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Five in number, one each of the fol- lowing: Mammaua; Bibdh; Reptiles and }<'i8iie8 ; Invshtkbbates; MiNEUALS, Rooks nnd Fossils. In all, over 7lK) lUuBtrations. Wholly hand colored ■ Price of each chart, $7.00. The set, $30.00. NATURAL HISTORY PRIMER. A concise descriptive work on Zool- OUY aud MiNKBALOOT. Price $1.00. CATALOOU8 POLYGLOTTUS, Or classiflnd list of the more important animals, minerals and fossils In Latin, Kngllth, French, German and Spanish : for Scientillc Travelers, Collectors, Curators of Musenras and others. Price $8.00. IN PREPARATION. THE CHEMISTRY OF BUILDING MATERIALS. COPYRIGHT C. GILBERT WHEEI ER. 1878. 1^ LER. the recogni- 8100. :l»ofthefol- "TEBIUTKS; 'n». Wholly $30.00. irk on Zooi, 8100. 9 important Jerman and MusenmB $8.00. ■J i I CONTENTS. U' — PAOE Inteoductort, - a 7 Classification of Orqanio CoMPOuifDS, 10 Homologous Series, _ 12 Hydrocarbons, - - 18 Alcohols, . 44 " MONATOMIO, - 46 " Diatomic, - 58 " Triatomio, - 64 E::hers, . 69 Aldehtds, - 86 Acids, • 90 " MONATOMIO, 96 " Polyatomic, - m 112 Alkaloids or Bases, s - 127 " Artificial, . 132, 170 " Natural, - 137 Neutral Fatty Bodies, . ' 174 Sugars, - 181 Glucosides, • 193 Vegetable Chkmistrt, - 199 Cklt-ulosb, - . 205 Starch, - 210 Dextrin, . 214 Gums, - • - - 216 Animal Chemistry, Albuminoids, Fibrin, - - - Casein, Digestion, - • Saliva, . . - Gastric Juice, Bile, . . - Pancreatic Juice, Chyle, Lymph, Blood, HiEMOQLOBULIN, - Chemical Pathology of the Blood, Respiration, Animal Heat — Muscular Power, Assimilation, Secretion — 'The Urine, Chemistry of Normal Urine, " " Abnormal " Urinary Sediments, ,- " Calculi, Analysis of Urine, " Urinary Deposits, " Calculi, - Sweat, - Milk, . . » The Soft Tissues, Osseous Tissue, Dental " - Exudations, « PAQR. 221 225 231 233 28G 237 242 250 261 270 272 286 294 301 316 321 333 339 347 852 353 356 364 368 370 876 383 896 403 407 221 226 281 288 286 287 242 250 261 270 272 285 294 301 816 321 333 339 347 352 353 356 364 368 370 376 383 396 403 407 PREFACE. Medical chemistry has not as yet secured in Ameri- can colleges sufficiently prononiiced attention to create a demand for text-books of considerable size or ex- tended scope. In these simple Outlines, therefoia, no more has been attempted than this circumstance would appear to warrant. It is hoped that the necessary conciseness in method and form of expression has not resulted in any important sacrifice of perspicuity in thought or arrangement. It would have been easier to prepare a larger work. From the bewildering wealth of results afforded by the labors of investigators in this branch of science, the ap- propriate selection of that suited to the wants of stu- dents was by no means an easy task. It is assumed in these Outlines that those entering upon the study of Medical Chemistry have previously made themselves acquainted with Inorganic Chemistry as taught by some recent author, such as Miller or Barker, or have at least become familiar with the gen- eral principles of modern chemical philosophy. The author taking this for granted, has not, therefore, en- cumbered the work with a .estatement of that which appertains to the theory of chemistry in general. In addition to the organic portion of Riche's Man- uel de Chimie, a translation of which by the author PREFACE. has served in part as basis for these Outlines, the works of Miller, Fownes, Williamson, Eoscoe, and others have been freely used, wiiile the chemical journals of Europe and America, including their latest numbers, have been consulted and the data which they afforded utilized. Where the excerpta have been ft-om journals of too recent issue to be found in standard authors, a refbiouce in brackets has been made to the original source. Of the three series of numbers thus employed, the first has reference to the list of journals given at the close of this work, the second usually refers to the number of ^ the volume, though sometimes to the year, the third indicates the page. Lest any regard the number of characteristic re- actions of the more important compounds as insuffi- cient, it should be stated, that it was not within the plan of the author to adapt this work to the requirements of an analytical manual. Not more than two or three analytical tests are therefore given as a rule, and even this number only in the case of the leading compounds. A similar explanation might be proffered to any who may miss the full technical de- tails relative to certain compounds which are usually given in works on applied, or technological chemistry. Throughout the work, the centigrade thermometer and the metric system of weights and measure^ are employed, unless otherwise specifically stated. C. GlLB-^ET WhEBO^E^ Univebsity of Chicaqo, December, 1878. ORGANIC CHEMISTRY. INTRODUCTORY. Organic chemistry is the science of the compouuds of carbon. Only a small number of other elements are met with in natural organic substances; they are hydrogen, ox3-gen and nitrogen, sometimes also, sulphur, phos- phoms, and very rarely certain other elements. Chemists have succeeded in incorporating most of the elemental substances In organic bodies, yet the larger number even of the artificial compounds include only the four elements first named. Parafflne is found by analysis to contain only carbon and hydrogen, and is therefore caued a hydrogen- carbide. The hydrocarbides are compounds so stable and fundamental that some chemists, as Schorlemmer for instance, have eveu defined organic chemistry as «* the chemistry of hydrocarbons and their derivatives." From alcohol, or sugar, we may obtain carbon and water. These bodies therefore are composed of three elements: carbon, hydrogen