a chromate precipitates yellow lead chromate (PbCr0 4 ) : 
 
 K 2 Cr0 4 +Pb (C 2 H 3 2 ) 2 = PbO0 4 +2KC 2 H 3 2 . 
 
 This precipitate is soluble in caustic soda solution, but 
 insoluble in NH 4 OH and in acetic acid. 
 
 82. Silver Nitrate added to a neutral solution of a chromate 
 precipitates a dark red silver chromate (Ag 2 Cr0 4 ) which is 
 soluble in ammonium hydroxid and in nitric acid : 
 
 K 2 Cr0 4 +2AgN0 3 = Ag 2 Cr0 4 -f 2KN0 3 . 
 
 The same reagent added to a slightly acid chromate solution 
 precipitates reddish-brown Ag 2 Cr 2 7 . 
 
INORGANIC BASES AND ACIDS. 
 
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106 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 117. 
 
 GROUP C. SILVER NITRATE GROUP. 
 
 STEP IV. To another portion of the neutral aqueous solu- 
 tion, add silver nitrate T.S., and observe effect. 
 
 Result. 
 
 Indication. 
 
 White ppt. insol. in dilute nitric acid; 
 sol. in ammonia. 
 
 White ppt. insol. in dilute nitric acid; 
 insol. in ammonia. 
 
 White ppt. sol. in dilute nitric acid. 
 
 White ppt. sol. in dilute nitric acid; 
 
 sol. in ammonia. 
 White ppt. sol. in dilute nitric acid, 
 
 ppt. darkens on heating. 
 White ppt. sol. in excess of sodium 
 
 thiosulfate. 
 Reddish-brown ppt. insol. in dilute 
 
 nitric acid. 
 
 Reddish-brown ppt. sol. in dil. HNO 3 . 
 
 Yellow ppt. sol. in dil. HNO 3 . 
 Black ppt. sol. in dil. HNO 3 . 
 
 Chlorid. 
 
 Bromid. 
 
 lodid. 
 
 Cyanid. 
 | Sulfocyanate. 
 \ Ferrocyanid. 
 f Borate. 
 1 Carbonate. 
 1 Oxalate. i 
 I Citrate. 
 ! Tartrate. 
 
 Meta and pyrophosphate. 
 
 Sulfite. 
 
 Hypophosphite. 
 Thiosulfate. 
 
 Ferricyanid. 
 
 f Chromate. 
 \ Arsenate. 
 / Phosphate. 
 1 Arsenite. 
 Sulfid. 
 
 CHARACTERISTIC TESTS FOR THE ACIDS OF GROUP C. 
 
 118. HYDROCHLORIC ACID AND CHLORIDS. 
 
 HYDROCHLORIC ACID (HC1) is a gas and occurs in commerce 
 in aqueous solutions. It is a powerful acid. 
 
 83. Manganese Dioxid added to hydrochloric acid, and the 
 mixture heated, gives off chlorin gas : 
 
 Mn0 2 + 4HC1 = MnCl 2 + 2H 2 + C1 2 . 
 
 84. Ammonium Hydroxid held over a glass rod near the 
 mouth of a vessel containing hydrochloric acid, produces dense 
 white clouds of NH 4 C1. 
 
INORGANIC BASES AND ACIDS. 107 
 
 85. Silver Nitrate produces a curdy white precipitate of 
 AgCl, soluble in NELiOH and reprecipitated upon acidulation 
 with HN0 3 . 
 
 86. CHLORIDS. Silver Nitrate added to a solution of a chlorid 
 in the presence of nitric acid gives a curdy white precipitate 
 which is soluble in ammonium hydroxid and reprecipitated 
 upon acidulation with nitric acid: 
 
 NaCl + AgN0 3 = AgCl + NaN0 3 . 
 
 87. Manganese Dioxid and Concentrated Sulfuric Acid added 
 to a chlorid and the mixture heated, evolves chlorin gas, which 
 may be recognized by its odor, and its bleaching power on 
 moist litmus or indigo paper, and by its liberating iodin from 
 iodids, and turning starch-iodid paper blue: 
 
 Mn0 2 + 2H 2 S0 4 + 2NaCl = MnS0 4 + Na 2 S0 4 + 2H 2 + C1 2 . 
 
 88. Lead acetate produces a white ppt. soluble in hot water. 
 
 119. HYDROBROMIC ACID (HBr) AND BROMIDS. 
 
 89. Silver Nitrate added to a solution of a bromid precipitates 
 dirty-white AgBr insoluble in nitric acid, sparingly soluble hi 
 strong ammonia water, but insoluble in dilute (5 per cent.) 
 ammonia water. 
 
 90. Chlorin Water added drop by drop to a solution of a 
 bromid liberates bromin. If a few drops of chloroform be 
 added to this mixture and shaken, the chloroform will dissolve 
 the liberated bromin, forming a golden yellow or reddish colored 
 bead, which settles to the bottom of the test-tube. The color 
 produced depends upon the amount of bromin present. 
 
 120. HYDRIODIC ACID (HI) AND IODIDS. 
 
 91. Silver Nitrate added to a solution of an iodid precipitates 
 yellow Agl, insoluble in nitric acid and only very sparingly 
 soluble in ammonia water. 
 
 92. Chlorin Water reacts with iodids in same manner as it 
 does with bromids, the liberated iodin dissolving hi the chloro- 
 
108 QUALITATIVE CHEMICAL ANALYSIS. 
 
 form, forming a violet bead. Free iodin may also be identified by 
 adding starch paste, with which it strikes a blue color. In 
 this test, as in the corresponding test for bromid, care must be 
 taken to avoid adding an excess of chlorin water, otherwise 
 colorless iodic acid (HI0 3 ) will be formed. 
 
 93. Mercuric Chic-rid added to an iodid precipitates red 
 HgI 2 , which dissolves as long as the iodid is in excess, but 
 remains precipitated if the mercuric chlorid is in excess : 
 
 HgCl 2 + 2KI = HgI 2 + 2KC1, 
 HgI 2 +2KI = K 2 HgI 4 . 
 
 121. SULFOCYANATES (Thiocyanates) (RONS). 
 
 94. Silver Nitrate, added to a solution of a sulfocyanate, 
 precipitates white silver sulfocyanate, insoluble in dilute nitric 
 acid and in ammonium hydroxid : 
 
 KCNS + AgN0 3 = AgCNS. + KN0 3 . 
 
 95. Ferric Salts brought in contact with a solution of sulfo- 
 cyanate gives a blood-red coloration due to the formation of 
 Fe(CNS) 3 . This color is destroyed by mercuric chlorid (dis- 
 tinction from meconate) but is not destroyed by hydrochloric 
 acid (distinction from acetate). 
 
 122. FERROCYANIDS (R' 4 Fe(CN) 6 ). 
 
 96. Silver Nitrate added to a solution of a ferrocyanid 
 produces a white gelatinous precipitate of Ag 4 Fe(CN)6 insoluble 
 in dilute nitric acid and in ammonium hydroxid, unless heated : 
 
 K 4 Fe (CN) 6 + 4AgN0 3 - Ag 4 Fe (CN) 6 + 4KN0 3 . 
 
 97. Ferric Salts produce with slightly acid solutions of 
 ferrocyanids a blue precipitate Fe 4 (Fe(CN) 6 ) 3 Prussian blue. 
 
 98. Copper Sulfate added to a solution of a ferrocyanid 
 produces a reddish-brown precipitate of Cu 2 Fe(CN) 6 . 
 
INORGANIC BASES AND ACIDS. 
 
 109 
 
 123. FERRICYANIDS (R' 3 Fe(CN) 6 ). 
 
 99. Silver Nitrate produces with ferricyanids a reddish-brown 
 precipitate (AgsFe(CN)6) insoluble in nitric acid but soluble 
 in ammonium hydroxid. 
 
 100. Ferrous Sulfate or any ferrous salt gives a blue precip- 
 itate (Fe 3 (Fe(CN) 6 )2Turnbuirs blue) insoluble in acids. Ferric 
 salts give no precipitate but a brownish coloration. 
 
 124. CHART FOR THE OBSERVATION OF THE REACTIONS OF 
 THE ACIDS OF THE SILVER NITRATE GROUP (C). 
 
 
 AgNO 3 . 
 
 Pb(C2H 3 02)2. 
 
 Chlorine Water. 
 
 Special Tests. 
 
 Chlorid, 
 -Cl. 
 
 White ppt. 
 Soluble i n 
 NH 4 OH. 
 
 White ppt. 
 Soluble in 
 hot water. 
 
 
 MnO 2 H 2 SO 4 = 
 Cl liberated. 
 
 Bromid, 
 Br 
 
 White ppt. 
 Sparingly 
 soluble i n 
 strong 
 NH 4 OH. In- 
 soluble i n 
 HNO 3 . 
 
 White ppt. 
 Soluble i n 
 hot water. 
 
 Liberates Br 
 Add CHC1 3 
 A golden yel- 
 low color is 
 imparted to 
 the latter. 
 
 
 lodid, 
 j 
 
 Yellow ppt., 
 very sparing- 
 ly soluble in 
 NH 4 OH. In- 
 soluble i n 
 HNO 3 . 
 
 Yellow ppt. 
 Soluble i n 
 hot water. 
 
 Liberates I, 
 which turns 
 starch paste 
 blue. 
 
 HgCl 2 = red 
 ppt. soluble 
 in excess of 
 the iodid. 
 
 Sulfocyanate, 
 
 CNS. 
 
 White ppt. 
 Insoluble in 
 NH 4 OH. In- 
 soluble i n 
 diluteHNO 3 . 
 
 White ppt. 
 
 
 Ferric salts 
 give blood 
 red color de- 
 troy ed b y 
 HgCl 2 , but 
 not by HC1. 
 
 Ferrocyanid, 
 
 4 Fe(CN) 6 
 
 White ppt. 
 Soluble i n 
 hot NH 4 OH. 
 
 White ppt. 
 
 
 Acidified so- 
 lution +ferric 
 salt = blue. 
 CuSO= red- 
 dish brown 
 ppt. 
 
 Ferricyanid, 
 
 3Fe(CN) 6 
 
 Reddish- 
 brown ppt. 
 Soluble i n 
 NH 4 OH,not 
 in HNO 3 . 
 
 No ppt. 
 
 
 Acidified so- 
 lution+ fer- 
 rous salt = 
 blue. 
 
110 QUALITATIVE CHEMICAL ANALYSIS. 
 
 125. GROUP D. DEFLAGRATING GROUP. 
 
 STEP V. A portion of the original dry substance or the 
 residue on evaporation, is placed in a shallow concavity on a 
 piece of charcoal and heated by means of a blow-pipe flame. A 
 more or less violent deflagration indicates nitrate, nitrite, chlor- 
 ate, br ornate, Mate, hypophosphite or permanganate. 
 
 CHARACTERISTIC TESTS FOR ACIDS OF GROUP D. 
 
 126. NITRIC ACID AND NITRATES. 
 
 NITRIC ACID (HNO) 3 . A powerful corrosive acid liquid. 
 It fumes in the air and dissolves most metals. 
 
 101. A piece of copper is put into a test-tube with some nitric 
 acid. Effervescence takes place and orange-red fumes of 
 N 2 04 are evolved. 
 
 102. A quill immersed in nitric acid is stained yellow; this 
 color is intensified on touching the stained quill with an alkali. 
 
 103. NITRATES. Copper foil or filings added to a nitrate and 
 the mixture then heated with sulfuric acid, produces orange- 
 red fumes of N 2 04 : 
 
 (a) KN0 3 +H 2 S04=KHS0 4 +HN0 3 . 
 
 (6) 3Cu + 8HN0 3 = 
 
 (c) N 2 2 + 2 =N 2 4 . 
 
 104. Ferrous Sulfate in the form of a freshly-prepared solu- 
 tion is mixed with an equal volume of a saturated solution 
 of a nitrate, and the mixture floated upon concentrated sulfuric 
 acid in a test-tube; a brown ring will form at line of contact. 
 
 105. When ignited, nitrates evolve oxygen, KN0 3 = KN0 2 + 0. 
 
 127. NITROUS ACID AND NITRITES. 
 
 NITROUS ACID (HN0 2 ). Commercial nitrous acid is nitric 
 acid containing nitrous anhydrid. It has a yellowish color 
 and evolves reddish fumes. 
 
INORGANIC BASES AND ACIDS. Ill 
 
 NITRITES. -All nitrites are soluble in water, silver nitrite 
 only sparingly. 
 
 106. Sulfuric Acid when dilute, decomposes nitrites (but 
 not nitrates) with evolution of reddish fumes. The gas evolved 
 in this reaction is N 2 2 , which in contact with the air is oxidized 
 to N 2 4 : 
 
 (a) 2NaN0 2 + H 2 S0 4 =Na 2 S0 4 +2HN0 2 . 
 (6) 3HN0 2 = HN0 3 +H 2 + N 2 2 . 
 (c) N 2 2 +0 2 = N 2 4 . 
 
 107. Potassium lodid and Starch Solution, when added to a 
 solution of a nitrite, and the mixture acidified with acetic acid 
 produces a blue color: 
 
 2HN0 2 + 2HI = I 2 + 2H 2 + N 2 2 . 
 
 108. Ferrous Sulfate T.S. mixed with an equal volume of 
 a solution of a nitrite when floated upon concentrated acetic 
 acid in a test-tube, produces a dark-brown ring at the line 
 of contact. This test distinguishes nitrites from nitrates, 
 the latter requiring sulfuric acid to produce the described 
 effect. 
 
 128. CHLORATES (R'C10 3 ). 
 
 109. When ignited, chlorates evolve oxygen and leave a residue 
 of the chlorid of the metal. KC10 3 = KC1+0 3 . Treat residue 
 as under paragraph 118. 
 
 110. Concentrated Sulfuric Acid is warmed and treated with 
 a crystal of potassium chlorate. The chlorate is decomposed, 
 producing (C10 2 ) , a greenish-yellow gas which explodes violently. 
 
 Caution. Perform this test with great care so as to avoid 
 harm to yourself and to your neighbor. 
 
 129. BROMATES and IODATES, like chlorates, are reduced 
 when heated, evolving oxygen and leaving a residue respectively 
 of bromid and iodid. Treat residue as under paragraphs 119 and 
 
112 QUALITATIVE CHEMICAL ANALYSIS. 
 
 120 respectively. Like chlorates, these salts deflagrate when 
 heated on charcoal. 
 
 Dilute Sulfurous Acid liberates respectively bromin and 
 iodin ; which can be recognized by the CHC1 3 , bead. 
 
 130. PERMANGANATES (R'Mn0 4 ). 
 
 111. Color. The color of permanganate solutions is violet 
 or pink according to the degree of concentration. 
 
 The color is destroyed by adding oxalic acid, and warming, 
 or by heating with hydrochloric acid and adding alcohol or 
 glycerin. 
 
 112. When ignited, permanganates yield oxygen. 
 
 131. HYPOPHOSPHITES (RTH 2 2 ). 
 
 113. When the dry salt is heated in a test-tube or porcelain 
 dish phosphoretted hydrogen (PH 3 ) is evolved, which bursts 
 into flame, a residue of pyrophosphate being left. 
 
 This test should not be made on a platinum foil because the 
 latter will be destroyed by it. 
 
 114. Silver Nitrate added to a solution of a hypophosphite 
 gives a white precipitate which rapidly turns brown, owing 
 to reduction to metallic silver. 
 
 115. Mercuric Chlorid, added to a hypophosphite solution 
 slightly acidulated with hydrochloric acid, gives a precipitate 
 of calomel (Hg 2 Cl 2 ) which darkens on heating, owing to reduction 
 to metallic mercury. 
 
 116. Free Hypophosphorous Acid, warmed to 55 C. with 
 copper sulfate solution gives a reddish-black precipitate of 
 copper hydrid (Cu 2 H 2 ) which is reduced to metallic copper upon 
 boiling. 
 
 This test may be applied to hypophosphites, by first removing 
 the metallic base. If the base is calcium precipitate it with 
 oxalic acid; if barium, use sulfuric acid; if a heavy metal use 
 hydrogen sulfid. 
 
INORGANIC BASES AND ACIDS. 
 
 113 
 
 132. CHART FOR THE OBSERVATION OF REACTIONS OF ACIDS 
 OF DEFLAGRATING GROUP "D." 
 
 
 Heating Dry Sub- 
 stance in a Test-tube. 
 
 H 2 S0 4 . 
 
 Special Testa. 
 
 NITRATES, 
 N0 3 
 
 Evolves O, which 
 kindles glowing 
 wood. 
 
 / 
 
 +Cu foil and heat 
 with H 2 SO 4 = 
 fumes of N 2 O 4 . 
 FeSO 4 (freshly pre- 
 pared) and float on 
 H 2 SO 4 = brown ring 
 at contact. 
 
 NITRITES, 
 NO 2 
 
 Evolves, O, N, and 
 nitrogen dioxid. 
 
 +dil. H 2 SO 4 = evo- 
 lution of N 2 O 2 , 
 which is oxidized 
 to N 2 4 . 
 
 FeSO 4 +equal vol. 
 of nitrite floated on 
 HC 2 H 3 O 2 = brown 
 ring at line of con- 
 tact. (Nitrates re- 
 quire H 2 SO 4 ). KI 
 +HC 2 H 3 2 + 
 starch = blue. 
 
 CHLORATES, 
 C1O 3 . 
 
 Evolves O and 
 leaves a chlorid ol 
 metal, which test. 
 
 Explosion with 
 production of a 
 greenish-yellow 
 gas. 
 
 
 BROMATES, 
 Br0 3 . 
 
 Evolves O and 
 leaves a bromid 
 of the metal, 
 which test. 
 
 Dil. H 2 S0 4 liber- 
 ates Br, which 
 gives a reddish 
 bead with CHC1 3 . 
 
 
 lODATES, IO 3 . 
 
 Evolves O and 
 leaves an iodid 
 of metal, which 
 
 test. 
 
 Dil. H 2 SO 4 liber- 
 ates I, which 
 turns blue with 
 starch. 
 
 
 PERMANGAN- 
 ATES, MnO 4 . 
 
 Evolves O, which 
 kindles glowing 
 wood. 
 
 
 Color of solution is 
 violet and is de- 
 stroyed by oxalic 
 acid or by heating 
 with HC1 and ad- 
 ding alcohol or 
 glycerin. 
 
 HYPOPHOS- 
 
 PHITES, 
 
 PH 2 O 2 . 
 
 Evolves PH 3 , 
 which bursts into 
 flame. 
 
 
 AgNO 3 = white ppt., 
 turns brown. 
 HgCl 2 +HCl = 
 white ppt. Dark- 
 ens on heating. 
 Free acid+CuSO 4 , 
 warmed to 55 C., 
 reddish-black ppt. 
 
114 QUALITATIVE CHEMICAL ANALYSIS. 
 
 CHARACTERISTIC TESTS FOR THE ORGANIC ACIDS. 
 133. GROUP E. FERRIC CHLORID GROUP. 
 
 STEP VI. To another portion of the neutral aqueous solu- 
 tion add ferric chlorid T.S., and observe effect. 
 
 Result. 
 
 Indication. 
 
 Red Colored Solution. No ppt. 
 Color gradually disappears. 
 Color is discharged by HgCl 2 and 
 
 HC1. 
 Color is discharged by HgCl 2 but 
 
 not by HC1. 
 Color changed to deep bluish-black 
 
 by ammonia. 
 
 Color is not discharged by HgCl 2 . 
 Color is fault. 
 Color is destroyed by heat. 
 
 Violet colored solution. 
 
 Pale green solution. 
 
 A darkening of the solution, no ppt. 
 
 Black ppt. 
 
 Dark blue ppt. 
 
 Buff or flesh-colored ppt. 
 
 Reddish-brown ppt. 
 Pink to brownish-red ppt. 
 
 Thiosulfate. 
 Acetate. 
 
 Sulfocyanate. 
 Pyrogallate. 
 
 Meconate. 
 
 Trichloracetic. 
 
 Sulfite. 
 
 f Salicylate. 
 
 | Carbolate. 
 
 [ Phenolsufonate. 
 Citrate. 
 Ferricyanid. 
 
 { Sulfid. 
 
 \ Gallate. 
 
 I Tannate. 
 Ferrocyanid. 
 Benzoate. 
 
 f Carbonate. 
 
 \ Hydroxid. 
 
 [ Chromate. 
 Succinate. 
 
 CHARACTERISTIC TESTS FOR ACIDS OF GROUP E. 
 134. ACETIC ACID AND ACETATES. 
 
 117. ACETIC ACID (HC 2 H 3 2 ) is recognized by its odor of 
 vinegar. 
 
 118. ACETATES. All normal acetates are soluble. Some 
 basic acetates, as ferric subacetate, and aluminum subacetate, 
 are practically insoluble. On ignition, acetates decompose, 
 with little or no charring, and evolve an inflammable gas. 
 
 Alkali acetates are converted on ignition into carbonates. 
 
INORGANIC BASES AND ACIDS. 115 
 
 Other acetates are converted by ignition into oxids, or reduced 
 to the metal. 
 
 119. Sulfuric Acid, heated with an acetate, liberates acetic 
 acid, recognized by its odor of vinegar: 
 
 NaC 2 H 3 2 + H 2 S0 4 = NaHS0 4 + CH 3 COOH. 
 
 120. Alcohol and Strong Sulfuric Acid, gently heated with 
 an acetate, yields acetic ether, recognized by its odor of apples: 
 
 CHaCOOH + C 2 H 5 OH = CH 3 COOC 2 H 5 + H 2 0. 
 
 121. Ferric Chlorid produces with acetates a red-colored 
 solution (ferric acetate) Fe 2 (C2H 3 2 )6. If this solution is 
 largely diluted with water and boiled, a precipitate of basic 
 ferric acetate (Fe(OH)(C 2 H 3 2 ) 2 ) is produced. The red color 
 first produced is discharged by both HC1 and HgCl 2 (distinction 
 from sulfocyanates). 
 
 135. BENZOIC ACID AND BENZOATES. 
 
 BENZOIC ACID (HC 7 H 5 2 ) occurs in yellowish-white lustrous 
 scales or friable needles having a slight benzoin-like odor. 
 It is only slightly soluble hi water but readily soluble in 
 alcohol. 
 
 122. Heated in a tube open at both ends it sublimes, and 
 evolves an irritating odor. 
 
 123. Slaked Lime, mixed with one-third its weight of benzoic 
 acid and heated in a test-tube, evolves benzene. 
 
 124. Ferric Chlorid, added to a neutralized solution of ben- 
 zoic acid in alkali hydroxid gives a flesh-colored precipitate of 
 ferric benzoate. 
 
 125. BENZOATES. When ignited, they char and leave a residue 
 of carbonate (see Citrates). 
 
 126. Ferric Chlorid, added to an aqueous solution of a ben- 
 zoate, gives a flesh-colored precipitate. 
 
116 QUALITATIVE CHEMICAL ANALYSIS. 
 
 127. Dilute Sulfuric or Hydrochloric Acid, added to an 
 aqueous solution of a benzoate, produces a white precipitate of 
 benzoic acid. 
 
 128. Silver Nitrate produces a white ppt. soluble in hot H 2 
 and NH 4 OH. 
 
 136. SALICYLIC ACID AND SALICYLATES. 
 
 SALICYLIC ACID (HC 7 H 5 03) occurs in white crystalline pow- 
 der or prisms. It is readily soluble in alcohol, but not in water. 
 
 129. SALICYLATES, upon heating, behave like the previously 
 described organic salts. 
 
 130. Ferric Chlorid, added to an aqueous solution, produces 
 an intense bluish- violet coloration. 
 
 131. On adding to a small portion of salicylic acid, or a salicy- 
 late, in a test-tube, some concentrated sulfuric acid, and then 
 continuously in drops some methyl alcohol, and heating the mix- 
 ture to boiling, an odor of oil of wintergreen (methyl salicylate) is 
 produced. 
 
 132. Copper Sulfate Solution added to an aqueous solution of 
 a salicylate gives a green coloration. 
 
 133. Dilute Sulfuric Acid precipitates salicylic acid out of 
 solutions of salicylates. 
 
 134. Silver Nitrate gives a white ppt. soluble in hot water. 
 
INORGANIC BASES AND ACIDS. 117 
 
 137. TANNIC, GALLIC, AND PYROGALLIC ACIDS. 
 
 TANNIC ACID, HCi 4 H 9 9 (C 13 H 9 7 COOH). 
 
 GALLIC ACID, HC 7 H 5 5 + H 2 (C 6 H 2 (OH) 3 COOH + H 2 0) . 
 
 PYROGALLIC ACID, C 6 H 6 3 (C 6 H 3 (OH) 3 ). 
 
 Reagent. 
 
 Tannic Acid. 
 
 Gallic Acid. 
 
 Pyrogallic Acid. 
 
 135. (a) Ferric 
 Chlorid. 
 
 A bluish - black 
 coloration or ppt. 
 
 Same effect. 
 
 Brownish - red 
 solution, changed 
 to deep bluish- 
 black upon addi- 
 tion of NH 4 OH. 
 
 136. (6) Pure Fer- 
 rous Sulfate. 
 
 
 Neither color nor 
 ppt. 
 
 A bluish-black 
 solution. 
 
 (c) Lime water 
 (in small amount) 
 
 (In moderate 
 excess). 
 
 (In large ex- 
 cess.) 
 
 A pale, bluish- 
 white ppt. which 
 does not dissolve 
 on shaking. 
 A more cuprous 
 and deeper blue 
 ppt. 
 
 Imparts to liquid 
 a pale pink tint. 
 
 Ppt. dissolved on 
 shaking. 
 
 Ppt. is perma- 
 nent, and the solu- 
 tion is blue by 
 reflected light and 
 green by trans- 
 mitted light. 
 Liquid becomes 
 pink. 
 
 A purple solu- 
 tion becoming 
 brown by oxida- 
 tion. 
 
 137. (d) Solu- 
 tions of gelatin 
 albumen, starch, 
 most alkaloidsand 
 glucosides. 
 
 A ppt. 
 
 No ppt. 
 
 No ppt. 
 
 138. PHENOLSULFONATES (Sulfocarbolates) 
 
 (R'C 6 H 4 (OH)S0 3 ). 
 
 Heated above 100 C. phenolsulfonates char, emit inflammable 
 vapors with an odor of phenol, and leave a residue of sulfate. 
 
 138. Ferric Chlorid added to a solution of a phenolsulfonate 
 gives a pale violet color. 
 
 139. Barium Chlorid gives no precipitate, but if a portion 
 of the salt is ignited and the residue dissolved in water, barium 
 chlorid will produce a white precipitate. 
 
118 QUALITATIVE CHEMICAL ANALYSIS. 
 
 139. PHENOLATES. 
 
 Ferric Chlorid gives a violet color. 
 
 Heated with sulfuric acid, phenolates give an odor of phenol. 
 
 140. MECONIC ACID (H 2 C 7 H 2 7 + 3H 2 0). 
 
 140. MECONATES. Neutral Ferric Chlorid Solution produces a 
 red color with meconic acid or meconates. This color is not 
 discharged by HgCl 2 , but is bleached by dilute HC1 (distinction 
 from sulf ocyanate) . 
 
 Compare with acetate. 
 
 141. Silver Nitrate gives a yellowish ppt. soluble in HN 4 OH. 
 
 141. SUCCINIC ACID (H 2 C 4 H 4 04). 
 
 Succinic acid does not char with strong hot sulfuric acid. 
 Sublimes in a tube open at both ends without giving off an 
 irritating odor (difference from benzoic acid). 
 
 142. SUCCINATES. Ferric Chlorid gives a brownish-red pre- 
 cipitate Fe2(C 4 H 4 04)3. 
 
 143. Barium Chlorid gives no precipitate unless alcohol 
 and ammonium hydroxid be added, when a white precipitate 
 is formed (difference from benzoic acid). 
 
 144. Lead Acetate gives a white precipitate soluble in suc- 
 cinic acid and excess of reagent. 
 
 145. Silver Nitrate gives in neutral solutions a white ppt 
 soluble in NH 4 OH. 
 
 142. TRICHLORACETIC ACID (HC 2 C1 3 2 ). 
 
 146. Is a deliquescent crystalline solid, soluble in water, 
 alcohol and ether. 
 
 147. The aqueous solution is decomposed on boiling, forming 
 chloroform and carbon dioxid. 
 
 148. On heating with Potassium Hydroxid T,S., it is decom- 
 posed, forming chloroform and potassium carbonate. 
 
 149. Ferric Chlorid, added to an aqueous solution of trichlor- 
 acetic acid develops a faint reddish color. 
 
INORGANIC BASES AND ACIDS. 
 
 119 
 
 II 
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120 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 
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 PQ'~ 
 
 
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 ft. 
 
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 ppt. soluble in excess. 
 
 Heated with KOH forms 
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 PHENOL SUL 
 
 FO N ATE S , 
 
 C 6 H 4 (OH)S( 
 
 PHENOLATE! 
 
 C 6 H 5 OH. 
 
 MECONATE 
 2 C 7 H 2 Ov3H 
 
 SUCCINATE 
 C 4 H 4 4 . 
 
 TRICHLORACET: 
 C 2 C1 3 O 2 . 
 
INORGANIC BASES AND ACIDS. 
 
 121 
 
 144. 
 
 GROUP F. CALCIUM CHLORID GROUP. 
 
 STEP VII. To another portion of the neutral aqueous solu- 
 tion, add some calcium chlorid T.S., and observe effect. 
 
 Result. 
 
 Indication. 
 
 A white ppt. is produced. 
 Soluble in NH 4 C1 Sol. 
 
 Sol. in acetic acid. 
 
 Insol. in acetic acid. 
 
 The ppt. chars when heated. 
 
 Sol. in NaOH, reprecipitated on boil- 
 ing. An excess of reagent must 
 be added to obtain this ppt. 
 
 Sol. in much water. 
 
 White ppt. in presence of alcohol. 
 
 ( Borate. 
 \ Carbonate. 
 I Citrate. 
 
 Borate. 
 
 Sulfite. 
 
 Carbonate. 
 
 Phosphate. 
 
 Citrate. 
 Oxalate. 
 / Tartrate. 
 \ Citrate. 
 Tartrate. 
 
 Sulfate. 
 Malate. 
 
 145. CITRIC ACID AND CITRATES. 
 
 CITRIC ACID (H 3 C6H 5 07) occurs in colorless crystals having 
 a distinct acid taste, deliquescent in moist air but efflorescent 
 when exposed in dry air. Soluble in water and in alcohol. 
 
 150. On igniting it slowly it is gradually decomposed, without 
 emitting an odor of burning sugar (difference from tartaric 
 acid). 
 
 151. Its addition to a solution of a ferric salt prevents precip- 
 itation of ferric hydroxid on adding ammonium hydroxid. 
 
 152. Upon adding to a solution of citric acid sufficient lime 
 water to render the mixture alkaline, the liquid remains clear. 
 Upon boiling this for one minute it becomes opaque, through 
 precipitation of calcium citrate, which redissolves on cooling. 
 
 153. CITRATES. Upon healing citrates char. The citrates of 
 the alkali and alkali earth metals char, and are reduced to 
 carbonates. Citrates of most other metals are reduced by 
 ignition to oxids, while silver citrate is reduced to the metal. 
 
 c&$ 
 
122 QUALITATIVE CHEMICAL ANALYSIS. 
 
 154. Calcium Chlorid Solution, added to a cold solution of a cit- 
 rate made slightly alkaline with ammonia water, gives no precip- 
 itate, until boiled, when a white granular precipitate is produced. 
 
 155. Strong Sulfuric Acid heated with a citrate slowly 
 blackens it, and evolves a slight odor resembling burning sugar. 
 
 146. TARTARIC ACID AND TARTRATES. 
 
 156. TARTARIC ACID (H 2 C 4 H 4 06) is a strong organic acid. It 
 is freely soluble in water and in alcohol. When heated it chars, 
 and finally burns away. Heated with strong sulfuric acid, it is 
 charred, and evolves an odor resembling that of burnt sugar. 
 
 157. A concentrated solution of tartaric acid, when treated 
 with potassium acetate, gives a white precipitate of potassium 
 bitartrate. The addition of alcohol facilitates this precipitation: 
 
 H 2 C4H 4 06 + KC 2 H 3 2 = KHC 4 H 4 6 + HC 2 H 3 2 . 
 
 158. TARTRATES. Tartrates char when heated. 
 
 159. Silver Nitrate added to a solution of a normal tartrate, 
 precipitates white silver tartrate (Ag 2 C 4 H 4 Oe) readily soluble in 
 ammonium hydroxid. If this ammoniacal solution be gently 
 heated, the silver will deposit on the sides of the test-tube, 
 forming a mirror. 
 
 160. Silver nitrate does not react with free tartaric acid. 
 
 161. Calcium Chlorid added to a concentrated solution of a 
 neutral tartrate precipitates white crystalline calcium tartrate 
 (CaC 4 H 4 6 ). This precipitate, when washed with water, dis- 
 solves in cold sodium hydroxid solution. If this solution is 
 boiled CaC 4 H 4 06 is again precipitated in gelatinous form, and 
 redissolves on cooling. The reagent must be added in excess to 
 obtain this precipitate, and ammonium salts must be absent. 
 
 This test differentiates tartrates from citrates. 
 
 162. Potassium Acetate and other Potassium Salts when 
 added to a solution of a tartrate slightly acidified with acetic 
 acid, gives a crystalline white precipitate of KHC 4 H 4 6 . The 
 precipitation is facilitated by stirring and by the addition of 
 alcohol. 
 
INORGANIC BASES AND ACIDS. 
 
 123 
 
 163. Neutral solutions of tartrates are not precipitated by 
 potassium salts. 
 
 164. Ferric chlorid gives in neutral solutions, a yellow crys- 
 talline ppt. on warming. 
 
 147. MALIC ACID (H2C 4 H 4 5 ). 
 
 165. MALATES. Calcium Chlorid, added to a neutral aqueous 
 solution of a malate, gives no precipitate because calcium malate 
 is soluble in water. The addition, however, of even a small 
 quantity of alcohol causes a precipitation of a calcium malate. 
 Calcium malate dissolves when boiled with lime water (difference 
 from citrate). 
 
 166. Hot strong Sulfuric Acid chars malic acid very slowly 
 (difference from tartaric acid). 
 
 167. Lead Acetate gives a white ppt. soluble in hot water. 
 
 148. CHART FOR THE OBSERVATION OF THE REACTIONS OF 
 THE ACIDS OF Cad* GROUP. GROUP F. 
 
 
 Citrates. 
 
 Tartrates. 
 
 Malates. 
 
 CaCl 2 and 
 NH 4 OH. 
 
 Cold = no ppt. 
 Boiled = white 
 granular ppt. 
 
 White ppt. soluble in 
 NaOH. Boiled = a 
 gelatinous ppt. redis- 
 solves on cooling. 
 
 In neutral solutions 
 =no ppt. Add al- 
 cohol = ppt. soluble 
 in lime water. 
 
 HEAT. 
 
 Chars. 
 
 Chars. 
 
 Chars. 
 
 H 2 S0 4 
 
 Blackens and 
 evolves a slight 
 odor resembling 
 burning sugar. 
 
 Chars and evolves odor 
 of burning sugar. 
 
 Chars very slowly. 
 
 AgN0 3 
 
 
 White ppt. soluble in 
 NH 4 OH. If heated, 
 a silver mirror will 
 deposit on sides. 
 
 
 POTASS. 
 
 ACETATE 
 
 
 -j-HC 2 H 3 O 2 = white 
 ppt. especially in 
 presence of aclohol. 
 
 
 FeCl 3 
 
 
 Yellow crystalline ppt. 
 on warming. 
 
 
 LEAD ACE- 
 TATE. 
 
 
 
 White ppt. soluble 
 in hot H 2 O. 
 
124 QUALITATIVE CHEMICAL ANALYSIS. 
 
 149. GROUP G. UNCLASSIFIED GROUP. 
 
 STEP VIII. Unless contra-indicated, make individual tests 
 for acids not mentioned in the foregoing steps, as for instance, 
 lactic, oleic, stearic, valeric, etc. 
 
 150. LACTIC ACID AND LACTATES. 
 
 LACTIC ACID (HCsHsOs). A colorless syrupy liquid. 
 
 168. Potassium Permanganate, added to a mixture of equal 
 parts of lactic and sulfuric acids and gently heated, evolves 
 odor of aldehyde. 
 
 169. On heating above 160 C., the acid emits inflammable 
 vapors and burns away with a pale flame. 
 
 170. Heated with Sulfuric Acid, it gives off a large quantity 
 of pure CO. 
 
 171. Strong solutions of an alkali lactate, when boiled with 
 HgNOs, deposit pink mercurous lactate, HgCsHsOs. 
 
 172. Silver nitrate solution when heated with lactic acid, 
 will be reduced and metalli< silver will deposit slowly. 
 
 151 OLEIC ACID AND OLEATES. 
 
 OLEIC ACID (HCi 8 H 33 2 ) is an oily liquid of a brownish 
 or yellowish color which when cooled to below 4 C. solidifies. 
 It is insoluble in water but is soluble in ether, chloroform, 
 alcohol, benzin and fixed and volatile oils. 
 
 173. OLEATES of sodium and potassium are soluble in water. 
 Other oleates are not. Acid oleates are liquid and dissolve 
 readily in absolute alcohol and ether. The alcoholic solution 
 is acid in reaction. 
 
 174. Oleates do not separate out from the above-named sol- 
 vents when a hot solution is cooled (difference from stearates 
 and palmitates). 
 
 175. Lead Acetate added to an aqueous solution of an oleate 
 gives a white precipitate of Pb(Ci 8 H 3 30 2 )2 which is soluble 
 
INORGANIC BASES AND ACIDS. 125 
 
 in ether (distinction from stearate). Stearate and oleate may be 
 separated one from the other in this way. 
 
 '152. STEARIC ACID AND STEARATES. 
 
 176. STEARIC ACID (HCi 8 H3 5 2 ) is a white fatty solid. 
 Melts on heating and is soluble in boiling alcohol and in ether. 
 The alcoholic solution is acid in reaction. 
 
 177. If stearic acid be dissolved in potassium hydroxid 
 solution, and the solution carefully neutralized, the addition 
 of lead acetate will give a precipitate of Pb(Ci 8 H 3 502)2, which 
 is not soluble in ether (difference from oleic acid). 
 
 STEARATES. The alkali stearates are alone soluble in water. 
 
 178. Stearates heated with dilute hydrochloric acid cause 
 a separation of stearic acid, which floats on the surface as an 
 oily liquid, and on cooling solidifies 
 
 153 . VALERIC ACID AND VALERATES (Valerianic Acid), 
 
 179. VALERIC ACID (HC 5 H 9 2 ) is a volatile bad-smelling, 
 colorless, oily liquid. 
 
 180. VALERATES have the characteristic odor of valerian, 
 especially when warmed. 
 
 181. Sulfuric Acid added in slight excess to a solution of a 
 valerate will decompose the latter, and an oily layer of valeric 
 acid will rise to the surface. 
 
 154. Detection of Acids in Insoluble Substances. Boil some 
 of the substance in a flask for five minutes or so with a strong 
 solution of Na 2 C0 3 , cool, filter, and neutralize the filtrate with 
 HN0 3 , carefully avoiding excess of the acid. 
 
 All the acid radicals of the substance will be converted 
 into corresponding sodium salts and dissolved in the aqueous 
 solution, which is then tested for the acid. 
 
126 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 155. CHART FOR THE OBSERVATION OF REACTIONS OF 
 ACIDS OF "UNCLASSIFIED" GROUP G. 
 
 
 Lactates. 
 
 Oleates. 
 
 Stearates. 
 
 Valerates. 
 
 HEAT. 
 
 Above 160 C. 
 emits an inflam- 
 mable vapor and 
 burns with a pale 
 flame. 
 
 Chars. 
 
 Chars. 
 
 Chars. 
 
 H,S0 4 
 
 Evolution of a 
 large quantity of 
 CO. 
 
 
 
 An oily 
 layer of 
 valeric 
 acid sep- 
 arates. 
 
 AgN0 3 
 
 The AgNO 3 is re- 
 duced and silver 
 deposits slowly. 
 
 
 
 
 KMnO 4 
 
 -fH 2 SO 4 +heat = 
 evolves odor of 
 aldehyd. 
 
 
 
 
 HgN0 3 
 
 Boil with a strong 
 solution of alkali 
 lactate-pink ppt. 
 
 
 
 
 Pb(C 2 H 3 2 ) 2 
 
 
 White ppt. 
 Soluble 
 in ether. 
 
 +KOH and solu- 
 tion neutralized, 
 +Pb(C 2 H 3 2 ) 2 = 
 white ppt. In- 
 soluble in ether. 
 
 
 HC1 
 
 
 
 Heated = s t e a r i c 
 acid separates 
 and solidifies on 
 cooling. 
 
 
PART III. 
 QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 
 
 156. If a substance chars when heated on platinum foil, or 
 burns with evolution of carbon dioxid, its organic nature is 
 established. 
 
 The Procedure for the Detection of the Ultimate Constituents 
 of Organic Substances is as follows : 
 
 (1) Carbon and Hydrogen. Mix a small quantity of the 
 substance with about six times its bulk of freshly ignited and 
 powdered cupric oxid, place the mixture in a small test-tube 
 and cover it with a layer of cupric oxid. Then close the tube 
 securely with a cork bearing a deli very- tube bent twice at right 
 angles, and apply heat, (a) Gas is evolved (C0 2 ). The gas 
 is passed into a clear solution of Ba(OH) 2 . If the solution 
 becomes turbid (through formation of BaCOs), carbon is indi- 
 cated. (6) If drops of water or moisture are deposited in the 
 upper, cold part of the tube, hydrogen .is indicated. 
 
 (2) Nitrogen. If a substance when heated on platinum, 
 emits an odor of burnt hair or horn, nitrogen is indicated. 
 
 The presence of nitrogen is, however, more accurately 
 determined as follows : Mix about 2 gm. of the substance with 4 
 gm. of dried powdered soda-lime, and heat. If nitrogen is 
 present, there will be observed an odor of NH 3 , recognized 
 also by its turning red litmus blue, and by its forming white 
 fumes when a glass rod moistened with HC1 is brought near 
 the mouth of the tube. 
 