and oxygen, and are called carbohydrates ; though by some chemists, this term is restricted to those compounds coutaining car- 8 ORGANIC OHEMISTBT. bon with hydrogen, and oxygen in such proportions as would form water. If albumen is decomposed by heat, the result is not onh' carbon and water, but also ammonia ; this sub- stance accordingly is nitrogenous. The number of organic bodies is verj' great. As they are composed of a small number of elements only, it may be concluded that the latter unite in a very great variety of proportions ; it is therefore of much impor- tance to know the molecular grouping of these ele- ments. .The mere fact that the kind and number of elements entci-ing into a compound are known, is not sufficient proof that its molecular structure is really determined. Synthesis must often be employed to confirm the results of analysis. Berthelot has specially occupied himself with the synthesis of organic bodies, and has artificially produced a great number of them. Other chemists have experimented in the same direction during the last 15 or 20 years. However, Gerh ..-dt's opinion advanced in 1854; viz., " The vital force alone operates by syn- thesis and reconstructs the edifice demolished by chemical afllnity," has ceased to be held as true. ISOMEEISM. Carbon, hydrogen, oxygen and nitrogen are not only capable of uniting in a great variety of proportions, but these elements also furnish numerous isomerio bodies ; these comprise substances which, while com- ikai^ ISOMERISM. 9 posed of the same elements, have different properties. Sometimes the physical properties alone are different; we then have physical isomeriam. When the chemical properties tiiemselves are modi- fied, this is denominated chemicaZ isomerism. Qi the latter, two kinds are recognized. I. Pclymerism; cyanogen and paracyanogen are exampli \ of this variety of isomerism ; the latter is to be considered as cyanogen, CIJ^" condensed, thus (CN)n ; it is a polymeride of cyanogen. The weight of the molecule of these two substances is therefore dif- ferent. II. Metamerism. At other times the isomerism results from a different grouping of elements in the compound, the molecular weight remaining the same. We will illustrate this by two examples : a) Methyl acetate, and b) Ethyl formiate. J^cetic acid — H-O-CallsO. Methyl hydrate, or methyl alcohol=H-0-CH3. When these two bodies react they furnish water and methyl acetate, CHs-O-CjHjO—OaHsOa. Formic acid=H-0-CHO. Ethyl hydrate, or ethyl alcohol=H-0-OBH5. Now formic acid contains CHg less than acetic acid, and hydrate of ethyl contains one molecule of CHg more than does hydrate of methyl. As tbese substan- ces in reacting lose one molecule of water, it is there- fore clear that the compound obtained will have, like the preceding one, the formula CjHjOg. But these 10 OBGANIO CHEMISTRY. two prodncta are not identical substances, for the for- mer treated with alkalies regains the molecule of water which it had lost, reforming acetic acid and methyl hy- drate, while the latter regenerates formic acid and ethyl hydrate. These bodies accordingly differ in the arrangement of their molecule ; they are called metameriG bodies. Finally there exist bodies which are isomeric, prop- erly so-oalled, possessing the same formula, having the same general reactions, the same chemical functions, and which differ only in a very few, chiefly physical, properties : such are oil of turpentine and oil of lemon, each having the formula C, ,H, ,. CLASSIFICATION" OF ORGANIC COM- POUNDS. Chemical Types. — The idea of referring organic bod- ies to some simple model, or type, was originally work- ed out by Laui-ent and Gerhaidt, 1846-53. though the germs of their ideas on classification are to be found in the earlier papers of the distinguished American chemist T. Sterry Hunt. {Am. Jour. Sci. [2] xxxi.) Tlie four principal types are : I. The hydrogen type, ^! I or H,. II. The oxide or water type, ^, \o" orHgO. H' ) III. The nitride or am moniatype,H' )-N"'orH,N". H' I ' ORGANIC TYPES. 11 IV. The marsh gas type ^ ' }■ C'^ or H^O. H' Of the leading groups of organic bodies, we refer to the hydrogen type: hydrocarbides, aldehyds and the compounds of metals and metalloids with organic radicals. To the water type are referred the alcohols, ethers, mercaptans and anhydrides. To the ammonia type belong the amides, amines, and alkalamides, all of which are denominated com- pound ammonias. Marsh-gas is the type to which carbon dioxide is referred, as well as some of the more complex organo- metallic bodies. Further details as to the relation of each of these classes of compounds to their respective types will be given as each particular class is studied. Besides the simple type, Kekul^ has proposed com- pound types formed by the combination of two of the four types already given. Thus the types of ammonia and water combined serve as a pattern for carbamic and oxamic acids: ;[n"' H' H H H' Carbamic acid. Oxamic Acid. 12 ORGANIC CHEMISTRY. HOMOLOGOUS SERIES. The members of a series of compounds which have the common difference of CHj are said to be homolo- gniis. Two or more such homologous series are termed isologoita. The first idea of progressive series in organic chemistry was enunciated by James Schiel, of SL Louis, Mo., in 1842. It was afterwards adopted by Gerhardt uncli .aged, save only in name. (100-5-195.) The subjoined table will illustrate the nature of these series. Each vertical column forms a homologous series in which the terms differ by CHg, and each hori- zontal line an isologous series in which the successive terms differ by Hg. The bodies of these last series are designated as the mouocarbon, dicarbon group, etc. C H4 C Hg CgH. CgH, Cg. CsHg CsHj C3H4 CsHg C4H10 C4H« C.H, C.H, C^Hg CsHjg CJIto CbH« C«H, C,H4 C«Hg CeHi^ CeHis CbHio CeHg CeH« C,H, CeHg The terms of the same homologous series resemble one another in many respects, exhibiting similar trans- formations under the action of given re-ngents, and a regular gradation of properties from the lowest to the highest ; thus, of the hydro-carbons, Cnlljn^ the low- est terms CH4^ CjHe, and'CsHg^ are gaseous at ordinary temperatures, the highest containing 20 or more car- HOMOLOOOUS SERIES. 