 (3) Chlorin. The presence of the halogens in most organi" 
 
 127 
 
123 QUALITATIVE CHEMICAL ANALYSIS. 
 
 compounds cannot be detected by the simple addition of 
 silver nitrate; therefore a method similar to the following 
 must be employed: 
 
 Mix 1 gm. of the substance with 2 gm. of pure CaO in a 
 test-tube and heat to redness. Then dissolve the residue in 
 distilled water strongly acidulated with HN0 3 , filter, and test 
 for chlorin with AgN0 3 . In this process the CaO is converted 
 into CaCl 2 . 
 
 (4) Sulfur. (In Solids.) Mix 1 gm. of the substance with 
 1 gm. each of KN0 3 and KOH and subject the mixture to 
 fusion. The sulfur is oxidized, and converted into K 2 S0 4 . 
 The fused mass is then dissolved in distilled water, acidified 
 with HC1, and tested with BaCl 2 . A white ppt. (BaS0 4 ) indi- 
 cates sulfur. 
 
 (In Liquids.) Sulfur is detected by heating 3 cc. of the 
 liquid with strong HN0 3 . This converts the sulfur into H 2 S0 4 , 
 which, after diluting with water, is tested with BaCl 2 . 
 
 (5) Phosphorus may be detected as described above (for 
 sulfur in solids). The fusion converts phosphorus into H 3 P0 4 . 
 The fused mass is dissolved in water and tested for phosphate 
 with magnesia mixture. 
 
 Another way is to heat about 2 gm. of the substance with 
 HN0 3 , dilute with water, filter, and test separate portions 
 of the filtrate with, first, FeCl 3 in presence of sodium acetate 
 = a brown ppt. ; and, second, ammonium molybdate solution = 
 a yellow ppt. 
 
 157. BEHAVIOR OF ORGANIC SUBSTANCES WITH 
 IMMISCIBLE SOLVENTS. 
 
 Upon agitating the substance with distilled water acidulated 
 
 with 2% of // 2 $0 4 , and adding half its volume of an immiscible 
 
 solvent (ether, chloroform, or benzene) the following are extracted: 
 
 (1) In the Acidulated Aqueous Liquid there may be dissolved 
 
 carbohydrates, soluble alkaloidal salts, acids, organic bases, and 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 129 
 
 proteids. Add a small excess of NaOH solution and half its 
 volume of an immiscible solvent and again shake, thus further 
 separating the above into (a) and (b). 
 
 (a) The Alkaline Aqueous extract may contain: 
 Carbohydrates; as, dextrin, sugars, gums. 
 Soluble Alcohols; as, methyl, ethyl, propenyl. 
 Soluble Acids ; as, acetic, tartaric, citric, lactic, malic, 
 
 oxalic. 
 Alkaloids and Organic ) as, urea, curarine, cinchonine, 
 
 Bases; ) pyridine, and morphine. 
 
 Coloring matters; as, indigo, cochineal, cudbear. 
 Proteids; as, albumin, casein, gelatin. 
 
 (b) The Immiscible layer may contain: 
 
 Vegetable Alkaloids; as, quinine, strychnine, aconitine, 
 
 atropine, nicotine. 
 Coal-tar Bases; as, aniline, chrysotoluidine, pyridine, 
 
 and their homologues. 
 
 (2) In the Immiscible Solvent there may be dissolved hydro- 
 carbons, oils, acids, coloring matters, resins, phenols, and glucos ids. 
 Add water containing a small excess of NaOH and shake again, 
 thus further separating the above into (a) and (b). 
 
 (a) The Alkaline Aqueous Extract may contain: 
 Fatty acids; as, stearic, oleic, palmitic, valeric. 
 Aromatic acids; as, benzoic, salicylic, phthalic. 
 
 } as, picric or chrysophanic acid; 
 Acid coloring matters I sa ffranin, alizarin, or 
 
 j bilirubin. 
 
 Acid Resins; as, colophony (common pitches). 
 Phenols; as, phenic and cresylic acids; thymol and 
 
 creosote. 
 Glucosids; as, santonin, picro toxin. 
 
 (b) The Immiscible layer may contain: 
 Hydrocarbons, solid; as, paraffin, naphthalene, an- 
 thracene. 
 
130 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 Hydrocarbons, liquid; as, petroleum products, rosin- 
 oil, benzene. 
 
 Essential oils; as, turpentine, terpene, and oxygenated 
 oils. 
 
 Nitro-compounds ; as, nitro-benzene. 
 
 Chloroform, also Ethers ; as, ethyl oxid, ethyl acetate, etc. ; 
 nitro-glycerin. 
 
 Fixed fats, oils, and waxes. 
 
 Neutral resins and coloring matters. 
 
 Camphors; as, laurel-camphor, borneol, menthol. 
 
 Insoluble Alcohols ; as, amyl, cetyl, and cholesterin. 
 
 Glucosids; as, saponin, santonin, and digitalin. 
 
 Weak Alkaloids; as, caffeine, narcotine, pipeline, col- 
 chicine. 
 
 158. BEHAVIOR OF ORGANIC SUBSTANCES WITH 
 FEHLING'S SOLUTION. 
 
 The substance should be made perfectly neutral and brought 
 into solution. One cc. of the solution is heated with 10 cc. 
 of Fehling's Reagent to boiling. In some cases the reduction 
 occurs in the cold or on gently heating the liquid. A yellow 
 or orange-red precipitate or turbidity caused by the precipita- 
 tion of cuprous oxid (Cu 2 0) indicates reducing substance, thus* 
 
 Fehling's Reagent is Reduced by 
 
 Carbohydrates. Lactose, dextrose, 
 
 Isevulose, maltose, mannitose, ara- 
 
 binose, galactose. 
 Alcohols and Phenols. Aldehyd, 
 
 chloral, chloroform, valeric aldehyd, 
 
 resorcinol. 
 Organic Acids. Pyrogallic, gallotan- 
 
 nic, trichloracetic. 
 Inorganic Adds. Arsenous. 
 
 Fehling's Reagent is Not Affected by 
 
 Carbohydrates. Mannite, saccharose, 
 dulcite, cellulose, dextrin, arabin. 
 
 Alcohols and Phenols. Alcohol, gly- 
 cerin, phenol, benzoic and salicylic 
 aldehyds. 
 
 Organic Acids. Acetic, oxalic, suc- 
 cinic, lactic, tartaric, citric, gallic, 
 mucic, benzoic, and salicylic. 
 
 Inorganic Acids. Sulfurous, etc. 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 131 
 
 159. CHART FOR THE DETECTION OF THE MORE 
 
 COMMON ORGANIC COMPOUNDS OF 
 
 PHARMACEUTICAL INTEREST. 
 
 Dissolve a small quantity of the dry substance in a little 
 dilute HC1, and add a drop or two of potassio-bismuthic iodid 
 solution or Mayer's reagent. If a reddish-brown ppt. forms, an 
 alkaloid is indicated. Apply Step I. If no ppt. forms, pass on 
 to Step V and then to Step VI. 
 
 STEP I. To a drop of HNOs on a white porcelain tile add 
 a small quantity of the substance and observe the color. 
 
 Red changing to yellow = Morphine. 
 
 H 2 SO 4 containing in each mil .005 
 Gms. of selenous acid, gives a blue 
 color, changing to green and then 
 to brown. 
 
 An aqueous solution of pot. ferricy- 
 anid containing a drop of FeCl 3 
 T.S. yields a blue solution and finally 
 a blue precipitate. 
 
 Frohde's Reagent gives a pui pie color. 
 
 Sulphuric acid containing a crystal 
 of KIO 3 = a dark brown. 
 
 A few drops of FeCl 3 sol. added to a 
 neutral solution (1 : 100) of mor- 
 phine = a blue color destroyed by 
 acids, alcohol or heat. 
 
 Sulphuric acid containing in each mil 
 1 drop of sol. of formaldehyde gives 
 with morphine an intense purple 
 color. 
 
 Blood-red = Brucine. 
 Color changes to purple on addition of 
 
 a drop of Na 2 S 2 O 3 solution. 
 To crystal of the alkaloid add 
 
 chlorin-water = an evanescent rose- 
 red. 
 To another crystal add HNOs, then 
 
 some solution of AgNOs, and warm 
 
 = a carmine red. 
 To another crystal add bromin- 
 
 water = a yellow ppt., and forming 
 
 a red sol. on warming. 
 
 Yellow changing to Red on heating = 
 Physostigmine, 
 
 With H 2 SO 4 Physostigmine yields a 
 faint yellow color. 
 
 With H 2 SO 4 containing a crystal of 
 KIO 3 = a purple color changing to 
 yellowish red. 
 
 KOH added to the aqueous sol. yields 
 a white ppt. which quickly turns 
 pink soluble in excess to a pink or 
 red sol. which fades to yellowish 
 green. 
 
 Evaporate about .005 Gms. of the salt 
 to dryness with a few drops of 
 NH 4 OH = a blue residue, soluble in 
 alcohol, and when thus dissolved, 
 produces a red solution on addition 
 of an excess of acetic acid. 
 
 Reddish Brown = Aconitine. 
 
 With H 2 SO 4 containing a crystal of 
 ammonium vanadate = orange color. 
 
 With H 2 SO 4 and a grain or two of 
 sugar = red color. 
 
 With H 2 SO 4 on gently warming = 
 violet color. 
 
 With Frohde's Reagent = a yellow- 
 brown color. 
 
132 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 Red Crystals with yellow-colored solu- 
 tion = Codeine. 
 
 With H 2 SO 4 and warming = a violet 
 color. 
 
 With H 2 SO 4 and a trace of FeCl 3 = a 
 violet-blue color. 
 
 With H 2 SO 4 containing a little HNO 3 
 upon heating gives a blood-red color. 
 
 H 2 SO 4 containing .005 gm. of selenous 
 acid in each mil produces a green 
 color changing rapidly to blue, then 
 slowly back to grass green. 
 
 Purple fading to orange = Apomor- 
 phine. 
 
 With H 2 SO 4 and a trace of FeCl 3 = 
 a pale blue. 
 
 With H 2 SO 4 containing a trace of 
 HNO 3 = a blood-red color. 
 
 With H 2 SO 4 containing a little par- 
 aldehyde = a green color fading to 
 reddish brown. 
 
 Dilute FeCl 3 sol. colors the alkaloid 
 solution red. 
 
 An aqueous solution (1 : 100) with a 
 solution of NaHCO 3 = a white or 
 pale-greenish-white ppt., rapidly 
 becoming green and dissolves in 
 ether with a violet color, and in 
 chloroform with a violet-blue color. 
 
 With AgNO 3 T.S. it produces a white 
 ppt. insoluble in HNO 3 , the ppt. 
 turns black by reduction to Ag, and 
 is instantly reduced by NH 4 OH. 
 
 160. STEP II. Cover a few grains of the alkaloid with a drop 
 or two of cone. H 2 S04 on a white porcelain tile, and add a 
 small fragment of potassium dichromate. Observe effect. 
 
 Green 
 
 color slowly formed = Caffeine (not an 
 
 Deep Blue 
 
 quickly changing to violet, purple, 
 cherry-red and finally to orange = 
 Strychnine. 
 
 With H 2 SO 4 containing 1% of ammo- 
 nium vanadate = a violet-blue, grad- 
 ually changing to cherry-red. 
 
 With H 2 SO 4 containing a trace of 
 KIO 3 = a violet color, changing to 
 purple. 
 
 alkaloid). 
 
 If .01 Gm. of salt be dissolved in 1 mil 
 of HC1 and .1 Gm. KC1O 3 , and the 
 sol. evaporated to dryness, the resi- 
 due, subjected to the vapor of am- 
 monia, will acquire a rich purple 
 color destroyed by fixed alkalies. 
 
 An aqueous solution yields a ppt. with 
 tannic acid T.S., soluble in excess. 
 
 Odor of bitter almonds = Atropine. 
 
 Heated with a few cc. of H 2 SO 4 = a 
 peculiar odor, resembling a mix- 
 ture of rose, orange flower and 
 melilot. The addition of a crystal 
 of K 2 Cr 2 O? develops an odor of 
 bitter almonds. 
 
 With AuCl 3 a yellow lusterless ppt. 
 is produced in a dil. HC1 solution 
 of atropine. 
 
 Evaporate .01 Gm. to dryness with a 
 few drops of HNO 3 = a yellow-col- 
 ored residue. Cool, add a few drops 
 of alcoholic KOH and a fragment 
 of KOH = an intensely violet color. 
 
 Pale Yellowish Pink = Cocaine. 
 
 If 5 drops of CrO 3 sol. (1 : 20) be added 
 to 5 mils of cocaine sol. (1-50) =a 
 yellow ppt., dissolved on shaking. 
 On now adding 1 mil of HC1 an 
 orange-colored ppt. is produced. 
 
 Its solution in HC1 gives with K 2 CrO 4 
 sol. an orange ppt. 
 
 1 mil of cocaine sol. is treated with 
 2 mils of N/10 V.S. of KMnO 4 . A 
 violet ppt. is produced, which when 
 examined under a microscope, is 
 seen to consist of rectangular plates. 
 
 A solution added to 2% hexamethylen- 
 amin+H 2 SO 4 = wine color on warm- 
 ing. 
 
 If AgNO 3 T.S. is added to a 1% solu- 
 tion = a white ppt. insol.in HNO 3 . 
 
CALIFORNIA COLLE6F 
 
 of PHARMACY 
 
 QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 
 
 133 
 
 161. STEP III. To a fragment of the alkaloid on a porcelain 
 crucible cover add a few drops of cone. HC1 and warm. 
 
 A Rose-red color = Veratrine. 
 
 Confirmatory tests : 
 
 Heated with H 2 S0 4 = a cherry-red color. 
 
 H 2 S0 4 added to a mixture of 1 part of veratrine and 6 parts 
 of sugar produces a green color which changes to blue and finally 
 becomes colorless. 
 
 With HN0 3 = a dirty-red color. 
 
 With Frohde's reagent = a cherry-red. 
 
 (See also Physostigmine.) 
 
 162. STEP IV. Heat a little of the original in a dry test-tube. 
 Vapors are evolved, first yellow then red = cinchona alkaloids. 
 Take 1 mil of a solution of the alkaloid, dissolved in water 
 with the aid of the least quantity of dilute ^SO-i, add 2 or 3 
 drops of bromin-water, and a slight excess (1 mil) of ammonia- 
 water. An Emerald Green Color indicates Quinine or Quinidine ; 
 a white ppt. may indicate Cinchonine or Cinchonidin. Apply 
 the following tests : 
 
 REAGENT. 
 
 Quinine. 
 
 , Quinidine. 
 
 A 1% solution of the alka- 
 loid, made by using the 
 smallest possible quantity 
 of dil. H ? SO 4 and neu- 
 tralized with NH 4 OH, is 
 treated with one drop of 
 H 2 O 2 and one drop of 
 CuSO 4 sol. and boiled. 
 
 Intense red color 
 changing to blue 
 and green. 
 
 Intense red color 
 changing to blue 
 and green. 
 
 Dissolve a small quantity of 
 the alkaloid in a mixture 
 of acetic acid and alcohol 
 with a few drops of H 2 SO 4 , 
 boil, and add tr. iodin 
 slowly. 
 
 Bronze or olive-green 
 crystals separate on 
 cooling. 
 (Quinine-iodosul- 
 phate.) 
 
 No ppt. or crystals. 
 
 To a neutral aqueous solu- 
 tion add (NH 4 ) 2 C 2 O 4 or 
 KNaC 4 H 4 O, sol. 
 
 White ppt. 
 
 Precipitate only on 
 addition of KI and 
 shaking. 
 
 Frohde's Reagent. 
 
 Green color. 
 
 Green color. 
 
134 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 REAGENT. 
 
 Cinchonin. 
 
 Cinchonidin. 
 
 Make a nearly neutral solu- 
 tion of the alkaloid. Add 
 some .sat. sol. of 
 KNaC 4 H 4 O 6 . 
 
 No white ppt. unless 
 excess of NH 4 OH is 
 added. 
 
 A white ppt. 
 
 Make a solution of the 
 alkaloid in HC 2 H 3 O,. Add 
 some NH 4 OH, and then 
 an excess of ether. 
 
 The ppt. does not 
 dissolve in the ether. 
 
 The ppt. dissolves in 
 the ether. 
 
 163. STEP V. If the substance is not an alkaloid, place a 
 small portion of it on a porcelain crucible cover, add a drop or two 
 of Frohde's Reagent and observe the color changes. 
 
 Salicin. 
 
 Santonin. 
 
 Intense violet color changing to 
 reddish brown. 
 
 With H 2 SO 4 = a bright-red color which 
 disappears on the addition of water. 
 
 To .1 Gm. of the substance add 2 mils 
 of dilute sulfuric acid and .2 Gm. of 
 K 2 Cr 2 O 7 and boil = odor of sweet 
 clover (salicylic aldehyd). 
 
 On heating a portion of the sub- 
 stance in a test-tube until it turns 
 brown, then adding a few mils of 
 water and a drop of FeCla sol. =a 
 violet color. 
 
 Slate-blue color on warming. 
 
 Add a drop of FeCls to 1 mil of 
 
 H 2 SO 4 , warm, and add .01 Gm. of 
 
 the substance = a violet-red color 
 
 changing to brown. 
 On heating .5 Gm. of the substance 
 
 with 5 mils of alcoholic KOH sol. 
 
 = a red color. 
 The substance is soluble in NaOH, 
 
 reprecipitated by acids. 
 
 Elaterin. 
 
 Aloin. 
 
 Faint red changing to olive-green on 
 warming. 
 
 Add 5 mils of phenol, then a few drops 
 of H 2 SO 4 , to .01 Gm. of the sub- 
 stance and warm = a crimson chang- 
 ing to a scarlet color. 
 
 With H 2 SO 4 = a yellow color changing 
 to red. 
 
 .01 Gm. with 1 mil H 2 SO 4 +a drop of 
 formaldehyde = a brown color. 
 
 With H 2 SO 4 +a trace of ammonium 
 vanadate = a blue, changing to 
 green and brown. 
 
 Yellow color changing to green. 
 
 Ammonia- water and alkali sols, dis- 
 solve aloin forming a yellow sol. 
 quickly turning red and exhibiting 
 a green fluorescence. 
 
 With cone. H 2 SO 4 +a crystal of K 2 Cr 2 O 7 
 = an olive green, and finally, on 
 standing, a blue color. 
 
 With bromine-water = a pink color. 
 
 With AuCl 3 in an aqueous solution = 
 
 a carmine-red changing to violet. 
 With a drop of FeCls sol. its alcoholic 
 
 sol. gives a brownish-green color. 
 HNp 3 gives with barbaloin a crimson, 
 
 with nataloin a red, and with 
 
 soraloin a brown, ppt. 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 135 
 
 164. STEP VI. Heat some of the substance in a dry test-tube 
 and observe odor or other effect. 
 (a) Odor of Phenol indicates: 
 
 Phenol (see paragraph 139). 
 
 Phenolates (see paragraph 139). 
 
 Phenolsulfonates (see paragraph 138). 
 (6) Odor is Pungent; may be Chloral, Benzoic Acid, Ben- 
 
 zoates, or Butyl Chloral. 
 
 Cblor 1. 
 
 ' c'd 
 
 B n^ 
 
 Bityl Cbl^rel. 
 
 Heated with KOH or 
 NH<OH an odor of 
 ch.oioform is evolved 
 and a formate of the base 
 is produced. 
 
 Warmed with a few drops, 
 of aniline and some 
 KOH = a very disagree- 
 able odor of phenyl- 
 isocyanide. 
 
 Warmed with a few drop ; 
 of NH 4 OH and a little 
 AgNO 3 sol . = a silver mir- 
 ror. 
 
 Boiled with Fehling's sol. 
 = a red ppt. 
 
 Upon heating benzoic acid 
 with freshiy siaked lime 
 in a dry test-tube ben- 
 zene (benzol) is evolved. 
 
 A sol. of benzoic acid in 
 NaOH neutralized care- 
 fully gives with neutral 
 ferric chloride sol. a pale 
 buff or flesh-colored ppt. 
 
 See par. 135 for j tests for 
 benzoates. 
 
 Sparingly soluble in 
 water. Boil with 
 NaOH, neutralize 
 with dilute 
 HC 2 H 3 O 2 and add 
 AgNO 3 sol. = a 
 white ppt. 
 
 (c) Odor is Pungent; with lodin Fumes indicates lodoform, 
 lodol, or Aristol. 
 
 Iolcf}rm. 
 
 lodol. 
 
 Aristol. 
 
 A yellow insol. powder. 
 When boiled with 
 NaOH and the so', 
 neutralized with 
 HNO 3 = a ye! ow ppt. 
 on adding AgNO, sol., 
 and a blue rolor on 
 adding starch sol. 
 
 A grayish-brown pow- 
 der very sparingly 
 soluble in water. 
 When dissolved in cone. 
 H 2 SO 4 a green sol. 
 results gradually 
 changing to brown. 
 
 A bright chocolntc-colored 
 powder, with an aro- 
 matic odor. 
 It is not sol. in alkaline 
 hydroxid solutions. 
 Heated with cone. H 2 SOL 
 it decomposes, ana 
 iodine separates. 
 
136 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 (d) Odor is Camphoraceous; may be Camphor, Thymol, or 
 Menthol. 
 
 Camphor. 
 
 Thymol. 
 
 Menthol. 
 
 Soluble in the volatile 
 
 An aromatic thyme- 
 
 Soluble in alcohol, chlo- 
 
 solvents, and in fixed 
 
 like odor. 
 
 roform and ether. It 
 
 oils. 
 
 .Soluble in ether, chlo- 
 
 has a peppermint-like 
 
 Its alcoholic solution 
 
 roform, alcohol, and 
 
 odor. 
 
 poured into cold water 
 
 oils, also in glacial 
 
 It is soluble in glacial 
 
 = a curdy white ppt. 
 
 acetic acid. 
 
 acetic acid, but does 
 
 When triturated with 
 
 Its sol. in the latter 
 
 not respond to the test 
 
 hydrated chloral lique- 
 faction ensues. 
 
 when treated with 
 6 drops of H 2 SO 4 and 
 
 for thymol. 
 Heated with diluted sul- 
 
 It is inflammable and 
 
 a drop of HNO 3 exhib- 
 
 furic acid 1 : 2 = a deep- 
 
 burns with a lumi- 
 
 its a bluish-green color 
 
 blue color. 
 
 nous smoky flame. 
 
 by reflected light. 
 
 
 
 If 1 Gm. is heated with 
 
 
 
 5 mils of a 10% solution 
 
 
 
 of NaOH in a test-tube 
 
 
 
 a pale-red sol. is 
 
 
 
 formed which becomes 
 
 
 
 darker on standing 
 
 
 
 without the separation 
 
 
 
 of oily drops. A few 
 
 
 
 drops of chloroform 
 
 
 
 added gives a violet 
 
 
 
 color. 
 
 
 (e) Odor is Acrylic (Fatty Acid); indicates Soap, Oleates, 
 
 or Stearales. 
 
 Soap. Dissolve in water, add HC1 and shake, add 
 some ether and again shake; then let the mixture 
 stand so that the ethereal layer can separate; remove 
 the upper layer and evaporate: the residue if liquid 
 is oleic, and if solid, stearic acid. The HC1 sol. is 
 evaporated to dry ness and tested for K and for Na. 
 Oleates and Stearates of the heavy metals are treated 
 in the same way. The acid sol. residue being tested 
 for the metals commonly combined with these fatty 
 acids, i.e., Zn, Pb, Hg, etc. 
 
 (/) Odor resembling Burnt Bones ; may indicate Oxgall. 
 To a warm solution of oxgall, 2 drops in 10 mils of H 2 
 add ft crystal of sugar; shake, and add H 2 S0 4 cau- 
 tiouslv until the ppt.' first formed is redissolved; a 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 137 
 
 brownish-red color gradually develops, changing to 
 carmine, purple, and violet. 
 
 (g) Odor of Burning Sugar; may be Sugars, Dextrin, 
 Starches, Gums, Tartaric Acid or Tartrates. Apply 
 special tests. For tartirates, see paragraph 146. For 
 the sugars, see the Table below. 
 
 Cane-sugar. 
 
 Milk-sugar. 
 
 Strong H 2 SO 4 chars it immediately. 
 
 Does not reduce Fehling's sol. 
 
 Mixed dry with KC1O 3 crystals and a 
 drop of cone. H 2 SO 4 added, it defla- 
 grates. 
 
 It does not ferment with yeast until 
 left in contact for some time. 
 
 Boiled with NaOH = no effect. 
 
 It does not form a compound with 
 phenylhydrazine. 
 
 Strong H 2 SO 4 chars it slowly. 
 
 It reduces Fehling's sol. 
 
 It does not ferment with yeast. 
 
 It combines with phenylhydrazine to 
 
 form phenyl-lactosazcne in acetic 
 
 acid solutions. 
 Boiled with NaOH solution becomes 
 
 yellow, then brown. 
 
 Gr p -sug r. 
 
 D x.rln. 
 
 Strong H 2 SO 4 does not char it until 
 heated. 
 
 It readily reduces Fehling's sol. It 
 also reduces alkaline solutions of 
 Bi, Ag, and Hg. 
 
 In a solution acidified by HC 2 H 3 O 2 
 it forms, with excess of phenyl- 
 hydrazine, a yellow ppt. of phenyl- 
 dextrosazone. 
 
 It ferments readily upon adding 
 yeast to its solution. 
 
 Boiled with NaOH = a deep-brown 
 color. 
 
 Strong H,SO 4 = no effect. 
 
 In aqueo is sol. reduces Fehling's sol. 
 
 only after long boiling. 
 Boiled with NaOH = no effect. 
 
 Starches. Insoluble in cold water, but on boiling it 
 
 forms a mucilage, which gives a blue color with iodin. 
 Boiled with dilute sulfuric acid, it is converted into 
 
 dextrose, and then reduces Fehling's sol. 
 Gums. Soluble in cold water, from which sol. it is 
 
 precipitated by alcohol, borax or lead-acetate solution. 
 Gum arabic is an arabate of calcium. Ignite some of 
 
 it, dissolve the ash in dilute acetic acid and test for 
 
 Ca, with (NH 4 ) 2 C 2 04. 
 
138 QUALITATIVE CHEMICAL ANALYSIS. 
 
 (h) If detonation occurs, it indicates Picric Acid. Dissolve a 
 little of the substance in NaOH sol., add a little sugar, 
 and warm the mixture = a blood-red color. 
 
 To an aqueous solution add a solution of gelatin = a 
 white ppt. 
 
 Its aqueous solution precipitates albumin, and gives a 
 
 green ppt. with ammonio- copper sulfate. 
 (i) If it burns with a smoky flame, it may be resin. 
 
 Resin. Insoluble colored substance. A small piece of 
 it treated with strong H 2 S0 4 gives a red coloration; 
 add a drop of H 2 to this = balsamic, turpentiny odor. 
 
 Guaiacum Resin. Insoluble colored substance. Dis- 
 solved in alcohol and treated with FeCl 3 gives a 
 blue coloration. A small piece of it treated with 
 strong H 2 S0 4 for a few seconds, then water added, 
 gives a characteristic balsamic odor. 
 
 0) If at first it melts and then upon highly heating burns 
 away entirely, it may be acetanilide, antipyrine, phen- 
 acetin, saccharin, naphthalene, or urethane. 
 
 Acetanilide; .1 Gm. of acetanilide heated with 5 mils of 
 concentrated solution of KOH, and 1 mil of chloroform 
 added = a disagreeable odor of phenyl isocyanide 
 (distinction from antipyrine and exalgine). 
 
 0.1 Gm. boiled with 2 mils HC1 and 3 mils of phenol solu- 
 tion (1 : 20) and then mixed with 5 mils of a clear solu- 
 tion of chlorinated lime = a brownish-red color, becom- 
 ing blue upon supersaturating with NH 4 OH. 
 
 1 Gm. heated with 10 mils of water, the solution cooled 
 and filtered and treated with bromin-water drop by 
 drop gives a whitish ppt. of parabromoacetanilide. 
 
 Antipyrine, Phenazonum, Phenyldimethylisopyrazolon. 
 If .1 Gm. of NaN0 2 and 12 mils of 1% solution of anti- 
 pyrine be mixed and 1 mil of dil. H 2 S0 4 added, a 
 deep-green color (iso-nitrosoantipyrine) develops. 
 
 2 mils of a solution of antipyrine (1 : 1000) treated with 1 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 139 
 
 drop of FeCl 3 solution = a deep-red color, which is 
 turned yellow by H 2 S0 4 . 
 
 Tannic acid solution gives a white ppt. HN0 3 produces 
 a red coloration. 
 
 Phenacetin, Acetphenetidin. A mixture of .005 Gm. with 
 1 mil of HNOs produces a yellow color which persists 
 on heating and becomes darker on standing. 
 
 Boil .1 Gm. with 1 mil of concentrated HC1 for 1 minute, 
 the solution diluted with 10 mils of water, cooled and 
 filtered, and then 1 drop of K 2 Cr 2 7 T.S. added, a 
 ruby-red color is produced. FeCl 3 solution produces a 
 yellow solution, which becomes blood-red on boiling. 
 
 Boil .1 Gm. with 10 mils of water, cool, filter, and add 
 bromin water, drop by drop, until solution remains 
 permanently yellow, no ppt. is produced. 
 
 A mixture of .3 Gms. with 1 mil of alcohol and 1 drop of 
 
 N 
 
 JQ I. V. S. does not acquire a red tint when diluted 
 
 with 3 times its volume of H 2 and boiled. 
 
 Saccharin Glusidum, Benzosulfinid. It has an intensely 
 sweet taste. It is soluble in alkali solutions and in 
 NaHC0 3 solution with evolution of C0 2 . If subjected 
 to a high temperature, it melts and finally burns, 
 giving off an odor of essential oil of bitter almonds. 
 
 Heated to redness with Na 2 C0 3 , it chars and gives off an 
 odor of benzene. 
 
 Its solution in NaHC0 3 , neutralized with HC1, gives with 
 FeCl 3 a reddish-brown color. 
 
 Fuse with 5 times its weight of NaOH = NH 3 is evolved. 
 Continue to heat, dilute with 10 mils of H 2 0, neutralize 
 with dilute HC1, add 1 drop of FeCl 3 T.S. = violet color. 
 
 Naphthalene. It melts and volatilizes; its vapor is 
 inflammable, burning with a luminous smoky flame. 
 
 It may be recognized by its characteristic odor, resem- 
 bling that of coal-tar. 
 
 CALIFORNIA COLLEGF 
 
 of PHARMACY 
 
140 QUALITATIVE CHEMICAL ANALYSIS. 
 
 It is insoluble in H 2 but soluble in the volatile solvents. 
 Urethane, Ethyl Carbamate. When heated it melts, 
 
 when highly heated it is decomposed, burning without 
 
 leaving a residue. 
 1 Gm. added to 5 mils of H^SC^ and gently heated is 
 
 decomposed, with evolution of CCb, while alcohol and 
 
 NH 4 HS04 remain in solution. 
 When 1 Gm is heated with 5 mils of concentrated solution 
 
 of KOH, ammonia is given off . 
 If .5 Gm. be dissolved in 5 mils of water, together with 1 
 
 mil of Na2COs and about .01 Gm. of iodin and warmed, 
 
 yellow crystals of iodoform are produced. 
 (&) If at first it melts and at red heat is decomposed without 
 
 burning it may be (1), if without odor, Chloralforma- 
 
 mide; (2) if with odor of SCb, Sulfonal or TrionaL 
 Chloralformamide, Chloralamide. It is soluble in water. 
 It is not affected by dilute acids. 
 Its solution is decomposed when warmed with KOH; it 
 
 becomes turbid, then clear, and gives off chloroform. 
 Sulfonal, Sulfomethane, Diethylsulfondimethylmethane. 
 
 Slightly soluble in cold, readily in hot water. When 
 
 heated it melts. At a red heat it is consumed and 
 
 S02 is evolved. 
 When .1 Gm. is heated with an equal weight of powdered 
 
 charcoal, in a dry test-tube, the disagreeable odor of 
 
 mercaptan is developed. 
 When heated with dry NaC 2 H 3 02, gaseous H 2 S is 
 
 evolved. 
 Trional, Sulfonethylmethane. The tests for trional are 
 
 the same as those described for sulfonal. 
 It differs in solubility, being soluble in 195 parts of water 
 
 at 77 F. while sulfonal requires 360 parts of water. 
 
 It is also more soluble in ether and in alcohol than 
 
 sulfonal. Trional has a bitter taste; sulfonal is 
 
 tasteless. 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 141 
 
 (0 If at first it melts and finally upon increasing the heat 
 volatilizes or sublimes, it may be Resorcinol, Cam- 
 phor Monobromated, Guaiacol Carbonate; and if it 
 has a phenol-like odor, Betanaphthol, or if an aro- 
 matic odor, Salol, Guaiacol, or Terpin Hydrate. 
 
 Resorcinol, Resorcin. It is very soluble in water, alcohol, 
 ether and glycerin, slightly soluble in chloroform and in 
 CS 2 . 
 
 10 mils of an aqueous solution (1 : 200) treated with a 
 few drops of Feds solution = a bluish color, changing 
 to brownish- yellow on adding NH 4 OH. 
 
 .1 Gm. heated with 1 mil of KOH solution and a drop of 
 chloroform gives a bright red color (due to formation 
 of rosolic acid). The addition to this of a slight 
 excess of HC1 changes the color to pale yellow. 
 
 On heating a fragment with a grain of tartaric acid, 
 and 10 drops of H 2 S0 4 , a thick, red liquid results, which 
 becomes pale yellow when diluted with water. 
 
 Camphor Monobromated. Almost insoluble in water, 
 freely soluble in volatile solvents and in cold concen- 
 trated H 2 S0 4 . 
 
 When heated it melts and sublimes. 
 
 Heat .1 Gm. each of camphor monobromate and AgN0 3 
 with 2 mils of HN0 3 and 2 mils of H 2 S0 4 until nitrous 
 vapors are no longer given off=a yellow ppt. of silver 
 bromide. 
 
 If a few crystals are fused in a dry test-tube with metallic 
 Na, the residue dissolved in water and acidulated 
 with HNOs gives with AgN0 3 solution a copious white 
 ppt. 
 
 It has a camphoraceous odor and taste. 
 
 Guaiacol Carbonate. A white, odorless, tasteless powder, 
 insoluble in water, very soluble in chloroform, less 
 soluble in alcohol, and in ether. It fuses at 87 C. 
 
 It is decomposed when treated with an alcoholic KOH 
 
142 QUALITATIVE CHEMICAL ANALYSIS. 
 
 solution, and from the solution so obtained guaiacol 
 may be separated on the addition of an acid, and iden- 
 tified by appropriate tests. 
 
 Betanaphthol, Naphthol U. S. P. 1890. A crystalline or 
 pale buff-colored or colorless powder, having a faint 
 phenoUike odor. Very sparingly soluble in water, very 
 soluble in volatile solvents and in alkali-hydroxid solu- 
 tions. A cold saturated solution mixed with NIUOH = 
 a faint bluish fluorescence. 
 
 .1 Gm. of betanaphthol in 5 mils of KOH solution (1 : 4) 
 treated with 1 mil of chloroform and heated, gives a 
 blue color changing to green and then to brown. An 
 aqueous solution treated with FeCl 3 gives a greenish 
 color, and after some time white flakes separate which 
 turn brown when heated. 
 
 Salol, Phenyl Salicylate. A white, crystalline powder, 
 having a faint aromatic odor. Insoluble in water, 
 very soluble in the volatile solvents. 
 
 With Fed- a violet color is produced. 
 
 If .2 or .3 Gm. of salol be dissolved in 2 mils of warm NaOH 
 solution and the resulting solution acidified with HC1, a 
 ppt. of salicylic acid forms, and the odor of phenol is 
 recognizable. 
 
 Guaiacol. A colorless crystalline solid or a colorless 
 refractive liquid having an agreeable aromatic odor. 
 Soluble in 53 parts of water, and in alcohol and ether in 
 all proportions, and in acetic acid. 
 
 The addition of FeCl 3 to 10 mils of an alcoholic solution 
 of guaiacol (1 : 100) = an immediate blue color changing 
 to emerald green and then to yellow or brown. 
 
 Terpin Hydrate. (a) It melts when quickly heated, and 
 sublimes in fine needles. When strongly heated on 
 platinum it burns with a bright smoky flame leaving 
 no residue. 
 
 (&) If to its hot aqueous solution a few drops of H 2 S04 be 
 

 QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 143 
 
 added, the liquid will become turbid and develop a 
 strongly aromatic odor. 
 
 165. STEP VII. If the substance is a liquid, possessing a 
 characteristic odor, limpidity or viscosity, place about 1 mil in a 
 test-tube and apply gentle heat (water-bath). If it is com- 
 pletely volatilized, look for it under A. If it is not completely 
 volatilized by gentle heat look for it under B. 
 
 1 66. STEP VIII. If the substance comes into Class A, place 
 1 mil of it into a test-tube and add 10 mils of water, and note 
 if it is miscible or not. 
 
 (a) If it is miscible, it may be Acetaldehyd, Acetic Ether, 
 Ether, Paraldehyd, Formaldehyd, Ethyl Akohol, Methyl 
 Akohol. 
 
 (6) If it is not miscible or soluble in 10 parts of water 
 or more, it may be Chloroform, Benzin, Benzene, 
 Cinnaldehyd, Amyl Alcohol, Amyl Nitrite, Benzaldehyd. 
 
 167. CLASS A. DIVISION a. LIQUIDS MISCIBLE WITH WATER. 
 
 Ethyl Alcohol, Grain Alcohol. A colorless, mobile, volatile and 
 inflammable liquid. Miscible with water in all proportions. 
 
 The Oxidation Test. To the alcohol add some K 2 Cr 2 7 and 
 a small quantity of H 2 S0 4 , and heat = a greenish color and 
 an odor of aldehyd. 
 
 3C 2 H 5 OH + K 2 Cr 2 7 + 4H 2 S0 4 
 
 = K 2 S0 4 + Cr 2 (S0 4 ) 3 + 3C 2 H 3 OH + 7H 2 0. 
 
 Aldehyde. 
 
 The Acetic Ether Test. To a small portion of the alcohol add 
 some KC 2 H 3 2 and a little H 2 S0 4 and warm the mixture = 
 an odor of apples due to formation of acetic ether. 
 
 KC 2 H 3 2 + C 2 H 5 OH + H 2 S0 4 - KHS0 4 + C 2 H 5 C 2 H 3 2 + H 2 
 
 Acetic Ether. 
 
144 QUALITATIVE CHEMICAL ANALYSIS. 
 
 The lodoform Test (Leiben). Warm a small quantity of the 
 alcohol with KOH and add some solution of iodin = a 
 yellow ppt. of iodoform, forming slowly. Detects 1:2000. 
 
 C 2 H 5 OH + 1 8 + 6KOH = CHI 3 + KCOOH + SKI + 5H 2 
 
 lodoform. Potass formate. 
 
 The Molybdic Test. A 10% solution of molybdic acid in strong 
 H 2 S0 4 warmed with the alcoholic liquid = a blue color. 
 Detects 1 : 1000. 
 
 Methyl Alcohol, Carbinol, Wood Alcohol. A colorless volatile,* 
 inflammable liquid having a characteristic odor, and mis- 
 cible with water in all proportions. It forms with dry 
 CaCU a crystalline compound. 
 
 The Salicylate Test. To a concentrated solution of sodium 
 salicylate add some methyl alcohol and a few drops of 
 H 2 S0 4 , and warm the mixture = an odor of oil of winter- 
 green (methyl salicylate) develops: 
 
 HC 7 H 5 3 + CH 3 OH = CH 3 C 7 H 5 03 + H 2 0. 
 
 Methyl Salicylate. 
 
 Methods for the Detection of Methyl Alcohol in Grain Alcohol, 
 Pharmaceutical Preparations, Beverages, etc. 
 
 The Resorcinol Test. A spiral of copper wire is heated to 
 redness and plunged into the liquid (which should not be 
 stronger than 10%). One drop of a 0.5% aqueous resorcinol 
 solution is added and the mixture floated on concentrated 
 H^SO* A rose-red zone at line of contact = methyl alcohol; 
 above the zone a scanty white or pinkish-white coagulum 
 appears which finally separates and rises in purplish flakes. 
 
 Similar reactions are given with tertiary-butyl alcohols, dimethyl- 
 ethylcarbinol and formic acid, but the succession of colors and 
 the deportment of the flaky coloring matter are different. If 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 145 
 
 the methyl-alcohol solution is very dilute, repeat the immer- 
 sion of the copper-wire coil several times. If the solution is 
 concentrated, it should be diluted so as to be about 10% by 
 volume. (Mulliken and Scudder, Am. Ch. J., Vol. XXL, 226.) 
 
 The Phloroglucin Test. The oxidation of methyl alcohol is 
 the same as in the foregoing; acetaldehyd is removed by 
 adding to the liquid remaining in the test-tube 6 mils of a 
 3% H202 solution and filtering into a porcelain dish. After 
 3 minutes add 2 mils of a 10% solution of Na 2 S 2 03, and then 
 3 mils of a phloroglucin solution made by dissolving 1 Gm. 
 of phloroglucin and 20 Gms. of NaOH in water to make 100 
 mils = a bright red color develops if methyl alcohol is present, 
 the intensity of the color being in some degree proportionate 
 to the quantity of methyl alcohol present. Authority same 
 as preceding test. 
 
 Prescott's Modification of the Foregoing Tests (see A. J. of Ph., 
 Vol. 77, 108, Sadtler). The spirit tested should be diluted 
 to about 10%. The copper wire is plunged into the liquid, 
 held there for a second or two, then withdrawn and dipped 
 into water to cool. This is repeated 5 or 6 times, the test- 
 tube being immersed in cold water to keep contents cool. 
 The liquid is then filtered into a wide test-tube and gently 
 boiled to drive off acetaldehyd. The boiling should be 
 continued until no odor of acetaldehyd is perceptible. 
 Then the liquid is poured into a white porcelain dish and 
 1 mil of the phloroglucin-alkali solution described in previous 
 test added. A deep-red persisting color = methyl alcohol 
 (formaldehyd reaction); a pale or slightly yellowish-red 
 fading rapidly is due to acetaldehyd and indicates only 
 ethyl alcohol. 
 