13 have molo- srmed ganic f SL d by ■195.) these DgOUS hori- 38sive ssare to. mble rans- nd a ) the low- nary caj*- bon-atoms, are solid, while the intermediate com- ponnds are liquids, becoming more and more viscid and less volatile, as they contain a greater number of car- bon-atoms, and exhibiting a constant rise of about 20° C. (36° F.) in their boiling points for each addition of CIIj to the molecule. The individual series are given in the following ta- ble, with the names proposed for them by A. W. HoiFmann: Methane Methene CII4 CHj Ethane Ethene Ethine CaH, C,H4 CjHa ( Propane Propene Propine Propone CsHs CsHj C3H4 C3H2 Quartane Quartene Quartine Quartone Quartune C4H,o C4H8 C4He C4H4 C4Ha Quintane Quintene Quintine Quintone Quintune CsHia CsHjo CsHa OsHe C5H4 Sextane Sextene Sextine Sextone Sextune CeHu CeHi, CeHjo CeHg CeHg The formulae in the preceding tables represent hydro- carbons all of which are capable of existing in the separate state, and many of which have been actually obtained. They are all derived from saturated mole- cules, OnHan+a, by abstraction of one or more pairs of hydrogen-atoms. But a saturated hydrocarbon, CH4, for example, may lifwiiiiii w 14 ORGANIC CHEMISTRY. give up 1, 2, 8, or any number of hydrogen-atoms in exchange for other elements ; thus marsh gas, CH4. subjected to the action of chlorine under various cir- cumstances, yields the substitution-products, CH3C], CH3CI2, CHOI3, CCI4, which may be regarded as compounds of chlorine with the radicles, (CHa)', (CH,)", (CH)'", C'-, and in like manner each hydrocarbon of the series, OnHan+a, may yield a scries of radicles of the forms, (C„H^O'» (C„H^)", (C„Ha„.0 '" (C^H^-^n&c each of which has an equivalent value, or combining power, corresponding with the number of hydrogen- atoms abstracted from the original hydrocarbon. Those of even equivalence contain even numbers of hydro- gen-atoms, and are identical in composition with those in the table above given ; but those of uneven equiva- lence contain odd numbers of hydrogen-atoms, and are incapable of existing in the separate state, except, perhaps, as double molecules. These hydrocarbon radicles of uneven equivalence are designated by Hoffmann, with names ending in yl, those of the univalent radicles being formed from methane, ethane, &c., by changing the termination ^^l Uh -««Wt Jl^ »tl'»l! ^W I* . » .>tf T;3WWHN« «gw i mjtflw i WM HOMOLOGOUS SERIES. 16 IS m OH4, cir- wiHa. nes, kc. ling jen- lose Iro- ose !va- md !pt, ace >m ion ane into yl ; those of the trivalent radicles by chang- ing the final e in tho names of the bivalent radicles, methene. &c., into yl; and similarly for the rest. The names of the whole series will therefore be as follows : CH, (CH3)' (CH,)" (OH)'" Methane Methyl Methene Methenyl C,He (CA)' (CJI4)" (CA)'" Ethane Ethyl Ethene Ethenyl CaHg (C3H,)' (CsHe)" (C3H5)'" Propane Propyl Propene Propenyl &c. &c. &c. From these hydrocarbon radicles, others of the same degree of equivalence may be derived by partial or total replacement of the hydrogen by other elements, or compound radicles. Thus ivova propyl, CsEj, may be derived the following univalent radicles: — CsH^Cl C3H8CI4 Chloropropyl Tetrachloropropyl CsHjClsO CsHeCCN)' Trichloroxypropyl CyanopropyL 03ll4(NH2)O C3He(CHa) Amidoxypropyl Methylpropyl C3HSO Oxypropyl CaHflCNOa) Nitropropyl CaHs(C2H«)a Diethylpropyl. From the radicles above mentioned, all well-defined organic compounds may be supposed to be formed by combination and substitution, each radicle entering into combination, just like an elementary body of the same degree of equivalence. 16 OBGANIO CHKM18TRY. TABLE TO ILLU8THATB THE ARRANGEMENT OF THE MORE Series. Hydro- catboui. Sniphldes. Chlorides or Haloid Kther.i. Alcohols. 1 General FormDift. CnHan CnTTaw+i 1 „ CnHj«+i \° CnHan+iCl CnHan+i 1 „ II fO I. C Ha (C H3)aB C H3 CI H3 no a. Ca H4 (uaH5)aS CaHs CI CaHs HO 3. C3Hg C,lH7 CI C3H7 no > 4. OiHg C4H9 CI C4H9 HO S. Cj Hio (CjHiOaS CsHnCl CsHiiHO 6. Cg Hia C6H13HO 7. C7H14 ■ 8. Cg H16 C8U17CI C8H17HO 9- C9 H18 1 10. CioHao t Types HI Hf HI Hf Sb t_- ORGANIC COMPOUNDS. 17 IMPORTANT OHQANIC COMPOUNDS IN HOMOLOOOUS BBHIE3. ■}o MercaptaD«. Aldehydi. Actdi. Simple £tberH Compound Bthers. OnHan+i (.„ C»Han-i H CoIbM-iO) » HfO CnHan+i 1 ^ CnHan+i t-. CnHan-iOj" 0^3 HS H 0,H HC U Oa (0 H3)aO C H3 H Oa 1. CaH5 HS Ca H3 0,H HCa H3 Oa (OaHs)aO CaHs Ca H3 Oa a. O3 Hs 0,H HC3 H5 Oa CaHs C3 Hs Oa 3. O4H9H8 0* H7 0,H HC4 H7 Oa CaHs C4 H7 Oa 4. C5H11HS Cs H9 0,H HCs H9 Oa (C5Hi.)aO CsniiCsH9 0a j. C6 HiiO.H H06 UiiOa CaHs Cg HiiOa 6. C7 Hi30,H HC7 Hi30a HCg H>s0a HC9 Hi70a • CiHs C7 Hi30a 7. CaHs Cg HisOa 8. CaHs C9 Hi70a 9. CioHrpHiO H0ioHi9Oa (CioHai)aO CaHs CioHi90a 10. S}o Hi Hf g[o g[o l}o KSmmi^smm m ' t m imi t f.. '^'^^^^^'^ ^'''^'^'imii^^sim^^ m iii , ii »; .