 The Rimini Test, Modified (Haigh, Ph. Rev., Oct., 1903). 
 The oxidation of the methyl alcohol and the removal of 
 acetaldehyd by boiling is effected as in foregoing tests. 
 
146 QUALITATIVE CHEMICAL ANALYSIS. 
 
 Then 1 mil of a dilute solution of phenylhydrazine hydrochlo- 
 rid is added, followed by a few drops of a fresh solution of 
 sodium nitroprusside and finally by 1 mil of 50% solution of 
 NaOH; if formaldehyd is present a light-blue or green color 
 results, depending upon the amount of CH 3 OH present. If 
 the latter is absent, the color is greenish yellow. 
 
 The U. S. P. Test (9th Decennial Revision). Transfer 5 mils of 
 the dilute alcohol (10%) to a test-tube. Add to it 2 mils of 
 a KMn0 4 solution (3 Gms. of KMn0 4 in 100 mils of distilled 
 water) and .3 mil of H 2 S0 4 and allow to stand for five 
 minutes. Dissolve the ppt. of Mn0 2 by H 2 SOs, drop by 
 drop, then add 1 mil H 2 S0 4 and 5 mils fuchsin-sulfurous 
 acid T.S., and mix them. After standing for 10 minutes, a 
 colorless liquid results. Indicates absence of methyl alcohol. 
 If methyl alcohol is present, the color of the fuchsin is 
 restored and the solution becomes pink or red. 
 
 Miller's Test. (Oxidation with Dichromate) P. J. Tr., 2d Ser. 
 VII, 318. Take J ounce of the spirit, distil off about 1 dram. 
 Then place in a small distilling-flask 30 grains of K 2 Cr 2 07, 
 4 fl. drams of water, and 30 minims of concentrated H 2 S0 4 . 
 To this add 30 to 40 minims of the above distillate and 
 let stand 15 minutes. Then distil off about J of the quan- 
 tity, and to the distillate add Na 2 C0 3 in slight excess, and 
 boil down to 2 fl. drams. Then acidulate feebly with 
 HC 2 H 3 2 and add 1 grain of AgN0 3 in 30 minims of water and 
 heat gently. If the liquid merely darkens, but remains trans- 
 lucent, CH 3 OH is absent, but if a copious ppt. of metallic 
 silver falls and a thin film of silver lines the tube, methyl 
 alcohol (CH 3 OH) is present. 
 
 NOTE. This test depends upon oxidizing CH 3 OH to 
 formic acid (HCOOH), which reduces silver. 
 
 CH 3 OH + 2 = HCOOH + H 2 0. 
 
 The ethyl alcohol present is oxidized to acetic acid, which 
 does not reduce silver. Aldehyd, which is produced at 
 the same time and which does reduce silver, is removed by 
 boiling with Na 2 COs. 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 147 
 
 Sieker's Method (Am. Dr., Mch. 25, '01, and Ph. Rev., '01, 117). 
 This method is based upon the oxidation to formalde- 
 hyd by a heated copper-wire spiral, and has the advantage 
 of rapidity. Pour 4 to 8 rails of the spirit into a test- 
 tube and warm gently; immediately insert into the tube 
 (not into the liquid) a copper-wire spiral which has been 
 previously heated to dull redness; withdraw and reinsert 
 the spiral several times, and it will be observed that a 
 strong odor of formaldehyd is evolved, while the spiral 
 will change in color from black CuO to red Cu upon in- 
 serting it, and will resume its black color each time it is 
 withdrawn into the air. 
 
 NOTE. Heating the copper wire oxidizes it to CuO. 
 The warm methyl-alcohol vapor reduces the CuO to Cu 
 and is itself oxidized to formaldehyd. 
 
 CH 3 OH + CuO = HCOH + H 2 + Cu. 
 
 Ethyl alcohol reduces CuO in the same manner, but the 
 odor of formaldehyd and of formic acid distinguishes the 
 methyl alcohol. 
 
 Acetaldehyd. Colorless, limpid, inflammable, possessing a 
 fruity odor. Boiling-point 20.8 C. Miscible with water, 
 alcohol, ether, and benzin. 
 
 (1) With solution of Ag 2 in ammonia, gives a bright 
 mirror of silver on warming. KOH facilitates the reaction. 
 
 (2) It reduces Fehling's solution on being boiled, deposit- 
 ing a red ppt. of Cu 2 0, and being thus converted into acetic 
 acid: 
 
 (3) Heated with KOH it acquires a brown color. 
 
 (4) Rosaniline solution bleached by S0 2 , gives a pinkish- 
 violet color with aldehyd. 
 
148 QUALITATIVE CHEMICAL ANALYSIS. 
 
 Paraldehyd. A limpid liquid, colorless, possessing an odor 
 resembling that of aldehyd. Soluble in 8 parts of water. 
 Boils at 124 C., evolving inflammable vapors. Distilled with 
 dilute H 2 S0 4 it is again converted into aldehyd, of which 
 paraldehyd is a polymer; its formula is CcH^Os (which is 
 the formula of aldehyd (C 2 H 4 0) taken three times.) 
 
 (1) 5 mils boiled with 5 mils of KOH gives no brown 
 color (distinction from aldehyd). 
 
 (2) Heated with Ammonio-Argentic-Nitrate, it pro- 
 duces a mirror of metallic silver. 
 
 Formaldehyd, Formalin, Formic Aldehyd (CHOH). Miscible 
 with water and alcohol, possessing a pungent odor of ham- 
 amelis extract; highly antiseptic liquid. 
 
 (1) Hehner's Test. Mix 2 mils of highly diluted solution 
 of Formaldehyd, with 2 mils of milk, and underlay with 2 
 mils of H2S04 containing a trace of Feds (Tinct. Ferri chlor. 
 1 part and C. P. H 2 S0 4 25 parts) (Lyons) as carefully as 
 possible = violet-blue zone. Reaction very delicate. 
 
 (2) With the Morphine-sulfuric Reagent (Morphine 0.12 
 gm. in strong C. P., H 2 S0 4 3mils). Underlay the distillate 
 (highly diluted), or a solution of CHOH very dilute with 2 
 mils of the reagent; a purple-red color changing to violet will 
 form. (By mixing 3 drops of 40% Formaldehyd with 3 mils 
 of pure strong H 2 S0 4 , a reagent is obtained which gives a 
 similar reaction with Morphine (very reliable) .) 
 
 Five mils diluted with 25 mils of water and heated with 
 3 mils of ammonio-argentic-nitrate solution = a gray ppt. of 
 metallic silver and a deposit of silver in form of a mirror on 
 sides of test-tube. 
 
 To a little H 2 S0 4 in which some salicylic acid has been 
 dissolved, the addition of two drops of formaldehyd solu- 
 tion will produce a permanent deep-red color on warming. 
 Ether, Ethyl Oxid. A colorless, mobile, highly inflammable 
 liquid of characteristic odor, boiling at 35.5 C., miscible 
 with 10 times its volume of water, and very readily miscible 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 149 
 
 with alcohol, chloroform, benzin, benzene, and oils. It 
 dissolves fats and resins. 
 
 Acetic Ether, Ethyl Acetate A. colorless, limpid, inflammable 
 liquid, possessing a fragrant acetous odor resembling that 
 of apples. It boils at 72 C., and is miscible in all propor- 
 tions with alcohol and with 7 parts of water. 
 
 Boiled with KOH solution the residue gives reactions of 
 acetates. Distilled with KOH solution alcohol is produced, 
 and distils over, and the distillate gives the reactions for 
 ethyl alcohol: 
 
 C 2 H 5 C2H 3 02 + KOH = KC 2 H 3 2 + C 2 H 5 OH. 
 
 168. CLASS A. DIVISION b. LIQUIDS NOT MISCIBLE WITH 
 
 WATER. 
 
 Chloroform, Trichlor Methane, CHC1 3 . A heavy, clear, colorless, 
 mobile liquid of a characteristic odor. It is very volatile, 
 not inflammable, and not miscible with water. 
 
 (1) To a small quantity of chloroform in a test-tube 
 add some alcoholic solution of NaOH, and a drop or two of 
 aniline, and warm gently. There will be developed a very 
 offensive odor of phenylisocyanid. 
 
 (2) Boil a few drops of chloroform with KOH solution and 
 add a fragment of resorcinol. An intense red color appears 
 (rosolic acid). 
 
 (3) A few drops of chloroform, heated with a solution of 
 betanaphthol in strong KOH solution develops a fine blue 
 color, changing to green and brown. 
 
 Benzin, Petroleum Ether. A clear, colorless liquid, of a strong 
 characteristic odor, resembling that of kerosene. It is very 
 inflammable, and is not miscible with water. It boils at 
 45 to 60 C. 
 
 Benzene = Benzol = Coal-tar Benzene. A limpid liquid possessing 
 an aromatic benzin-like odor. Should not be confounded 
 with petroleum benzin. 
 
150 QUALITATIVE CHEMICAL ANALYSIS. 
 
 Boiling-point 80 C. Miscible with alcohol, ether and 
 chloroform, insoluble in water. Chemical formula CeHe. 
 
 (1) Mixed with strong HN0 3 (avoiding overheating) 
 nitrobenzene (oil of mirbane), C 6 H 5 N0 2 , is formed, which, 
 poured into cold water, separates in oil drops possessing 
 the characteristic odor of essential oil of bitter almonds. 
 
 (2) Mixed with strong H 2 S0 4 and boiled with KOH, 
 a phenolsulfonate is obtained which should be tested for. 
 (Paragraph 138.) 
 
 Amylic Alcohol (Fusel Oil). A limpid oily liquid possessing 
 the odor of whiskey; miscible with alcohol, but very spar- 
 ingly with water. Boils at 127 C. 
 
 (1) Warmed with dilute H 2 S0 4 and NaC 2 H 3 2 , it 
 forms amyl acetate ^Hi^HsC^) possessing the odor of 
 pears, and known as " pear oil." 
 
 (2) Distilled with H 2 S0 4 and K 2 Cr 2 7 and the distillate 
 boiled with KOH, it forms potassium valerate. Apply 
 the tests for valerates. (Paragraph 153.) 
 
 Amyl Nitrite, CsHnNC^. A clear yellowish liquid of an ethereal 
 banana-like odor. 
 
 Insoluble in water. Freely miscible with alcohol or ether, 
 very volatile even at low temperature and very inflammable, 
 burning with a smoky flame. 
 
 Add 2 mils H 2 S0 4 to a mixture of 2 drops of amyl nitrite 
 and 2 drops of H 2 0. Amyl valerate is formed, and is rec- 
 ognized by its odor, on diluting with H 2 0. 
 
 When mixed with potassium iodid and a drop or two of 
 sulfuric acid, iodin is liberated, and colors starch paste blue. 
 
 A few drops of amyl nitrite added to a mixture of 
 1 mil FeS0 4 T.S. and 5 mils of dil. HC1 = a greenish-brown 
 color. 
 
 Benzaldehyd, Benzoic Aldehyd. A colorless, strongly refrac- 
 tive liquid having an odor like that of essential oil of bitter 
 almonds. Insoluble in water. It is converted into ben- 
 zoic acid by oxidation. 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 151 
 
 169. CLASS B. 
 
 Phenol, Carbolic Acid Phenic Acid. The liquefied carbolic 
 acid is a colorless liquid having a peculiar characteristic 
 aromatic odor, miscible with water, and readily sol. in 
 alcohol, ether, chloroform and the alkalies. It cauterizes 
 and whitens the skin when concentrated. 
 
 Creosote, an almost colorless or yellowish (pinkish or 
 
 PHENOL. 
 
 The Bromin Test. Its aqueous sol. 
 yields with bromin-water a white 
 ppt. of tribromphenol, which at first 
 redissolves, but on adding more of 
 the reagent becomes permanent. 
 
 The Ferric Chlorid Test. 10 mils of 
 an aqueous solution of phenol 
 (1 : 100) + 1 drop of FeCls solution. 
 The solution becomes violet-blue, 
 and the color is permanent. 
 
 The Collodion Test. Equal volumes of 
 phenol and collodion, stirred to- 
 gether in a dry test-tube, will form 
 a permanent coagulum. This also 
 occurs with albumen. 
 
 The Glycerin Test. 1 volume of cold 
 liquefied phenol forms with 1 vol- 
 ume of glycerin a clear liquid, which 
 is not rendered turbid on the addi- 
 tion of 3 volumes of water. 
 
 The KOH Test. Does not correspond 
 to KOH test under Creosote. 
 
 Solidification Test. Phenol solution 
 solidifies when cooled. 
 
 4 parts of phenol solution mixed with 
 1 part of NH 4 OH and a few drops 
 of NaCIO added and gently warmed 
 = a blue to green color. 
 
 Add H 2 SO 4 to some benzaldehyd until 
 the latter darkens, then add some 
 phenol, and a red color is produced; 
 now add some KOH =a violet color. 
 
 CREOSOTE. 
 
 The Bromin Test. Its aqueous solu- 
 tion yields with bromin-water a 
 reddish-brown ppt. 
 
 The Ferric Chlorid Test.W mils of 
 an aqueous solution of creosote 
 + 1 drop of FeCl 3 T.S.: the liquid 
 develops a violet-blue tint, which is 
 transient, changing rapidly to green- 
 ish and brown, and forming a 
 brown ppt. 
 
 The Collodion Test. No permanent 
 
 coagulum results, if equal parts of 
 
 creosote and collodion are mixed. 
 
 The Glycerin Test. 1 volume of creo- 
 sote forms with 1 volume of glycerin 
 a clear liquid, from which J volume 
 of water will cause separation of a 
 creosotic layer equal to more than 
 1 volume and render the liquid 
 turbid. 
 
 The KOH Test. I mil of creosote 
 mixed with 10 mils of KOH in abso- 
 lute alcohol (1 :5)=a solid crys- 
 talline mass. 
 
 Solidification Test. Creosote cooled 
 to 4 F. does not solidify, but it 
 gelatinizes. 
 
152 QUALITATIVE CHEMICAL ANALYSIS. 
 
 brown if impure), highly refractive, oily liquid having a 
 penetrating, smoky odor; soluble in HC 2 H30 2 . 
 Glycerin. Glycerol Propenylakohol. A clear, colorless, thick, 
 syrupy liquid, smooth to the touch, sweet to the taste, 
 odorless, producing a sensation of warmth hi the mouth. 
 It absorbs moisture; soluble in all proportions in water and 
 alcohol, but not soluble hi ether, chloroform, carbon disulfid, 
 benzin or oils. 
 
 (1) The Borax-bead Test. Add a few drops of glycerin 
 to a little powdered borax; mix and dip the looped end of a 
 platinum wire into the mixture, and hold hi a Bunsen flame = 
 a transient green color. 
 
 (2) The Acrokin Test. Heated alone or with .5 Gm. of 
 potassium bisulfate to a high temperature an irritating odor 
 of acrolein is produced. 
 
 (3) The Borax Test. A piece of blue litmus paper is 
 shaken in a test-tube with a solution of borax, and a few 
 drops of glycerin added. The litmus paper immediately 
 becomes red. This is due to the liberation of boric acid by 
 the glycerin. The addition of a little bicarbonate of soda 
 to this mixture will cause effervescence. 
 
 (4) The Permanganate Oxidation Test. Glycerin in a 
 strongly alkaline solution is oxidized by KMn(>4 and con- 
 verted into oxalic acid. 
 
 Take 1 mil of a weak solution of glycerin, make it strongly 
 alkaline with KOH, and add an excess of a saturated solution 
 of KMnCU, i.e., until the mixture is blackish. Boil and 
 add some Na 2 S03 to destroy excess of KMn04, then filter, 
 acidulate with HC 2 H 3 02 and add CaCl 2 =a white ppt. of 
 CaC 2 04 forms : 
 C3H 5 (OH)3+4KMn04=K 2 C 2 04+K 2 C0 3 +4Mn0 2 +4H 2 
 
 Potassium 
 Oxalate. 
 
 K 2 C 2 4 + CaCl 2 = CaC 2 4 + 2KC1. 
 
 Calcium 
 Oxalate. 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 153 
 
 Nitrobenzene = Nitrobenzol (Oil Mirbane) . A limpid, yellowish, 
 oily liquid, possessing the odor of essential oil of bitter 
 almonds. 
 
 (1) Placed in contact with zinc dust and dilute H 2 S04, 
 it is decomposed into aniline and water: 
 
 C 6 H 5 N0 2 + 3H 2 = C 6 H 5 NH 2 + 2H 2 0. 
 
 (2) Heat the aniline solution as obtained above with 
 a few drops of CHCla and KOH. The characteristic odor of 
 phenylisocyanid will be recognized. 
 
 (3) Drop a small crystal of KC10 3 into some nitrobenzene, 
 and underlay this with H 2 S(>4; a violet color will develop. 
 
154 QUALITATIVE CHEMICAL ANALYSIS. 
 
 170. IDENTIFICATION OF SCALED IRON COMPOUNDS * 
 
 STEP I. Heat about 1 gram of the substance in a porcelain 
 crucible to dull redness, allowing free access of air. 
 
 If an odor resembling that of burning sugar is given off, the 
 substance is probably a citrate or tartrate. Confirm in Step IV. 
 
 When all the combustible matter is consumed, dissolve 
 out the soluble part of the residue with a few mils of hot water, 
 and filter. 
 
 Test the filtrate with red litmus paper. 
 
 The paper turns blue; sodium or potassium, or both are 
 present. 
 
 The paper remains unchanged in color; proceed to Step II. 
 
 Divide the solution which has turned red litmus blue into 
 two parts. 
 
 (a) Heat on a clean platinum wire in a colorless flame : The 
 flame becomes intensely yellow; sodium is present. Observe 
 this flame through cobalt glass. If violet-red, potassium also 
 is present. 
 
 . The flame is colored violet only; potassium is present. Con- 
 firm under (fe). 
 
 (b) Add to the solution some test solution of sodium-cobaltic 
 nitrite : 
 
 A copious yellow precipitate indicates potassium. 
 
 STEP II. Dissolve a small quantity of the original sub- 
 stance in water, acidulate with hydrochloric acid and divide 
 into two parts. To one part add test solution of potassium 
 ferrocyanid: 
 
 A blue precipitate indicates ferric iron. 
 
 To the other part add potassium ferricyanid : 
 
 A blue precipitate indicates ferrous iron. 
 
 STEP III. Dissolve 2 grams of the original substance in 
 
 * Joseph L.Mayer, Drugg.Cir., Feb. 1901. 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 155 
 
 20 mils of 10% solution of potassium hydroxid and boil; an 
 odor of ammonia indicates the presence of ammonium. 
 
 Whether ammonium is present or not, cool the solutior 
 and filter; examine the filtrate as directed in Step IV, and 
 the precipitate as in Step V. 
 
 STEP IV. The filtrate obtained in Step III should be clear 
 and colorless and measure about 10 mils. Divide it into three 
 portions of 2.5, 2.5 and 5 mils, respectively. 
 
 (a) Slightly acidulate one of the smaller portions with acetic 
 acid and add test solution of calcium chlorid: 
 
 A precipitate occurs; the salt is probably a pyrophosphate. 
 Confirm by (c) . 
 
 Filter and boil the filtrate (or the clear solution if no pre- 
 cipitation has occurred) : 
 
 A white crystalline precipitate occurring after a few minutes 
 indicates a citrate. 
 
 (b) Slightly acidulate the second smaller portion with 
 acetic acid and add an equal volume of alcohol : 
 
 A white crystalline precipitate occurring after a few minutes 
 indicates a tartrate. 
 
 (c) To the remaining portion of (5 mils) add 5 mils of a 10% 
 solution of ammonium chlorid, and then add, a few drops at 
 a time, 1.5 mils of a 10% solution of magnesium sulfate, agitating 
 after each addition: 
 
 A white crystalline precipitate indicates a phosphate. 
 
 Confirm as follows: Thoroughly wash the precipitate until 
 the wash-water gives no cloudiness with silver-nitrate solu- 
 tion, dissolve in dilute nitric acid, neutralize with ammonium 
 hydroxid, acidify with acetic acid and add 5% solution of 
 silver nitrate. 
 
 If a phosphate is present, a canary-yellow precipitate appears. 
 
 To the filtrate from the precipitate obtained by the addi- 
 tion of ammonium chlorid and magnesium sulfate to (c), or to 
 the clear liquid if no precipitate was produced, add a little 
 acetic acid and heat to boiling: 
 
156 QUALITATIVE CHEMICAL ANALYSIS. 
 
 A white flocculent precipitate indicates a pyrophosphate. 
 
 Confirm by the silver-nitrate test applied as above : 
 
 A white precipitate appears if a pyrophosphate is present. 
 
 STEP V. Wash the precipitate obtained in Step III. into 
 a test-tube with about 15 cc. of chloroform, shake well for a 
 few minutes, filter, and divide the filtrate into two portions 
 (a) and (&). Heat both portions of the filtrate in porcelain 
 capsules on a water-bath until the chloroform is all evaporated. 
 
 (a) Add a small quantity of hot water slightly acidulated 
 with sulfuric acid to the residue in one of the capsules, and 
 filter. Divide the filtrate into three equal parts. 
 
 1. Add to one portion, Mayer's reagent: 
 A precipitate indicates an alkaloid. 
 
 2. Add to the second portion, Labarraque's solution, using 
 a quantity sufficient to destroy blue fluorescence if observed, 
 and then a few drops of ammonium hydroxid : 
 
 An emerald-green color indicates quinine. 
 
 3. To the third portion add ammonium hydroxid in slight 
 excess, filter, reject the filtrate, dissolve the precipitate in 
 about 1 mil of water, containing a few drops of diluted acetic 
 acid, neutralize exactly with potassium hydroxid, and add 
 about 1 mil of a saturated solution of Rochelle salt: 
 
 A white precipitate indicates quinine or cinchonidine. 
 
 Filter off the precipitate, dissolve in diluted hydrochloric acid, 
 add potassium-hydroxid solution and 2 mils of ether, and shake 
 well. The quinine dissolves, while the cinchonidine remains as a 
 crystalline precipitate at the line of separation of the two liquids. 
 
 To the filtrate from the precipitate in 3, or the clear solu- 
 tion if no precipitate was produced, add an excess of potassium 
 hydroxid: 
 
 A white precipitate insoluble in ether indicates cinchonine. 
 
 (b) To the residue in the other capsule add a drop of sulfuric 
 acid; into this put a fragment of potassium dichromate, and after 
 a few minutes draw this drop, by means of a glass rod, across 
 the capsule: 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 157 
 
 A beautiful violet color, changing quickly to yellow and red, 
 indicates strychnine. 
 
 NOTES. As the foregoing scheme is intended partly for the 
 benefit of students, I add some notes regarding the chemistry 
 involved in its construction. 
 
 STEP I. When organic salts of the alkali metals are ignited, 
 they leave their carbonates, which affect red litmus paper; 
 the qualitative reactions then separate the two. 
 
 STEP II. This introduces the qualitative reaction for fer- 
 rous and ferric iron. 
 
 STEP III. This depends upon the fact that compounds 
 containing ammonium give off ammonia when brought in con- 
 tact with an alkali hydroxid. In addition, this step plays the 
 role of precipitating the iron as a hydroxid, thus making it 
 possible to operate with a colorless filtrate in Step IV. It 
 then goes farther by rendering Step V assistance by precipi- 
 tating the alkaloids and keeping them in the iron magma until 
 the time arrives to proceed with their identification. The alka- 
 loidal salts when treated with an alkali give up their acid and, 
 being insoluble in the solution, they precipitate. Upon this 
 fact the process depends. It is easy to see that the alkaloids 
 remain on the filter, while the acidulous radicals appear as 
 potassium salts in the filtrate. 
 
 STEP IV. The rationale of this step is simple. The object 
 of adding acetic acid is to prevent the precipitation of calcium 
 citrate in the cold. This is made necessary through the fact 
 that pyrophosphates (most "iron pyrophosphates" are citro- 
 pyrophosphates) produce with calcium- chlorid test solution a 
 precipitate insoluble in acetic acid, whereas the citrate pre- 
 cipitate is soluble; if therefore acetic acid is first added, the 
 citrate remains unaffected until the solution is boiled. There- 
 fore if a precipitate forms in the cold, filter and test the filtrate 
 as directed. Unless there be an excess, the citrate precipitate 
 does not form in the cold, but calcium citrate, being insoluble 
 in hot solution, precipitates when the solution is boiled. 
 
158 QUALITATIVE CHEMICAL ANALYSIS. 
 
 If the filtrate containing potassium hydroxid also contains 
 a tartrate, the addition of acetic acid produces potassium acid 
 tartrate which is practically insoluble in water, and totally 
 insoluble in alcohol. 
 
 Phosphates produce with magnesia mixture the white 
 crystalline ammonio-magnesium phosphate and as pointed 
 out by Nagelvoort (Am. Journ. Pharm., 1895, page 210) an excess 
 of magnesia mixture is objectionable and apt to lead to erroneous 
 conclusions. The magnesia mixture is prepared in the course 
 of the process, acting upon the suggestion of Steiglitz (Am. 
 Journ. Pharm., 1891, page- 583), as follows: The nitrate con- 
 taining potassium hydroxid has added to it ammonium-chlorid 
 solution, whereupon, as shown in a previous reaction, ammonium 
 hydroxid is generated. There remains, however, enough am- 
 monium chlorid in the solution to prevent precipitation of mag' 
 nesium hydroxid when the magnesium-sulfate solution is added. 
 Having subjected the sample to the test and obtaining what 
 gives every evidence of being a phosphate, the reaction with 
 silver nitrate acts in a confirmatory manner. Orthophosphates 
 give with this reagent a yellow precipitate and pyrophosphates 
 a white one. The separation of the pyrophosphate from the 
 phosphates is made possible in this step as a result of the fact 
 pointed out by Fresenius, that pyrophosphates produce with 
 magnesium sulfate a precipitate of magnesium pyrophosphate 
 soluble in excess of magnesium sulfate and not precipitated by 
 ammonium hydroxid, which, being the contrary of the behavior 
 of orthophosphates, serves to separate the two acids. The 
 nitrate from the phosphate precipitate, or the solution in which 
 the reagent has produced no effect, is then acidified with acetic 
 acid and heated to boiling: a white flocculent precipitate in- 
 dicates a pyrophosphate. 
 
 STEP V. The fact upon which this step is based has been 
 partly explained in Step III., where the alkaloids remained in 
 the magma, and being soluble in chloroform, that solvent, after 
 being thoroughly shaken with the residue, takes them up. By 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 159 
 
 treating the residue with hot water containing a few drops of 
 diluted sulfuric acid, the sulfates of the alkaloids are formed, 
 and being more soluble in hot water than in cold, the process 
 directs that condition. Mayer's reagent precipitates all the 
 alkaloids included in the scheme, and if no reaction occurs, 
 their absence is safely reported. 
 
 The test for quinine is made with Labarraque's solution, 
 and as this is a new method a word regarding it will not be 
 amiss. Every one who has had occasion to qualitatively test 
 for quinine with chlorine or bromin water must know the diffi- 
 culties encountered through the inconvenience of obtaining 
 either of the above two reagents in a condition to be depended 
 upon. The Labarraque's solution is always at hand. The 
 chemistry concerned in the reaction is easily understood: 
 The Labarraque's solution coming into contact with the acid 
 of the solution under examination has its chlorin liberated, 
 which, if quinine is present, forms with it and a few drops of 
 ammonia the characteristic thalleoquin shown by an emerald- 
 green-colored solution. Having in many qualitative quinine 
 determinations applied the test as above directed, with the 
 most satisfactory results the writer has no hesitation in advo- 
 cating its use in preference to the others referred to. 
 
 It might be of interest to here mention that quinidine also 
 gives a green color with this test, but as its higher price precludes 
 any possibility of its ever being substituted for quinine, it is 
 unnecessary to point out the method of differentiation. 
 
 The cinchonidine reaction is dependent upon the fact that 
 sodium and potassium tartrate (Rochelle salt) produces with 
 it the insoluble cinchonidine tartrate. Quinine behaves in a 
 similar manner towards this reagent, but the identification 
 in solution 2 of this step eliminates that source of error. If 
 necessary, the alkaloid can in the event of a doubt be further 
 identified as directed. 
 
 Cinchonine is identified by its behavior towards ether. 
 Potassium-hydroxid precipitates it; ether is added and the 
 
 CALIFORNIA COLLE6K 
 
 of PHARMACY 
 
160 QUALITATIVE CHEMICAL ANALYSIS. 
 
 cinchonine being insoluble, remains as a white bulky pre- 
 cipitate. 
 
 In another portion of the residue the strychnine is identified. 
 The reaction is characteristic, and if applied as directed will 
 detect minute quantities. 
 
 The entire process is simple, accurate, inexpensive to operate, 
 quickly carried out, and has everything to commend it. 
 
 171. A SCHEME FOR THE DETECTION OF POISONS. 
 
 Divide the suspected sample into 3 parts, A, B, and C, and 
 treat as follows : 
 
 A. (1) If a liquid, place in a capsule, and on a water-bath 
 evaporate to a syrupy consistency 
 
 (2) If a solid, chop up or cut up with scissors into smallest 
 possible pieces. 
 
 (3) Transfer product of either (1 or 2), to a flask provided 
 with a reflux (upright Liebig's) condenser or a long 
 tube drawn through the cork of flask. Cover the sub- 
 stance with twice its bulk of a 1% solution of tartarir 
 acid in alcohol, and heat on a water-bath for one hour 
 (Stas-Otto). 
 
 (4) Remove from the water-bath, cool, filter, and carefully 
 concentrate the filtrate on a water-bath until all the 
 alcohol is dissipated. 
 
 (5) Filter the concentrated extract through a wetted 
 filter and again evaporate on water-bath to a syrupy 
 consistency. 
 
 (6) Dissolve the syrupy extract in absolute alcohol, stirring 
 carefully to aid in effecting as complete a solution as 
 possible. Filter once more, and again drive off the 
 alcohol on the water-bath. 
 
 (7) Dissolve the residue from (6) in distilled water, render 
 alkaline with sodium hydroxid, pour into a separatory 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 161 
 
 funnel, and extract it with ether, making at least two 
 ' extractions. 
 
 (8) Divide the ethereal extract from (7) into two portions, 
 each contained in an evaporating dish, and allow the 
 ether to volatilize spontaneously; the alkaloids, strych- 
 nine, and veratrine should be tested for according to 
 Chart 89, Steps 2 and 3, respectively, in one of the 
 dishes, and in the other atropine and cocaine should 
 be tested for according to Step 2. 
 
 (9) The residue from the separatory funnel is poured into 
 an evaporating dish, NH 4 OH added until ammoniacal, 
 and placed on a water-bath, heating it until all the 
 remaining ether is dissipated, and then set aside for 
 12 hours. 
 
 (10) After 12 hours, warm the product of (9), pour into a 
 separatory funnel, and extract it with amylic alcohol. 
 The amylic alcohol extract is carefully evaporated in 
 a porcelain capsule and morphine, identified as in 
 Step 1, Chart 89. 
 
 B. (1) Stir this portion prepared just as in A (1) and (2), 
 with about 200 mils of distilled water, and acidify (if alka- 
 line or neutral, not otherwise) with 1 or 2 mils HC1 (C. P.). 
 
 (2) Place the solution prepared as in (1) on a dialyzer and 
 float it in a liter of distilled water contained in a porcelain 
 vessel. 
 
 (3) After 24 hours, concentrate the water in the porcelain 
 dish by evaporation on a water-bath. (This method 
 separates from amorphous organic matter any crys- 
 talloid substance, be it inorganic or organic.) 
 
 (4) Divide the dialyzed extract (evaporated to about 50 mils 
 in (3)) into two equal portions. 
 
 Test 1st portion for As, Hg, Sb, Zn, Pb, with H 2 S. 
 Test 2d portion for Phenol, Chloral, Chloroform, Aniline, 
 
162 QUALITATIVE CHEMICAL ANALYSIS. 
 
 Nitrobenzene, Hydrocyanic Acid, Acetanilide, Phe- 
 nacetin and the mineral acids. 
 
 C. (1) Prepare as in A ((1) and (2)) ; place in an evaporating 
 dish, add an equal bulk of strong pure HC1, and warm 
 on the water-bath, from time to time adding a crystal of 
 KNOs and replacing water lost on evaporation. Con- 
 tinue until all the organic matter is destroyed, expel 
 chlorin by a higher heat, pass H^S in the warm solution, 
 and test precipitate, according to the tables, for inor- 
 ganic substances and the acids (except HC1). 
 
 172. A SCHEME FOR URANALYSIS. 
 
 Observe: 
 
 1. Quantity passed in 24 hours. It should be from 1200 
 to 1500 mils. 
 
 2. Color and transparency. Colorless, yellow to brown, 
 clear, cloudy or opaque. 
 
 3. Reaction. Acid, alkaline or arnphoteric; normal urine 
 is faintly acid. 
 
 4. Specific Gravity. Should be 1.015 to 1.025 at 15 C. 
 
 5. Sediment. Note its quantity, and examine its character 
 with a microscope. 
 
 NOTES: 1. When it is directed to warm the urine do not boil. 
 
 2. If not perfectly clear, the urine should be filtered before 
 applying tests. 
 
 3. If much albumin is present, it should be removed before 
 testing for sugar. 
 
 4. Putrid urine should not be tested for sugar by any 
 reagent containing copper or bismuth. 
 
 5. If the quantity of U (abbreviation used in this scheme 
 for urine) is too small to float the urinometer, it may be diluted 
 with an equal volume of water, and the last two figures of 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 1Q3 
 
 the specific gravity of this diluted urine, multiplied by two, or 
 the specific gravity may be taken by a specific-gravity bottle. 
 
 6. To calculate the quantity of total solids from the specific 
 gravity, multiply the last two figures of the specific gravity 
 by 2.33. This will give the number of grms. in 1000 mils of 
 urine. The last two figures also indicate approximately the 
 number of grains in a fluid ounce. 
 
 ORGANIC CONSTITUENTS (Abnormal): 
 
 173. Albumin. 
 
 (a) Heat Test. Add 10 drops of strong acetic acid 
 to 10 mils of U. Heat; cloudiness or precipitate, if 
 any, indicates albumin. 
 
 (6) Nitric-acid Test. Heller's. Put 2 mils of colorless 
 HNOs into a test-tube, incline the tube, and add 
 slowly, by means of a pipette, 4 mils of U. 
 
 A sharp white band (zone) at point of contact 
 indicates albumin. 
 
 Precautions. 
 
 1. Mixed urates if present in excess will also 
 give a band higher up. It is dissipated by warming 
 (not boiling). 
 
 2. After the administration of resinous drugs 
 (copaiba, etc.) or turpentine, a yellowish clouded 
 zone also forms, which is redissolved by alcohol 
 (albumin zone does not dissolve). 
 
 (c) Tanret's Test. Acidify 5 mils of U with acetic acid, 
 add Tanret's reagent drop by drop until 2 mils have 
 been added. Then warm. Any ppt. remaining is 
 albumin. 
 
 Precaution. 
 
 This test precipitates also peptone, alkaloids, 
 urates, and pine acids, which, however, redissolve on 
 warming. 
 
164 QUALITATIVE CHEMICAL ANALYSIS. 
 
 (d) Potassium-ferrocyanid Test. Take half a test-tube 
 full of urine, add about one-fourth its volume of 
 5 per cent, potassium-ferrocyanid solution, mix well 
 and then add a few drops of acetic acid. If albumin 
 is present a milky cloud will appear throughout the 
 whole volume of the liquid. This test precipitates 
 albumin only. 
 
 (e) Quantitative Estimation. Fill an Esbach albumino- 
 meter to the letter " U " with urine, and then to the 
 letter " R " with Esbach's reagent. Cork securely, 
 mix thoroughly, by carefully inverting tube, and set 
 aside for 24 hours then read. Each one of the 
 main divisions read off indicates 1 grm. of albumin 
 in a liter of urine. 
 
 174. Peptones. 
 
 (a) The urine is slightly acidulated with acetic acid and 
 then saturated with ammonium sulfate. The pre- 
 cipitate, if any (which consists of albumin and the 
 albumoses), is removed by filtration. The filtrate 
 then treated with Tanret's reagent ppts. peptone 
 only. 
 
 (6) Ralfe's Test. Place 4 mils Fehling's reagent in a 
 test-tube, and gently overlay with urine. At point 
 of contact a zone of phosphates forms; above this 
 another rose-colored zone, or " halo," will .float if 
 peptone is present. 
 If mixed with albumin the halo will be purple. 
 
 (b) Randolph's Test To 5 mils of faintly acid urine add 
 4 drops of a saturated solution of KI and 4 drops of 
 Millon's reagent. If peptones or bile acids are 
 present, a yellow ppt. falls. Test for bile acids; if 
 these be absent, the yellow ppt. indicates peptones. 
 
 175. Glucose (Sugar). 
 
 (a) Fehling's Test. Place 5 mils of Fehling's reagent in 
 a test-tube, and heat to boiling. Add now drop 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 165 
 
 by drop 5 mils of urine, heating after each addition. 
 A yellow or orange coloration or a brick-red ppt. 
 of copper suboxid (Cu20) indicates glucose. 
 
 (b) Pavy's Test. Place 5 mils of Pavy's reagent in a test- 
 tube and warm. Now add 5 mils of U; a partial or a 
 total disappearance of the blue color indicates sugar. 
 
 (c) Haine's Test. Heat 5 mils of Haine's reagent in a 
 test-tube to boiling. Drop by drop add 6 to 8 drops 
 of U, and boil again; an orange-red ppt. of Cu 2 0, 
 indicates glucose. 
 
 (d) Bdttger's Bismuth Test. Place in a test-tube 3 mils 
 of U, 3 mils of liquor potassa and a little (0.3 grm.) 
 bismuth subnitrate; boil these together for 2 min- 
 utes. If sugar be present in quantity, black metallic 
 bismuth deposits; if a small quantity only is pres- 
 ent the solution will assume a grayish color. 
 
 (e) Nylander's Test. Boil together in a test-tube 10 mils 
 of U with 1 mil of Nylander's reagent. If a light- 
 gray or black precipitate forms it indicates glucose. 
 
 (/) Benedict's Test. (Qualitative). Place 5 mils of 
 Benedict's reagent in a test-tube, add 8 to 10 drops 
 (not more) of the U to be examined, heat to vigor- 
 ous boiling and keep it at this temperature for one 
 or two minutes, then allow the mixture to cool 
 spontaneously. In the presence of glucose the 
 entire body of the solution will be filled with a precip- 
 itate, which may be red, yellow or greenish in color. 
 If the quantity of glucose be low (under 0.3 per 
 cent.) the precipitate forms only on cooling. If no 
 . glucose is present, the solution remains blue and 
 clear, but may show a faint turbidity. 
 
 Dr. J. L. Mayer * applies the test as follows: 
 Into a very small Erlenmeyer flask introduce 5 
 mils of Benedict's reagent. Then by means of a 
 * Journal American Pharmaceutical Association, 1914, page 687. 
 
166 QUALITATIVE CHEMICAL ANALYSIS. 
 
 medicine dropper add 8 drops of U, place the flask 
 on a hot plate and heat to boiling. When the solu- 
 tion starts to boil time it for 1| minutes, and then 
 pour it into a test-tube and allow it to cool spon- 
 taneously; a greenish tinge extending throughout 
 the solution, upon 1J minutes boiling, is regarded 
 as a positive reaction. If the greenish color does 
 not appear until the liquid has cooled, the amount of 
 glucose present is very slight. 
 
 (g) Trommer's Test. Fill the test-tube one-third full of 
 U, add an almost equal volume of 10% NaOH solu- 
 tion, and then, drop by drop, CuSCU T.S., until the 
 copper hydrate which is at first formed, is no 
 longer dissolved on shaking, then apply heat. A 
 yellow precipitate of cuprous oxid indicates glucose. 
 
 (h) Phenyl-hydrazine Test. To 10 mils of the U in a 
 test-tube add 1 gm. of phenyl hydrazine hydro- 
 chlorid and 2 gms. of sodium acetate, and place the 
 test-tube in boiling water for half an hour. Then 
 cool. Crystals of phenyl-glycosazone will sep- 
 arate and when viewed under a microscope, appear 
 in bundles or sheaves. 
 
 (i) Quantitative Estimation (by Fermentation.) Take 
 jL part of a cake of Fleischmann's yeast, shake thor- 
 oughly with 10 mils urine, pour into an Einhorn sac- 
 charometer, and set aside for 24 hours in a room of 
 ordinary temperature (25 C. = 77 F.). Read off 
 the percentage of glucose present. 
 
 (/) Quantitative Estimation (with Fehling's Reagent). 
 Place in a 200-mil flask 10 mils of Fehling's solu- 
 tion; to this add 10 mils of a freshly prepared 10% 
 solution of K 4 Fe(CN) 6 and 30 mils of water. Heat 
 mixture on a water-bath (best temperature for the 
 operation being between 80 and 90 C.) ; then run in 
 thell (diluted if it contains much sugar), drop by 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 167 
 
 drop, until the blue color just disappears. Excess 
 of glucose quickly turns the solution yellowish-brown 
 (copper ferrocyanid forms). This method is both 
 reliable and rapid. 
 
 (A:) Quantitative Estimation (Benedict's). Fill a burette 
 with the U diluted 1 : 10. Then introduce 25 mils of 
 Benedict's Quantitative Reagent into a porcelain 
 evaporating dish add 10 to 20 gms. of crystallized 
 sodium carbonate and a small quantity of powdered 
 pumice and heat to boiling over a free flame, until 
 the carbonate is entirely dissolved. Keep the 
 solution boiling vigorously, and run the U rather 
 rapidly into it from the burette until a chalk-white 
 precipitate forms and the blue color of the solution 
 begins to lessen perceptibly, after which deliver the 
 U slowly, a few drops at a time, until the last trace 
 of blue disappears. This marks the end point. 
 