^»i> i , j ii iiiiii M i i ' ■ mi ! . *; ss l^. ORGANIC CIIEMISTUTf. CAKBIDES OF IIYDEOGEN. The origin or preparation of these componnds, also called hydrocarhides, and their properties, physical and chemical, all differ largely. They are unlike the hydrogen combinations studied in inorganic chemistry inasmuch as they possess b>it feeble chemical energy Among the carbides are: acetylene, marsh-gas or methane, ethylene, oil of tnr. pentine and of lemon, benzol, naphthalin, petroleum, caoutchouc, gutta-percha, etc. The hydrocarhides will be divided into six series, they are all built upon the type of a molecule of hy- drogen, or H' ) H' r FIRST SERIES. General Eormula, CiiH2q..2. ACETYLENE, OE DI IIYDEOGEN DIOAEBISB. Disqpveied by Davy and composition determined by Berthelot Formula, C2H2. Specific Gravity, 0.92. Density, 13. Molecular weight, 26. Direct combvnatioiv of Carbon and Hydrogen. Up to comparatively recent times it has been con- sidered in^possible to unite carbon and hydrogen di- rectly. Berthelot, however, succeeded in doing this in the year 1863. Peepaeation. — The apparatus which he employed »'■ ' f » Mtm y Mt t wU a i memtm CARBIDES OF UYDBOOE2). 19 , also 'sical mes, ogen. con- n di- lifi in loyed in this remarkable synthesis, consisted of a glass flask, provided with two lateral tubal iires through which passed two metallic rods, terminating in carbon points, and which approached so as to form, when connected with a powerful battery, an electric arc. The corks through which these rods passed were provided with another opening each, to which a tube was adapted. Through one of these tubes hydrogen was admitted and through the other the products of the reaction passed as they were formed. The gas was collected in a solution of cuprous chloride in ammonia. A red-precipitate, acetylide of copper was formed, which was thrown upon a filter and treated with hydrochloric acid in a flask, whereupon acetylene was set free. Many organic compounds produce acetylene on subjecting their vapors to the action of electric dis- charges. Acetylene is also produced, as a rule, whenever or- ganic matter is decomposed by heat. PiioPEETiEa — Acetylene is a colorless gas, having a disagreeable odor. It is moderately soluble in water, and is ditiicultly liquified. It is decomposed, at about the temperature at which glass melts, into carbon, hydrogen, ethylene, ethyl hydride and condensed hydrocarbides, among which Berthelot has found ben- zol. Thenard has recently obtained it both as a liquid and a vitreous solid. (9 — 78 — 219.) Acetylene burns with a fuliginous flame. It de- tonates violently and without residue when mixed with 'If wamd 20 OROANIO 0IIEMI8TRY. 2.6 volumes of oxygen. CuprouB acotylide is an ex- plosive body. It is sometimes formed in brass gas- pipes, and has been the cause of fatal accidents. Chlorine acts upon acetylene with extreme energy; there is often detonation accompanied by light. Qn moderating the action the compound 0,11,01, can be obtained, which, as well as the body 0,H,Cl4, can also be prepared by the action of antimonic chlo- ride upon acetylene. As acetylene is not uncommonly studied in con- nection with inorganic compounds, a more detailed ac- count of this hydrocarbide need not be given here. Acetylene is the prototype of a homologous series of bydrocarbides, of which the general formula is, The following members of this eeries are known: Allylene, - - - - C, H4 Crotonylene, - - - C4 Hj Valerylene, - • - Cj Hg Rutylene, fienzylene, r^niMaaaiinmi*^- ' jm w ii. i mMit ii in >i iw»i ii ,ii ■ m wi j^fcn BTHYLENIC. 21 SECOND SERIES. General formula, C"Hto. ETHYLENE. Synonymi: Elayl, Oleflant gaa. Formula C, H4. 8p. Gr. 0.97. Molecular weight, 28. This jjas, for no good reason other than custom, is always studied in inorganic cheraistiy, usually in con- nection' with the consideration of illuminating gas, of which, with methane, it forms a prominent constit- uent. Ethylene is the type of a class of homologous hydro- carbides, f which the general formula is: OnH jn* Each member of the series is related to an alcohol from which it may be obtained on treatment with bodies having a great affinity for water, as sulphuric acid or zinc chloride. C„H,„+, + 0, — HgO-=C„fl in. immmmmmm m W' — 22 OEQANIO CHEMISTRY. note the following members of this series : Ethylene, - - - - Cg H4 Propylene, - - - C3H. Butylene, - - - - C4 Hg , Amyleue, - - C5 H,o Hexylene, _ - - Co Hja Heptylene, C, H,4 Octylene, - - - - Cs Hi, Nouylene, - - - C» H18 Paramylene, - - - CioHgo Cctene, - - - - CiiHgj Duodecylene, - 0jgHg4 Tridecylene, (Paraffin?)* CisHjjj Tetradecylene, C14H28. « •A. G. Pouchet(66— [3] 4—868) has prepared from paraffin, by oxydation with nitric acid, paraffin acid, C24H43O2, from which he deduces CmHso as the formula for paraffin. ' 'mvm $m mjmm miimi>imaimmfMa* mMiMm i> i t m H immi i Kta METHANB. 23 Bn, by which THIRD SERIES. General formula, Gn H^ota* METHAI7B. Discovered by Volta in 1778. Synonyms; Methyl hydride, Marsh gas, Formene. Formula CHior CHs. H. Sp. Gr. 0.559. Molecular weight, 16. Permanent gas, not liquifiable, neutral. !Nbt discussed in detail here for the same reasons as given under Ethylene. Methane is the first member of the following very important homologous series: C Hi methyl hydride, or methane, ethyl propyl butyl amy^ C,H« CsHs C4H,o CgHia C6Ht4 CtHu CgHia Cailao CioIIj2 CuHae he^l heptyl octvl » nonyl decyl undecyl bidecyl " ethane. '* propane. " .butane. " amane. " hexane. " heptane. " octane. " nonane. " decane. " undecane. " bidecane. \-'m i-- 24 ORGANIC CHEMISTRY. CisHas tridecyl " « trfdecane. Ci4Hao tetradecyl " " tetradecane. CisHsa pentadecyl" " pentadecane. CijHsi hexadecyl " « hexadecane. Nearly all the members of this series have been found in American petroleum, mixed with members of the preceding, or ethylene, series. Crude petroleum, refined by fractional distillation, is still a mixture of various hydrocarbons. The commercial names given to the products sep- arated at the difibrent boiling points, do not appertain to chemical compounds, or bodies having a definite composition. Subjoined is a table based on Dr. C. F. Chandler's Eeport on Petroleum, (100— '72^1) showing the PBODUCTS OF THE DISTILLATION OF CRUDE PETROLEUM.* Mija. U) 3 S2 OHiBF vsaa. Cymogene Bhigolene 55 19H .625 .666 .706 .78* .804 .847 .833 Solid. 0=0. 18.3 48.8 8S.S lOt.4 148.8 176.6 sts.s 801.6 i Qenarally uncondeneed — used In ice machines. Condensed br ice and salt— need as Gaoolene 1 an aniesthetlc. Used In msklng "air-gas." Used for oil cloths, cTeaniiig, adul- < terating kerosene, etc. For paints and varnishes, Used to adalterata kerosene oil. Ordinary oil for lamps. Lubricating machinery. Mannfacture of candles. CNaphtha B Naphtha ....... A Naphtha.. ...... Benzine Kerosene oil Mineral eperm Lnbricatingoil.... Paraffin *Re-arranged from Dr. C. F. Chandler's Report on Petroleom, presented to the Board of Health, of the City of New York, 1870. U.i >i>i i Ai, .. i. i[y;ai»w METHANE. 25 been mbers ation, ;s sep- Brtain sfiDite diet's UM.* Bed in ased as ?. adul- ■ paiiitg oil. Q ted to UNaAJTE KEROSENE. Many accidents occur by explosion of lamps, when kerosene oil contains too much of the lighter oils, ben- zine and naphtha. Thir ^es the oil too readily in- flammable, for the light is are driven out by heat- ing (as when a lamp oi kerosene stove is burning), and their vapors mixed with the oxygen of the air form a dangerous explosive mixture. Tiiere is a law requir- ing manufacturers to keep kerosene oil free from these lighter oils, unfortunately not always faithfully en- forced. The temperature at which kerosene, on heating in an open vessel, emits vapors which readily catch fire on approaching a burning body, is called, technically, the " flash point,-' and that at which the kerosene itself inflames is called the "burning point." FOSSIL EEsras, Am) BrrUMKN. These substances include amber, retinasphalt, as- phalt, retinite, and many other allied bodies which are chiefly contained in the tertiary strata. In many in- stances they are the products of the action of an ele- vated temperature upon vegetable bodies; and when this is the case, they form irregular deposits which im- pregnate the strata around. In many cases the bitu- mens occur in regular beds, which appear to have been formed in a manner similar to the deposits of true coal. Certain important building stones have been found to be more or loss impregnated with bitumen. Such is the limestone obtained at the artesian well ■I rfWiitfiiMi mm m^ 86 ORGANIC CHEMISTRY. quarry in the city of Chicago, and the celebrated Buena Vista, (Ohio,) sanddtone used extensively in Cincinnati; also employed at Chicago in various prominent public buildings, as the post-ofRce and Chamber of Commerce. The author, in making a chemical examination of the latter stone for the United States Treasury Department, found it to con- tain 2.3 per cent, bituminous matter. r?ww BENZOL. 97 FOURTH SERIES. General formula GnH2ii-<. mwzoL. Synonyms ; Benzene, Benzine. Formula C« Ha- sp. Gr. 0.88. Molecular weight, 78. Sp. Gr. of vapor 2.70. Density" " 39. Solid at 4 ° . Boils at 80.5 ° . Benzol is obtained, with acetylene and ethylene, in the decomposition ot organic substances by heat, and its production is especially favored when the temperature is kept at a high point for some time. Etliylene and methane form at a tolerably low temperature. Acetylene, which is richer in carbon, is produced at a higher temperature. Benzol and especially napthalin, being still more carbonaceous, are formed at an extremely high temperature. Berthelot has prepared benzol synthetically by con- ducting methane tribromide, CHBrg, over red-hot copper: 6(OHBr8)+9Cu=C«H«+9CuBrg. Benzol may be considered as condensed acetylene: C6H«==(OgHa)8. 28 OBGANIO CHEMISTRY. Originally, benzol waa prepared by a process analo- j^us to that which ibrnishes methane, i. e., by distill* ing benzoic acid with lime, 0,H,0,-|-0aO = Ca C 0,+0,H,. At present it is obtained in immense quantities from the tar which is formed as an accessory product in the manufacture of illuminating gas. At the high temperature of the gas-retort other pro- ducts, homologous with benzol, are formed as wellj viz.: Toluene C, H, boils at 110° Xylene CaH.o " " 139° Cumene Cg H,g " " 165° Cymene C10H14 " " 180° and other hydrocarbides, as napthalin CiqHsj anthra- cene, also various sulphur compounds, notably carbon bisulphide; several oxygenated compounds, as phenol CgHgO, cresylol 0,HgO ; nitrogenous compounds, as aniline OgH,N, and various members of its homologous series. Benzol is a colorless, neutral liquid, with a specific gravity of 0.89, almost insoluble in water but soluble in alcohol and ether. It dissolves sulphur, phosphorus, iodine, the differ- ent resins, and fatty substances; this latter property causes it to be employed similarly with commercial " benzine' ' for cleansing purposes. Care must be taken to rub with a piece of cloth having an open texture, \MS .imat^-isitiaimmmii •fcf BENZOL. 