 If during the titration the solution becomes too 
 concentrated, through evaporation, add water to 
 replace the volume lost. 
 
 The calculation of the quantity of glucose in the 
 original sample of urine is as follows: 25 mils of 
 Benedict's reagent are reduced by 0.05 gm. of glu- 
 cose. Therefore the volume of urine required to 
 effect the reduction contains 0.05 gm. of glucose. 
 When the U is diluted 1 : 10 as in the usual titration 
 of diabetic urines, the formula for calculating the 
 per cent.. of glucose is 
 
 xiooxio=%. 
 
 * 
 
 x is the number of mils of diluted U employed in 
 
 the titration to effect the complete reduction. 
 
 Dr. Jos. L. Mayer * applies the method as follows: 
 
 * J. A. Ph. A., 1914, page 688. 
 
168 QUALITATIVE CHEMICAL ANALYSIS. 
 
 Into a 100-mil Erlemneyer flask, measure 25 mils of 
 Benedict's Quantitative Reagent, add about 10 
 gms. of anhydrous sodium carbonate, a couple of 
 pieces of pumice stone, which have been heated to 
 white heat and plunged into water, and about 10 
 mils of distilled water. Place the whole on a hot 
 plate until the solution boils and the sodium car- 
 bonate is dissolved. Then begin adding the U in 
 small amounts from the burette, allowing sufficient 
 time between each addition for the reaction to pro- 
 ceed. The end reaction is known by the disap- 
 pearance of the last trace of blue. 
 176. Indican (Uroxanthine Indoxyl-potassium sulfate). 
 
 (a) Place 4 mils of HC1 in a test-tube, add an equal vol- 
 ume cf urine and a few drops of nitric acid, boil, cool 
 and then shake with a few drops of chloroform. The 
 latter becomes violet if excess of indican is present. 
 (6) Obermeyer' s Test. Place 4 mils of urine in a test-tube, 
 add an equal volume of hydrochloric acid containing 
 FeCl 3 (2 gm. in 1000 cc.). Shake with chloroform, 
 and a violet-blue color occurs in the latter. 
 Precaution. 
 
 If biliary acids or phosphates are present, remove 
 them before testing for indican by adding to 10 mils 
 of U, 8 drops of Pb(C 2 H 3 02)2 solution and filtering. 
 The nitrate is now tested for indican. 
 (c) Place in a test-tube 4 mils each HC1 and U, agitate, 
 add 2 or 3 drops of a very dilute solution of chlor- 
 inated soda, and shake; a reddish-blue or bluish- 
 black coloration indicates indican (indigo is formed 
 in this reaction; a weak solution of NaCIO is 
 directed, as an excess would bleach the indigo). 
 If now 2 mils of CHCls be added and the mixture 
 agitated, the indigo is dissolved out and with the 
 chloroform settles at the bottom as a blue bead (the 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 169 
 
 depth of the blue color is indicative of the quantity 
 of indican present). 
 
 177. Blood. 
 
 (a) Heller's Test. To 5 mils of U contained in a test- 
 tube add 2 mils of KOH solution and warm. 
 
 The earthy phosphates which precipitate carry 
 with them the blood coloring-matter, and if blood 
 is present the precipitate will be blood-red, in ab- 
 sence of blood, white. 
 
 (6) Almeris Test. Shake together in a test-tube 5 mils 
 each of tincture guaiacum and hydrogen dioxid 
 (or old resinified turpentine oil), and drop by drop 
 add about 5 mils of U. Let stand a few minutes; if 
 blood is present, a blue or bluish-green coloration is 
 formed in the upper layer. If much blood is present, 
 on agitating the tube it will diffuse through the entire 
 liquid, giving it a creamy-bluish color. 
 
 178. Bile. 
 
 (a) Gmeliris Test (for bile pigments). 
 
 Place into a narrow test-tube some nitric acid 
 containing a little yellow nitrous acid (or nitric acid 
 which is partly decomposed by adding a fragment 
 of zinc, or a piece .of wood to it), and carefully 
 float upon this about an equal volume of urine. 
 There will appear in the middle zone a play of colors 
 from below, upward, green, blue, violet, red, and 
 yellow. 
 
 This test may be modified by moistening a piece 
 of white filtering paper with the urine and then 
 placing in the center a drop of nitric acid containing 
 a little ntirous acid. A pale yellow spot is formed, 
 . surrounded by colored rings. Instead of filtering 
 paper a plaster of paris disk may be used. 
 
 (6) lodin Test. Upon the surface of 5 mils of U, care- 
 fully float 10 drops of tincture of iodin, which has 
 
170 QUALITATIVE CHEMICAL ANALYSIS. 
 
 been diluted with alcohol until it has a sherry wine 
 color. At the point of contact an emerald-green 
 zone is formed if bile is present. 
 
 (c) Pettenkofer's Test (for Biliary Acids). Add to 5 mils 
 of U contained in a test-tube 4 drops of a solution of 
 cane-sugar (saccharose 1:3), shake, and carefully 
 underlay with strong H^SO^ Let stand for a few 
 minutes; if biliary acids be present, a purple band 
 is formed at point of contact. 
 
 (d) Oliver's Peptone Test (for Biliary Acids). Clarify the 
 U by filtration, and dilute to the sp.gr. of 1.008. 
 Place in a test-tube 4 mils of Oliver's reagent and 
 run into it 1 mil of the U, diluted as above. If 
 biliary acids are present, a distinct milkiness 
 promptly appears, which becomes more intense 
 after a few minutes. Oliver's reagent is composed 
 of pulverized peptone, 2 gms., salicylic acid, 0.25 
 grm.; acetic acid, 2 mils; and sufficient distilled 
 water to make 250 mils. 
 
 Precaution. 
 
 The above test is very delicate and reliable, but 
 only in the absence of albumin, which should be 
 removed by boiling the U with a few drops of 
 HC 2 H 3 2 and filtering. 
 179. Acetone. 
 
 (a) Legal 's Test. Pour into a test-tube 2 mils of a 
 strong freshly prepared solution of sodium nitro- 
 prussid, and add 4 mils of U and 2 mils NaOH solu- 
 tion. The mixture acquires a red coloration, which 
 may be due to creatinin (a normal constituent of U) 
 as well as to acetone. Add 6 or 8 mils of glacial 
 HC 2 H 3 02; if the mixture now assumes a claret-red 
 or violet color, acetone is present in considerable 
 quantity; if the color is discharged by the acid, it 
 was due to creatinin only. 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 171 
 
 A better method of applying this test is to add 
 to about 5 mils of urine a few drops of freshly pre- 
 pared solution of sodium nitroprussid, then make 
 strongly acid with glacial acetic acid and after thor- 
 oughly mixing, carefully float some strong ammonia 
 water on top a violet zone at the line of contact 
 indicates acetone. 
 
 (b) Lieben's Test. Pour into a test-tube 6 mils of U, 
 add 10 drops solution of iodin and about 1 mil of 
 NH40H, and heat. If acetone be present, crystals 
 of iodoform will form and deposit; the iodoform may 
 be recognized by its characteristic aromatic odor. 
 
 (c) Ehrlich's Diazo Reaction for Typhoid Fever. The 
 reagent consists of two solutions: No. I. Sodium 
 nitrite 1 gm. dissolved in distilled water to make 
 200 mils. No. II. Sulphanilic acid 5 gms., hydro- 
 chloric acid 50 mils, distilled water to make 1000 
 mils. 
 
 For use, 1 mil of No. I should be mixed with 50 
 mils of No. II. 
 
 The test is applied as follows: Take a portion 
 of the reagent mixed as above, and add an equal 
 volume of U, make strongly alkaline with am- 
 monia water, and shake well. Both the foam and 
 the solution will become rose-colored, and a greenish 
 precipitate will be observed at the end of 24 hours. 
 
 ORGANIC CONSTITUENTS (Normal): 
 
 180. Urea (Carbamid, CH 4 N 2 0), Quantitative Estimation of. 
 (a) Fill a Doremus ureometer to the double mark with 
 hypobromite solution (made, by dissolving 100 gms. 
 of NaOH in 250 mils of water, and to this adding 
 25 mils of bromin), then add enough water to half 
 fill the bulb. Now add 1 mil of U by means of a 
 nipple-pipette, forcing it as far up into the graduated 
 
172 QUALITATIVE CHEMICAL ANALYSIS. 
 
 cylinder as possible, stopper securely, let stand 15 
 minutes or until all the nitrogen is evolved, then 
 read off, grains per fl. oz. or gms., per 1000 mils. 
 (b) A better instrument for this estimation is the Hind's 
 modification of the Doremus ureometer. This 
 instrument is provided with a side arm, graduated 
 to deliver one or two mils of urine, a glass stop-cock 
 is situated in the lower part of the short arm, and 
 this when open permits the urine to flow into the 
 long arm of the instrument where the reaction takes 
 place. 
 
 181. Uric Acid, C 5 H 4 N 4 03. 
 
 (a) Murexid Test. Evaporate 10 mils of U to dryness in 
 a porcelain capsule, and then add a drop or two of 
 HN0 3 to dissolve the residue. Dissipate the uncom- 
 bined HN0 3 by heating on a water-bath. When 
 dry, moisten the residue with 1 or 2 drops of NH 4 OH, 
 or expose it to the vapor of NH 3 , by inverting the 
 capsule over a bottle containing ammonia water. 
 A purple-red color of murexid indicates uric acid. 
 
 (b) Silver Carbonate Test. One or two drops of silver 
 nitrate T.S. are dropped upon a piece of white filter- 
 ing paper, and then touched with the urine made 
 alkaline with sodium carbonate. A black color 
 appears if 0.001 per cent, of uric acid is present. 
 
 INORGANIC CONSTITUENTS: 
 
 182. Chlorids. 
 
 (a) Acidify with HN0 3 , add a few drops of AgN0 3 
 T.S. A curdy ppt. indicates chlorids. 
 
 (b) Quantitative Estimation. Dilute 10 mils of U with 
 40 mils of distilled water, add 10 drops of 10% 
 potassium-chromate solution (free from chlorids), 
 and from a burette run in drop by drop tenth normal 
 AgN0 3 solution, until a permanent reddish-brown 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 173 
 
 color of silver chromate is produced, indicating end- 
 
 N 
 reaction. Each mil ^ AgN0 3 solution =0.005846 
 
 gm. of chlorids, calculated to NaCl. 
 (c) A better and much more accurate method is the 
 Volhard's. 
 
 Dilute 10 mils of urine with 40 mils of distilled 
 
 N 
 water, add an excess (say 12 mils) of -^AgNOa V.S., 
 
 2 mils of strong HNOs and 2 mils of ammonio- 
 ferric sulfate T.S. (ferric alum); mix well, and 
 
 N 
 then titrate with j^ KSCN V.S. until a permanent 
 
 reddish color appears. The number of mils of 
 KSCN solution used, are deducted from the quan- 
 tity of AgN0 3 V.S. taken and the difference mul- 
 tiplied by .005846 or by .003546 gives the grammes, 
 respectively, of the NaCl and Cl in the 10 mils of 
 urine taken for analysis. 
 
 Assuming that 5 mils of the KSCN V.S. were 
 required, then 12 5 = 7 mils. 
 
 .005846X7 = .040922 gm. or 4.0922 gms. in 1000 
 mils. 
 
 183. Phosphates (1. Earthy). 
 
 (a) Add to 5 mils of U 3 mils of NH 4 OH; the earthy 
 phosphates are precipitated. 
 
 These may be separated by filtration, dried at 
 a low heat, and weighed if required. 
 
 (6) (2. Alkaline). Approximate Estimation. Filter out 
 the earthy phosphates as precipitated in (a), and to 
 the filtrate contained in a test-tube add one-third its 
 own volume of magnesia mixture. If the entire 
 fluid presents a cloudy appearance or a milkiness, 
 the alkaline phosphates are normal. If, however, a 
 decided, dense, milk, or cream-like precipitate forms, 
 
174 QUALITATIVE CHEMICAL ANALYSIS. 
 
 the alkaline phosphates are present in greater than 
 normal quantities. 
 
 If the fluid is but very slightly cloudy, transmit- 
 ting light, the phosphates are present in less than 
 the normal quantities. 
 
 (c) For a more accurate method of estimating phos- 
 phates, see U. S. P. IX, page 22. 
 
 184. Sulfates. An approximate method for the estimation of 
 
 sulfates is the following: To 6 mils of U contained 
 in a test-tube add 8 drops of HC1; the mixture 
 is shaken and 2 mils of BaCl 2 added. An opaque 
 milky cloudiness indicates that the sulfates are 
 present in normal quantity. 
 
 If the opacity is intense, the whole mixture pre- 
 senting a creamy appearance, the sulfates are 
 present in excess above the normal quantity. 
 
 If the cloudiness is so slight as to transmit light, 
 the quantity of sulfates is subnormal. 
 
 185. Microscopical Examination. Besides the chemical ex- 
 amination as given in the above scheme, a microscopic examina- 
 tion of the sediment should likewise be made. It is advisable to 
 centrifuge the urine. The more important constituents revealed 
 in this way are the following : 
 
 (a) Epithelium, whether single cells or squamous masses 
 are present. 
 
 (6) Crystals of uric acid, triple phosphates, calcium oxalate, 
 cystin plates, etc. 
 
 (c) Amorphous deposits of urates, broken-up cellular 
 structures, detritus, etc. 
 
 (d) Blood, discs and casts. 
 
 (e) Pus, single cells and sacs. 
 
 (/) Casts (tube, waxy, hyaline, granular, epithelial, etc.) 
 (g) Mucus, cells and casts. 
 
 Also, Fungi, Bacteria, and Spermatozoids are sometimes 
 reported. 
 
QUALITATIVE ANALYSIS Of ORGANIC SUBSTANCES. 175 
 
 1 86. Report. The findings of a urinalysis may be reported 
 according to the following scheme used by the author: 
 
 New York, 190. 
 
 REPORT ON URANALYSIS. 
 
 When Received 
 
 Dr Patient ; 
 
 PHYSICAL EXAMINATION. 
 
 Odor Color 
 
 Spec. Gravity Reaction 
 
 Appearance 
 
 Sediment 
 
 Quantity passed in 24 hours 
 
 CHEMICAL ANALYSIS. 
 Albumin 
 Sugar 
 Urea 
 Bile 
 
 Acetone 
 Indican 
 Chlorids * 
 Phosphates * 
 
 MICROSCOPICAL EXAMINATION 
 Epithelium 
 Crystals 
 
 Amorphous Deposits 
 Blood 
 Pus 
 Casts 
 Mucous 
 Fungi 
 
 Spermatozoa 
 Bacteria 
 
 Analyst. 
 
 * Chlorids and phosphates are usually not reported unless a request is 
 made for the same, when an exact quantitative estimation is made. 
 
176 
 
 QUALITATIVE CHEMICAL ANALYSIS. 
 
 PREPARATION OF REAGENTS. 
 
 Reagents should be prepared only from chemically pure 
 substances, or, better, such as are guaranteed as to their purity 
 and strength, and are marketed as reagent chemicals. The 
 success of the analytic operations depends very largely on the 
 purity of reagents. 
 
 The water used in the preparation of reagents should be 
 freshly distilled and tested for impurities. 
 
 ACIDS. 
 
 When " acids" are mentioned in the text, dilute acids are 
 meant unless otherwise specified. 
 
 When " strong" or " concentrated " acids are mentioned 
 use the undiluted acids of the strength specified by the U. S. P. 
 
 HC1, 
 
 H 2 S0 4 , 
 
 HN0 3 , 
 
 Aqua Regia HN0 3 , 
 
 1 part to 4 parts H 2 by volume. 
 1 M ".4 " H 2 " 
 1 " "5 " H 2 " 
 
 1 " " 3 " HC1 " 
 
 SALTS. 
 
 
 Parts 
 
 by Volume 
 
 
 (NH 4 ) 2 C0 3 , 
 
 1 part to 4 
 
 parts H 2 0, add 
 
 1 part NH 4 OH, 
 
 (NH 4 ) 2 C 2 4 , 
 
 1 " " 25 
 
 " H 2 
 
 
 NH 4 C1, 
 
 1 " " 10 
 
 " H 2 
 
 
 KOH, 
 
 1 " " 10 
 
 " H 2 
 
 
 NaOH, 
 
 1 " " 10 
 
 " H 2 
 
 
 K 2 Cr0 4 , ' 
 
 1 " " 10 
 
 " H 2 
 
 
 K 2 Cr 2 7 , 
 
 1 " " 10 
 
 " H 2 
 
 
 K 3 Fe(CN) 6 , 
 
 1 " " 20 
 
 " H 2 
 
 
 K 4 Fe(CN) 6 , 
 
 1 - 20 
 
 " H 2 
 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 177 
 
 Na 2 C0 3 , 
 
 1 
 
 part to 10 parts H 2 
 
 Na 2 HP0 4 , 
 
 1 
 
 " " 10 " H 2 
 
 BaCl 2 , 
 
 1 
 
 " " 10 " H 2 
 
 HgCl 2 , 
 
 1 
 
 " " 20 " H 2 
 
 AgN0 3 , 
 
 1 
 
 " " 20 " H 2 
 
 Pb(C 2 H 3 2 ) 2 , 
 
 1 
 
 " " 10 " H 2 
 
 MgS0 4 , 
 
 1 
 
 " " 10 " H 2 
 
 Co(N0 3 ) 2 , 
 
 1 
 
 " " 10 " H 2 
 
 (NH 4 ) 2 Mo0 4 , 
 
 1 
 
 " " 3 " NH 4 OH (strong), add 6 
 
 
 
 parts HN0 3 (34%) 
 
 KCN, 
 
 1 
 
 " " 10 " H 2 
 
 KI, 
 
 1 
 
 " " 5 " H 2 
 
 FeS0 4 , 
 
 3 
 
 " "90 " add H 2 S0 4 10 parts 
 
 (NH 4 ) 2 S0 4 , 
 
 1 
 
 " " 10 " H 2 
 
 H 2 C 4 H 4 Oe, 
 
 1 
 
 " " 3 " H 2 
 
 Ba(OH) 2 , 
 
 a 
 
 saturated solution 
 
 BaS0 4 , 
 
 " 
 
 U 11 
 
 CaS0 4 , 
 
 " 
 
 " " 
 
 NaHC 4 H 4 6 , 
 
 " 
 
 (( (I 
 
 GASES. 
 
 H 2 S. Generate the gas from FeS by a dilute H 2 S0 4 (1 part 
 acid to 12 parts water). 
 
 NH 4 HS. Pass H 2 S in a slow current into some pure NH 4 OH 
 until the latter is saturated. This solution is sometimes called 
 yellow ammonium sulfid. 
 
 (NH 4 ) 2 S solution is made by mixing 3 parts of the foregoing 
 with 2 parts of ammonia-water. 
 
 SPECIAL REAGENTS. 
 
 Alcohol U. S. P., 95%. 
 
 Alphanaphthol. 15 parts to 100 parts of alcohol. 
 
 Benedict's Reagent (Qualitative): 
 
 Copper sulfate (pure, crystallized) 17.3 gms. 
 
 Sodium or potassium citrate 173 gms. 
 
178 QUALITATIVE CHEMICAL ANALYSIS. 
 
 Sodium carbonate (crystallized) 200 gms. 
 
 Distilled water to make 1000 mils. 
 
 Dissolve the citrate and the carbonate in about 200 mils of water 
 with the aid of heat. Filter the solution, if necessary, and place 
 in a large beaker or capsule. Dissolve the copper sulfate in 
 100 mils of water, and pour this solution slowly with constant 
 stirring into the first solution. Cool the mixture and dilute with 
 distilled water to 1000 mils. 
 
 Benedict's Reagent (Quantitative) : 
 
 Copper sulfate (pure, crystallized) 18 gms. 
 
 Sodium carbonate (crystallized) '. . . .200 gms. 
 
 Sodium or potassium citrate 200 gms. 
 
 Potassium sulfocyanate 125 gms. 
 
 5% potassium ferrocyanid solution ... 5 mils. 
 
 Distilled water to make 1000 mils. 
 
 With the aid of heat dissolve the carbonate (half the amount 
 of anhydrous salt may be used), citrate and sulfocyanate in 
 enough distilled water to make about 800 mils, filter if necessary. 
 Dissolve the copper in about 100 mils of distilled water, and pour 
 this solution slowly with constant stirring, into the other solution. 
 Add the ferrocyanid solution cool and dilute to exactly 1000 
 mils. 
 
 Twenty-five mils of this reagent are reduced by 0.05 gm. of 
 glucose. 
 
 BROMIN WATER. Add 3 mils of Br to 100 mils of water, 
 agitate, allow to stand and decant for use. 
 
 DIAZO REAGENT. No. I sodium nitrite 1 gm. Distilled 
 water to make 200 mils. 
 
 No. II. Sulphanilic acid, 5 gms. Hydrochloric acid U. S. P. 
 50 mils. Distilled water to make 1000 mils. 
 
 The solutions should be mixed, just before using, in the pro- 
 portion 1 part of No. I and 50 parts of No. II. 
 