29 that it mav remove the benzol by absorption, without which the spot would reappear after evaporation of the solvent. Benzol burns with a fuliginous flame. Nascent o^yg^n gives with it various products, and notably oxalic acid and carbon dioxide. Chlorine and bromine yield crystalline compounds with benzol. Benzol is the simplest member of a group of bodies known as the aromatio compovmda, of which we shall proceed to describe some of the more important. For distinguishing benzol from the benzine of com- merce, which is made from petroleum, Brandberg recommends to place a small piece of pitch in a test tube, and pour over it some of the substance to be ex- amined. Benzol will immediately dissolve the pitch to a tar-like mass, while benzine will scarcely be col- ored. NrrRo-BSJTzoL CjHjNOj. T^is body is obtained by treating benzol with fuming nitric acid. 0,H,+HN03= CeH»(]Sr02)+H,0. Nitro-benzol is a yellowish oil, crystallizing at 87°, has a sweet taste and an odor which has led to its use in perfumery under the name of essence of nmJxme. Taken internally it acts as a poison. On treatment of nitro-benzol with nascent hydrogen, hydrogen sulphide, or other reducing agent, we obtain ■MKtawMWHK.: -^i "TRS 80 OKGANIO CHEMISTRY. ctniline, which is a colorless liquid, boiling at 182°. It does not act upon litmus, yet combines with the acids, forming crystallizable compounds. Aniline gives with chlorine, bromine and nitric acid products of substitution which are very numerous and well defined. It reacts upon the iodides of methyl, ethyl, etc., forming the corresponding aTO*ra<3S, or bodies constructed on the type of ammonia, having one or more of the hydrogen atoms replaced hy an organic compound radicle.; Aniline Methylaniline C,H,N C,H,N C.H« Ethylmethylaniline CjHuN 0«H, or, when free,(CflH5)3, is the radicle i>Aeny?, hence aniline is properly phenylamine. Aniline has, during the last score of years, acquired great importance, as, under the influence of oxydizing bodies, it forms most remarkable tinctorial com- pounds. If a small quantity of aniline is added to a solution of chloride of lime, the liquid is colored violet, which color disappears in a ffew moments. In 1858, Perkins obtained, by the action of potassium bichromate and sulphuric acid, a beautiful purple, which is known in -SSSMiiSimi assussessaBii 8IIK4.. BENZOL. ai corn- commerce as mauve. Shortly after, Vergiiin obtained a magnificent red coloring matter on heating aniline with tin dichloride. This substance, known under the names of cmiUne- red, fuchairiy magenta, etc., is now very econoini- cally obtained with arsenic oxide in place of the tin dichloride, which is reduced to arsenous oxide by the reaction. Hoffmann has shown that aniline-red is » salt of a colorless base, which he calls rosaniline; this substance has the formula CjoHaiNsO, or CaoHi»N8,ll20. In the past few years there have been produced green, yellow and black colors, all originating from aniline. These substances dissolve in alcohol, and dye wool and silk without in any way weakening the fabric. They have a xnagnificent lustre, but their permanency is not of the highest grade. The consumption of aniline for dyeing has now come to something enormous, amounting in Germany alone to over 16,000 tons per annum. The aniline colors are employed in injecting tissues for microscopic preparations. For a fuller account of the aniline colors, a larger work should be consulted. The history of aniline affords one of the most re- markable instances of the value of scientific chemical research, when perseveringly and skillfully applied, for at first few substances seemed to promise less ; and the gigantic manufacturing industry at present connected with this compound, in its applications as a 8MR;.' ?" ■ i:, iik'jii!.'JMHW 82 ORGANIC OHEMISTBY. tinctorial agent, offers a Bingular contrast to the early experiments upon this body, when a few onncea fur- nished a supply which exceeded the most sanguine ex- pectations of the early discoverers of this body. Phenol, CelleO. Byrnnymt: Hydrate«of phenyl, carbolic acid or phenic acid. It occurs in castoreum, though usually procured from the portions of coal-tar distilling over between 170° and 195°. They are agitated with caustic soda, water added to separate the insoluble oils, and the phenol dissolved in the alkali is liberated as a crys- talline mass, on decomposing the potassium compound with hydrochloric acid. ^ Salicylic acid, distilled with an excess of lime, also furnishefl phenol; OtHbOs + CaO = CaCOs + 0,^.0. Ifphenyl-sulphuricacid,^''g' ISO4, obtained by di- rect action of sulphuric acid upon phenol, is heated with potassium hydrate to about 300°, potassic phenol CsHflKO is obtained. Phenol is therefore obtained from benzol under the same conditions as alcohol is obtained from ethylene, the corresponding hydro- carbide. Phenol crystallizes in handsome needles, fusible at 84° and boiling at 188°, It is little soluble in water, •^mmm -WWIM ■MM PHKNOL. 88 very soluble in alcohol and ether. Phenol furnishes with chlorine, bromino and iodine numerous substitu- tion products. Phenol has come, like alcohol, to have a generic signification, there being a number of analogous com- pounds, though only this, the ordinary phenol, is an important body. Heated with concentrated nitric acid, it furnishes yellow, very bitter, crystals of the body known as PiCBio or Cabbazotio aoid. Picric acid is also formed when silk, benzoin, aloes, indigo, etc., are treated with nitric acid. Tliis acid is very largely used in dyeing, either di- rectly to produce a yellow color, or, combined with in- digo, to pn)duce a green. Phenol, though called carbolic acid, does not decom- pose the carbonates, or combine with the metals to form true salts. Phanol dissolves in sulphuric acid without coloration, if pure, and forms phenyl-sulphuric acid or sulpho-carbolic acid H )^^*» which gives definite salts with the metals. One of these, the phenyl-sulphate or sulpho-carbolate of so- dium NaC6H6S04, is claimed to have valuable proper- ties as a prophylactic against scarlet fever. Phenol gives certain reactions of the alcohols ; this 84 OROANIO 0IIKMI8TRT. Bomewhat explains the origin of the name given it by Bertliclot. This body is the type of a class of com- pounds which contains: Cresylol obtained from creosote O7 Hg O Phlorylol " " " CbHioO Thymol " " essence of thyme doHuO. PHTSIOLOOIOAL ACTION OF PHENOL. Phenol attacks the skin, producing a white stain. It coagulates albumen and is employed with great success as an antiseptic and disinfectant. It is used externally in a diluted state to dress wounds which suppurate, also in many surgical cases. It is sometimes used internally. Large doses of it are poisonous. Carbonate and especially saccharate of calcium are considered as antidotes for phenol. Grace Calvert has announced that olive or almond oil is a still better antidote. OIL OF TUKPENTINE. 85 FIFTH SERIES. General Formula, Cn Han-4. BflSKKOK, OH OIL OF TUBrKNTINE. Formula OioHi«. Density of vapor compared with air 4.7. Molecular weight, 180. Boils at 160° Turpentine is extracted from several varieties of the family of Con(ferai, notably from the piue, fir and larch. The products vary pjmewhat with the nature of the tree, but they have many common characteristics; their composition is the same, thei density is nearly identical and their boiling point very nearly so. Their rotary action on the solar ray varies largely. Isomeric carbides are found in other families of plants, in the aurantiaoem family for instance, as the lemons and oranges. These contain carbides very dif- ferent, as evidenced by their odors and other physical properties, also diflferent in certain chemical relations, yet having the same composition as oil of turpentine. There are also various polymers of this carbide. This entire series of hydrocarbons can be divided into three croups. The first contains carbides having fl -mP 36 OBGANIO CHEMISTRY. the formula OioH,fl, their boiling points being below 200°, and including : Density. Oil of turpentine, 0.86 cloves, 0,92 lemon, 0.86 orange, 0.83 juniper, 0.84 bergamot, 0.85 pepper, 0.86 elemi, 0.85 u « «( « Boiling at 167° to. 160". 140° « 145°. 170° « 175°. 175° « 180°. about 160°. " 183°. " 167°. " 180°. The carbides of the second group have the formula CjjoHaj, their boiling point ia above 200°, they are: Oil of copaiva, 0.91 " cubebs, 0.93 245°. 240°. The third group contains the non-volatile carbides, such as Density Caoutchouc, - . - . 0.92. Gutta-percha, ... 0.98. The rotary power, constant for each, varies with the different species. Frencli oil of turpentine causes the plane of polar- ization to deviate to the left; the American variety turns it 13° to the right; oil of lemon causes a devia- tion of 60° to the right; in the case of essence of elemi the deviation amounts to 100°. Some of the mum ^^^^ OIL OF TU.iPENTINE. 87 g below formula are: iarbides, with the >f polar- i variety a devia- 3ence of 3 of the eesential oils of the first group contain oxygen com- pounds as well as the carbohydrides. The principal chemical difierencea between the members of the group are the facility with which they are oxydized and their reaction with hydrochloric acid. Essence of turpentine becomes resinous rapidly when exposed to the air and finally solidifies. Es- sence of lemon becomes viscid after a considerable time. Hydrochloric acid produces, with essence of turpentine, a liquid and a solid compound, having each the same composition, OioHigjHCl, which, after a few weeks, becomes a dichlorhydride, (by some denomi- nated a dichlorhydrate), CioHjg,2HCl. Essence of lemon also gives two dichlorhydrides at once, one liquid, the other solid. Oil of turpentine may be obtained in a pure state, on distilling the commercial article in a vacuum. Thus obtained, turpentine is colorless, limpid, very volatile, and has a characteristic odor. It is insoluble in water; very soluble in alcohol and ether. It burns with a smoky flame; on exposure to the air it oxydizes and becomes resinous. The same effect is produced more rapidly with oxide of lead and some other ox- ides which render the oil siccative and suitable for use in painting. J. M. Merrick (100-4-289) has noticed the circumstance, important in its technical applica- tions, that oil of turpentine attacks metallic lead quite strongly; tin, on the other hand, not at all. Turpen- tine, if exposed to the air, mixed with a solution of indigo, absorbs oxygen and transfers it to the indigo, ■w^miiiijiiwilW loai 88 ORGANIC CHEMISTRY. whicli loses its color, yielding a product of oxydation called isatin. Under these circumstances, the turpen- tine does not change, and a given quantity of the es- sence can absorb several hundred times its volume of oxygen, and oxydize an indefinite quantity of indigo. This oxygen is probably the active modification, or ozone. Heated to 300° in a hermetically sealed tube, it changes into two products, one, isomeric, called iso- turpentifie, which boils at 177°, and which exerts a rotatory power of 10° to 15° to the left; the other, a polymer called metOrterebenthene, C20H32 boiling at 860°. OTHER SERIES OF HYDBOOARBIDEa Ciimamme CgHg is a very refractive liquid with a density of 0.924, boiling at 146°. Styrol which is produced from storax is converted at 205°, into a polymeric solid, termed Meta-styrol or Draconyl. If styrol is made to act upon acetylene, or ethylene, at a red heat, there is obtained the very important hydro- carbide ncupMJudin CoHg. This is a body crystalliz- able in very handsome plates, and is ordinarily obtained from coal tar by distillation between 200° and 300°; heavy oils pass over, out of which naphtha- lin crystallizes; on cooling, the mass is pressed and purified by sublimation. It ftifees at 79° and distils at 220°. Naphthalin is associated in coal tar with a hydro- carbide, beautifully crystallizing in long needles, fus- ing at 93° and boiling at 285°. This is acmaphtene ALIZARIN. 