 DIMETHYL- AMINOAZO-BENZENE. 1 gm. in 200 mils alcohol. 
 DRAGENDORFF'S REAGENT. 1.5 gm. BiONOs, boil with 
 
QUALITATIVE ANALYSIS OF ORGANIC SUBSTANCES. 179 
 
 20 mils of water, add 7 gms. KI, shake and add 20 drops of dilute 
 HC1. 
 
 ESBACH'S REAGENT. 10 gms. picric acid, 20 gms. citric 
 acid and water to make 1000 mils. 
 
 FEHLING'S REAGENT. No. 1. Dissolve 34.66 gms. of care- 
 fully selected, small crystals of cupric sulfate in sufficient dis- 
 tilled water to make 500 mils at 25 C. 
 
 No. 2. Dissolve 173 gms. of crystallized Rochelle salt and 
 50 gms. of sodium hydroxid U. S. P. in sufficient distilled water 
 to make 500 mils at 25 C. Keep the solutions separately in 
 small rubber-stoppered bottles. For use, mix equal volumes of 
 the two solutions at the time required. 
 
 FROEHDE'S REAGENT. 1 gm. sodium molybdate and 10 
 mils strong sulfuric acid. 
 
 FUCHSIN-SULFUROUS ACID T.S. To a solution of 0.5 gm. 
 of fuchsin and 9 gms. of sodium bisulphite in 500 mils of distilled 
 water, add 10 mils of strong hydrochloric acid. Preserve in well- 
 stoppered bottles protected from light. 
 
 FUSING MIXTURE. 1 part of Na 2 C0 3 and 3 parts of KNOs. 
 
 GUNZBERG'S REAGENT. 1 gm. vanillin, 2 gm. phluroglucin 
 and 100 mils of alcohol. 
 
 HAINE'S SUGAR REAGENT. 2 gms. copper sulfate dis- 
 olved in 15 mils of water. Add 15 mils of glycerin. Mix well 
 and add 150 mils liquor potassa U. S. P. 
 
 IODIN SOLUTION. 1 gm. iodin, 3 gm. potassium iodid, and 
 50 mils of water. 
 
 MAGNESIA MIXTURE. 5.5 gms. magnesium chlorid, 7 gms. 
 ammonium chlorid, 35 mils ammonia water, and water to make 
 100 mils. 
 
 MAYER'S REAGENT. 1.358 gms. mercuric chlorid in 60 mils of 
 distilled water, add 5 gms. of potassium iodid in 10 mils of dis- 
 tilled water. Mix the two solutions and add enough water to 
 make 100 mils. 
 
180 QUALITATIVE CHEMICAL ANALYSIS. 
 
 MILLON'S REAGENT. 1 part of metallic mercury by weight, 
 and 2 parts of strong nitric acid by weight; warm gently until 
 all of the mercury is dissolved, and then dilute with 6 parts of 
 water. 
 
 NESSLER'S REAGENT. Dissolve 10 gms. of potassium iodid 
 in 10 mils of distilled water and add gradually in portions a 
 saturated solution of mercuric chlorid with constant agitation 
 until a slight red precipitate remains undissolved. To this mix- 
 ture add 30 gms. of potassium hydroxid and when solution has 
 taken place, 1 mil more of the mercuric chlorid solution. 
 Dilute this solution with distilled water to make 200 mils. Allow 
 the precipitate to subside, and draw off the clear fluid. 2 mils 
 of this reagent added to 50 mils of distilled water containing 0.05 
 milligram produces a yellowish brown coloration. 
 
 NYLANDER'S REAGENT. 4 gms. Rochelle salt, 2 gms. bis- 
 muth subnitrate and 10 gms. sodium hydroxid (dissolved in 90 
 mils of distilled water). Keep in amber-colored vials. 
 
 OBERMEYER'S REAGENT. 0.4 gm. of pure ferric chlorid 
 are dissolved in sufficient pure, strong hydrochloric acid to make 
 100 mils. 
 
 PICRIC ACID T.S. (Trinitrophenol T.S.) C 6 H 2 (N0 2 )30H.- 
 Dissolve 1 gm. of picric acid in 100 miis of distilled water by the 
 aid of heat'. 
 
 TANNIC ACID T.S. Dissolve 1 gm. of tannic acid in 1 mil 
 of alcohol, and add sufficient distilled water to measure 10 mils. 
 Prepare freshly when needed. 
 
 TANRET'S REAGENT. No. I. 1.35 gms. of mercuric chlorid 
 dissolved in 30 mils of hot water. No. II. 3.32 gms. of potas- 
 sium iodid dissolved in 30 mils of water. Mix the two solutions. 
 Add 20 mils of acetic acid and make up to 100 mils with water. 
 
INDEX. 
 
 Acetaldehyde, 147 
 Acetanilid, 138 
 Acetates, 114 
 Acetic acid, 114 
 Acetic ether, 149 
 Acetone, 170 
 Acetphenetidin, 139 
 Acid salt, 13 
 Acid, acetic, 114 
 
 arsenic, 102 
 
 arsenous, 103 
 
 benzoic, 115-135 
 
 boric, 99 
 
 carbolic, 151 
 
 carbonic, 91 
 
 chromic, 103 
 
 citric, 121 
 
 gallic, 117 
 
 hydriodic, 107 
 
 hydrobromic, 107 
 
 hydrochloric, 106 
 
 hydrocyanic, 94 
 
 hydrofluoric. 101 
 
 hydrofluorsilicic, 97 
 
 hydrosulfuric, 91 
 
 hypophosphorous, 112 
 
 lactic, 124 
 
 malic, 123 
 
 meconic, 118 
 
 meta-phosphoric, 99 
 
 nitric, 110 
 
 nitrous, 110 
 
 oleic, 124 
 
 oxalic, 100 
 
 phenic, 151 
 
 phosphoric, 97 
 
 Acid, picric, 138 
 
 picric, T. S., 180 
 pyrogallic, 117 
 pyrophosphoric, 99 
 salicylic, 116 
 succinic, 118 
 sulfuric, 97 
 sulfurous, 92 
 stearic, 125 
 tannic, 117 
 tannic, T. S., 180 
 tartaric, 122 
 trichloracetic, 118 
 uric, 172 
 valerianic, 125 
 valeric, 125 
 Acid3, preliminary examination of the 
 
 dry substance, 89 
 Group A, characteristic tests 
 
 of, 91 
 
 Group A, chart for observa- 
 tion of the reactions of, 95 
 chart of ; 89 
 table of, 87 
 Group B, characteristic tests 
 
 of, 97 
 
 chart for observa- 
 tion of reactions 
 of, 105 
 chart of, 96 
 table of, 87 
 Group C, characteristic tests 
 
 of, 106 
 
 chart for observa- 
 tion of reactions 
 of, 109 
 181 
 
182 
 
 INDEX. 
 
 Acids, preliminary examination of the 
 dry substance -continued 
 Group C, chart of, 106 
 
 table of, 87 
 Group D, characteristic tests 
 
 of, 110 
 
 chart for observa- 
 tion of reac- 
 tions of, 113 
 table of, 88 
 Group E, characteristic tests 
 
 of, 114 
 
 chart for observa- 
 tion of reac- 
 tions of, 119 
 chart of, 114 
 table of, 88 
 Group F, characteristic tests 
 
 of, 121 
 
 chart for observa- 
 tion of reac- 
 tions of, 123 
 chart of, 121 
 table of, 88 
 Group G, characteristic tests 
 
 of, 124 
 
 chart for observa- 
 tion of reac- 
 tions of, 126 
 table of, 88 
 names of, 13 
 
 systematic analysis of, 88 
 Table of, 10 
 Aconitine, 131 
 Adhesion, 5 
 Albumen, 163 
 Alcohol, 143 
 Alloys, 78 
 Aloin, 134 
 Aluminum, 50 
 Ammonium, 70 
 Amyl alcohol, 150 
 nitrite, 150 
 Analysis, dry way, 18 
 
 microscopical, 18 
 
 Analysis, polariscopic, 18 
 qualitative, 17 
 spectroscopic, 18 
 wet way, 18 
 Anhydrid, 16 
 Antimony, 37 
 
 Reinch's test for, 36 
 Antipyrine, 138 
 Apomorphine, 132 
 Aristol, 135 
 Arsenates, 102 
 Arsenic, 34 
 
 acid, 102 
 
 Bettendorff's test, 36 
 Fleitman's test, 35 
 Marsh's test, 35 
 Reinch's test, 36 
 U. S. P. test, 36 
 Arsenites, 103 
 Arsenous acid, 103 
 salts, 34 
 Atom, 2 
 
 Atomic weight, 5 
 Atropine, 132 
 
 Barium, 61 
 
 Bases, 12 
 
 Basic salt, 13 
 
 Benedict's reagent, qualitative, 177 
 
 quantitative, 178 
 Benzaldehyde, 150 
 Benzene, 149 
 Benzine, 149 
 Benzoates, 115-135 
 Benzoic acid, 115-135 
 Benzoic aldehyde, 150 
 Benzol, 149 
 Benzcsulfmid; 139 
 Betanaphthol, 142 
 Bettendorff's test for arsenic, 36 
 Bicarbonates, 91 
 Bile, 169 
 Bismuth, 32 
 Blood, 169 
 Bonds, 5 
 
INDEX. 
 
 183 
 
 Borates, 99 
 Boric acid, 99 
 Bromates, 111 
 Bromids, 107 
 Bromin water, 178 
 Brucine, 131 
 Butyl chloral, 135 
 
 Cadmium, 33 
 Caffeine, 132 
 Calcium, 63 
 Camphor, 136 
 
 monobromated, 141 
 Cane sugar. 137 
 Carbamid, 171 
 Carbinol, 144 
 Carbolates, 118 
 Carbolic acid, 151 
 Carbon, detection of, 127 
 Carbonates, 91 
 Carbonic acid, 91 
 
 Chart, for the comparative observa- 
 tion of the reactions of 
 metals with three com- 
 monly used reagents, 78 
 for comparison of phenol and 
 
 creosote, 151 
 
 for comparison of tannic, gallic 
 and pyrogallic acids, 117 
 for detection and separation 
 of a mixture of five groups 
 of metals, 83-86 
 for separation of alloys and 
 
 hard metals, 78 
 for separation of insoluble 
 
 phosphates, 75 
 
 for separation of a solution 
 into groups of metals, 82 
 showing effect of group rea- 
 gents on the naetals, 23 
 Chemical change, 3 
 Chemism, 4 
 
 Chemistry, definition of, 3 
 inorganic, 3 
 organic, 3 
 
 Chloral, 135 
 Chloralamid, 140 
 Chloralformamid, 140 
 Chlorates, 111 
 Chlorids, 107 
 
 in urine, 172 
 
 Chlorin, detection of, 127 
 Chloroform, 149 
 Chromates, 104 
 Chromic acid, 103 
 Chromium, 50 
 Cinchonidin, 134 
 Cinchonjn, 134 
 Citrates, 121 
 Citric acid ; 121 
 Cobalt, 52 
 Cocaine, 132 
 Codeine, 132 
 Cohesion, 5 
 Compounds, 2-4 
 
 classification of, 12 
 Copper, 32 
 Creatinin, 170 
 Creosote, 151 
 Cyanids, 94 
 
 Dextrin, 137 
 
 Diazo reagent, 178 
 
 Diethyl sulfondimethylmethane, 140 
 
 Dimethyl-aminoazo-benzene, 178 
 
 Double salt, 13 
 
 DragendorfPs reagent, 178 
 
 Elaterin, 134 
 Elements, 2 
 Equations, 12 
 Esbach's reagent, 179 
 Ether, 148 
 
 acetic, 149 
 
 petroleum, 149 
 Ethyl acetate, 149 
 
 alcohol, 143 
 
 carbamate, 140 
 
 oxid, 148 
 
184 
 
 INDEX. 
 
 Fehling's reagent, 179 
 Ferric salts, 48 
 Ferricyanids, 109 
 Ferrocyanids, 108 
 Ferrous salts, 49 
 Fleitman's test, 35 
 Fluorids, 101 
 Fluorsilicates, 97 
 Formaldehyd, 148 
 Formalin, 148 
 Formic aldehyd, 148 
 Formula, 11 
 Froehde's reagent, 179 
 Fuchsin-sulfurous acid, 179 
 Fusel oil, 150 
 Fusing mixture, 179 
 
 Gallates, 117 
 Gallic acid, 117 
 Glucose, 137 
 
 in urine, 164 
 Glusidum, 139 
 Glycerin, 152 
 
 Glycerol propenyl alcohol, 152 
 Grain alcohol, 143 
 Grape sugar, 137 
 Guaiacol, 142 
 
 carbonate, 141 
 Guaiacum, 138 
 Gums, 137 
 Giinzberg's reagent, 179 
 
 Haines reagent, 179 
 Hydriodic acid, 107 
 Hydrobromic acid, 107 
 Hydrochloric acid, 106 
 Hydrocyanic acid, 94 
 Hydrofluoric acid, 101 
 Hydrofluorsilicic acid, 97 
 Hydrogen, detection of, 127 
 Hydrosulfuric acid, 91 
 Hypochlorites, 96 
 Hypophosphites, 112 
 Hypophosphorous acid, 112 
 
 lodates, 111 
 lodids, 107 
 Iodine reagent, 179 
 lodoform, 135 
 lodol, 135 
 Indican, 168 
 Iron salts, 48-49 
 
 scaled salts, 154 
 
 Lactates, 124 
 Lactic acid, 124 
 Lead, 24 
 Lithium, 69 
 
 Magnesia mixture, 179 
 Magnesium, 67 
 Malates, 123 
 Malic acid, 123 
 Manganese, 51 
 Marsh test, 35 
 Mass, 2 
 
 Matter, continuity of, 1 
 Mayer's reagent, 179 
 Meconates, 118 
 Meconic acid, 118 
 Menthol, 136 
 Mercuric salts, 31 
 Mercurous salts, 25 
 Metals, classification of, 7 
 
 Group I: comparative obser- 
 vation of reac- 
 tions of, 27 
 Identification in a 
 simple salt, 28 
 Notes on separa- 
 tion of, 29 
 Separation of, 29 
 Special tests for, 24 
 Synopsis of separa- 
 tion of, 28 
 
 Group II: Comparative ob- 
 servation of 
 reactions cf, 
 39-40 
 
INDEX. 
 
 185 
 
 Metals, classification of Continued 
 Group II: identification in a 
 simple salt, 41 
 notes on separa- 
 tion of, 45 
 observations on 
 separation of, 
 44 
 
 separation of, 43 
 special tests for, 30 
 synopsis of sepa- 
 ration, 42 
 
 Group III: comparative ob- 
 servation of 
 reactions of, 
 54-55 
 
 identification in a 
 simple salt, 
 56 
 
 short method of 
 separation in 
 a simple salt, 
 57 
 
 notes on separa- 
 tion of, 60 
 observations on 
 separation 
 of, 59 
 
 separation of, 58 
 special tests for. 
 
 48 
 
 synopsis of sepa- 
 ration of, 57 
 
 Group IV: comparative ob- 
 servations of 
 reactions of, 
 64 
 
 identification in a 
 simple salt, 
 65 
 
 notes on separa- 
 tion of, 67 
 observations on 
 separation of, 
 66 
 
 Metals, classification of Continued 
 Group IV: separation of, 66 
 special tests for, 
 
 61 
 
 synopsis of sepa- 
 ration, 65 
 
 Group V : comparative obser- 
 vation of reac- 
 tions of, 71 
 identification in a 
 simple salt, 72 
 notes on separation 
 
 of, 73 
 
 observations on 
 separation of, 
 73 
 
 separation of, 73 
 special tests for, 67 
 synopsis of separa- 
 tion, 72 
 hard, 78 
 
 separation of groups of, 20 
 table of, 9 
 
 Metaphosphoric acid, 99 
 Methyl alcohol, 144 
 Milk sugar, 137 
 Millon's reagent, 180 
 Mixture, mechanical, 4 
 Molecular attraction, 4 
 
 weight, 5 
 Molecule, 2 
 Morphine, 131 
 
 Naphthalene, 139 
 Naphthol, 142 
 Nessler's reagent, 180 
 Nickel, 53 
 Nitrates, 110 
 Nitric acid, 110 
 Nitrites, 111 
 Nitrobenzene, 153 
 Ntirobenzol, 153 
 Nitrous acid, 110 
 Nitrogen, detection of, 127 
 Non-metals, table of, 8 
 
186 
 
 INDEX. 
 
 Normal salt, 13 
 Nylander's reagent, 180 
 
 ObermByer's reagent, 180 
 Oil mirbane, 153 
 Oleates, 124-136 
 Oleic acid, 124 
 Oxalates, 100 
 Oxalic acid, 100 
 Oxgall, 136 
 Oxid, 16 
 
 Paraldehyd, 148 
 Peptones, 164 
 Permanganates, 112 
 Petroleum ^ther, 149 
 Phenacetin, 139 
 Phenazonum, 138 
 Phenic acid, 151 
 Phenol, 135-151 
 Phenolates, 118-135 
 Phenolsulfonates, 117-135 
 Phenyldimethyliso-pyrazolon, 138 
 Phenyl salicylate, 142 
 Phosphates, 97 
 
 insoluble, 74 
 
 in urine, 173 
 Phosphoric acid, 97 
 Phosphorus, detection of, 128 
 Physical change, 3 
 Physostigmine, 131 
 Picric acid, 138 
 Picric acid T. S., 180 
 Potassium, 68 
 Precipitate, 19 
 Pyrogallates, 117 
 Pyrogallic acid, 117 
 Pyrophosphoric acid, 99 
 
 Quantivalence, 5 
 Quinidine, 133 
 Quinine, 133 
 
 Reagents, 18-176 
 
 acid, 176 
 
 Reagents, confirmatory, 19 
 gases, 177 
 general, 18 
 salts, 176 
 separatory, 19 
 special, 19-177 
 
 Reinch's test, for antimony, 36 
 for arsenic, 36 
 
 Report on uranalysis, 175 
 
 Resin.. 138 
 
 Resorcin, 141 
 
 Resorcinol, 141 
 
 Saccharin, 139 
 Salicin, 134 
 Salicylates, 116 
 Salicylic acid, 116 
 Salol, 142 
 Salts, acid, 13 
 
 basic, 13 
 
 double, 13 
 
 normal, 13 
 
 names of, 14 
 
 scaled iron, 154 
 Santonin, 134 
 Silica, 101 
 Silicates, 102 
 Silver, 25 
 Soap, 136 
 Sodium, 69 
 
 Solubilities, table of, 81 
 Stannic salts, 37 
 Stannous salts, 38 
 Starches, 137 
 Stearates, 125-136 
 Stearic acid, 125 
 Strontium, 62 
 Strychnine, 132 
 Succinates, 118 
 Succinic acid, 118 
 Sugar, cane, 137 
 
 grape, 137 
 
 milk, 137 
 Sulfates, 97 
 
 in urine, 174 
 
INDEX. 
 
 187 
 
 Sulfids, 92 
 Sulfites, 92 
 Sulfocarbolates, 117 
 Sulfocyanates, 108 
 Sulfomethane, 140 
 Sulfonal, 140 
 Sulfonethylmethane, 140 
 Sulfur, detection of, 128 
 Sulfuric acid, 97 
 Sulfurous acid, 92 
 Symbols, 7 
 
 importance of, 10 
 Synthesis, 17 
 
 Table, acids, 10 
 metals, 9 
 non-metals, 8 
 
 Tannates, 117 
 
 Tannic acid, 117 
 
 Tannic acid T. S., 180 
 
 Tanret's reagent, 180 
 
 Tartaric acid, 122 
 
 Tartrates, 122 
 
 Terpin hydrate, 142 
 
 Thiocyanates, 108 
 
 Thiosulfates, 93 
 
 Thymol, 136 
 
 Tin, 37-38 
 
 Trichloracetic acid, 118 
 
 Trichlormethane, 149 
 
 Trinitrophenol T. S., 180 
 
 Trional, 140 
 
 Uranalysis, 162 
 Urea, 171 
 Urethane, 140 
 
 Uric acid, 172 
 Urine, 162 
 
 acetone in, 170 
 
 albumen in, 163 
 
 bile in, 169 
 
 blood in, 169 
 
 carbamid in, 171 
 
 chlorids in, 172 
 
 creatinin in, 170 
 
 glucose in, 164 
 
 indican in, 168 
 
 microscopical examination of, 
 174 
 
 peptones in, 164 
 
 phosphates in, 173 
 
 report on, 175 
 
 sulfates in, 174 
 
 urea in, 171 
 
 uric acid in, 172 
 
 Uroxanthine indoxyl-potassium sul- 
 fate, 168 
 
 Valence, 5 
 Valerates, 125 
 Valerianic acid, 125 
 Valeric acid, 125 
 Veratrine, 133 
 
 Weights, atomic, 5 
 
 molecular, 5 
 Wood alcohol, 144 
 
 Zinc, 51 
 
QD81 
 
 S33 
 
 1917 
 
 ST. 
 
 Schimpf, ] 42221 
 A systematic vourse of 
 qualitative chemical anal- 
 ysis of organic and inorgan 
 ic substances.^ 3d ed....