89 C12H10. Another hydrocarbide is also found in this tar, anthracene. Its formula is CuHjo. It forms very •limlnutive crystalline plates fusing at 210° and boil- ing at 360°. Its vapor is extremely acrid. This body has recently enabled chemists to repro- duce the coloring principle of madder; alizarin Ci4rig04. It ia obtained on oxydizing anthracene by means of a mixture of bichromate of potassium and sulphuric acid, which gives oosyanthracene OuIlgOj. This, with fused potassa, furnishes a combination of potassium and alizarin, from which the latter is pre- cipitated by an acid. It has the form of brilliant bronze-colored, needles, identical with natural alizarin obtained from madder. Alizarin sublimes at 215° and is very stable, little soluble in cold water, but readily soluble in boiling water. It is easily dissolved in alcohol, ether.and car- bon bisulphide. * Its chemical character, not quite well defined as yet, appears to place it among the phenols. (See page 33.) The artificial production of alizarin from anthra- cene, thus furnishing a cheap substitute for madder, the chief dye-stuif used in printing calicoes, is one of the latest and most noteworthy triumphs of organic chemistry. Thousands of ai es of land in Europe, especially in Alsatia, now devoted to the culture of madder, may be restored to cereal or other food agri- culture. Before leaving the hydrocarbons proper, it should urn OBGANIO CHEMISTRY. be stated that compounds of carbon and hydrogen of extra-terrestrial origin have been found in certain met- eorites, by J. Lawrence Smith. (80-76-888.) OAMPHOB. Camphor is usually considered at this point, on ac- count of its intimate relation to the oxydized essential oils in composition, and to turpentine in many chemical reactions. Berthelot regards camphor as an aldehyd. Kekule places it among the ketones. Camphor exists in various parts of the Zaurua camphora. To obtain it, the wood is finely divided and heated with water in a metallic vessel, closed by a cover filled with straw. The camphor is condensed in grayish crystals on the straw, forming the ernde cam- phor pf commerce ; it is afterwards sublimed in a glass retort as a further purification. Camphor is a crystallized body, having a burning taste and an aromatic odor. Its density is 0.99 at 10°. It is elastic and with difficulty pulverized, wldch can, however, be easily effected on moistening with a few drops of alcohol. Water dissolves only about ^Ar part of it; thrown upon pure water it floats on the surface with a gyratory motion. It -' , soluble in alco- hol, ether, acetic acid and essential oils ; it is sublimed at ordinary temperatures where kept inclose vessels. and deposits again on' the cooler side of the recep- tacle. , It burns with a smoky flame and oxydizes on being -J taaaaaaK Bsaa asts g a aa fflsa a ia sr assiaa^^ Tm BE8INS, BALSAMS, OUM-RESINS. 41 boiled with nitric acid, yielding oamphorio acid C,oHi604 which is bibasic. Heated with zinc chloride or anhydrous phosphoric acid, it furnishes Cymol OioHu. The author found (1-146-Y3) that on treatment of camphor with hypochlorous acid he obtained the new body, OioHiflClO, which he denominates monoehlor- camphor', this, on treatment with alcoholic potassium hydrate, yielded oxyGamphor C,oH,e02 . Camphor is very extensively employed in medicine and pharmacy. BESINS, BALSAMS, 9UM-KE8IN8. These bodies are products of the oxidation of essen- tial or volatile oils. The name of gxum-resin is applied to those which contain a gum, and balsam/ to those which contain essential oils and an acid, usually cin- namic or benzoic, in addition to the resin which is presented in both, A. B. Prescott, the eminent au- thority on proximate analysis, defines balsams as " natu- ral mixtures of volatile oils with their oxidation pro- ducts, — resins and solid volatile acids." They are substances more or less colored, hard and brittle. They are fiisible, non-volatile, and burn with a fuliginous flame. They are insoluble in water, gen- erally soluble in alcohol, ether and essential oils. Several of them are acid. This is the case with the most important of them, us the resin of the pine, called colophony, from wliich three isomeric acids have been obtained— the^'»*o, syMo, and ptmaric, CjoHjoOa. it ' - Vrt i 'J ui •42 ORGANIC CHEMISTRY. This resin constitutes the fixed residue obtained on distilling crude turpentine. It is used for preparing varnish, in soldering, and in certain combinations with the alkalies, called resin-soaps. Subjoined are given the names and the origin of the principal resins, oleo-resins, gum-resins and balsams. With some, the position assigned them in this classi- fication is not definitely settled. BESINS. Amber is found in the lignites and in the alluvial sands of the Baltic. Amicin, the active principle of Arnica Eoot. Cannabin, the active principle of Indian Hemp. Castorin, a secretion of the Beaver {Castor). Ergotin(?), the active principle of Ergot of common rye. Mastic, a resinous exudation of the Mastic, or Lent- isk tree. Burgundy Pitch, an exudation of the Spruce Fir, Abies excelaa. Pyrethrin, the active principle of the Pellitory root. Eottlerin, a crystalline resin from Kamala, the min- ute glands which cover the capsules of Rottlera tino- toria. ■ . . OLEO-KKSINS. Copaiva, a resinous juice of the copaifera offioimalis found in Spanish America. Wood-oil, an oleo-resin from the Dipterooarpus tv/rhinatus. ,-»-...-—•«■-■,:-,.■..„-., ..»■,. PI .-,.^.- RESINS, BA.L8AMS, GUM-RESINS. 48 Elemi, an exudation of an unknown tree, (probably Cannariv/m commune). Conimon Frankincense, a concrete turpentine of the Pinua tceda. Canada balsam, the turpentine of the Balm of Gilead Fir, {Abies halaamea). Storax, from the Liquidarhhar orientale. GtJM-RESINS. Ammoniacum, an exudation of the Dorema ammo- niacum. Assafcetida, a gum resin obtained by incision from the living root of the Narthex assafcetida. Gamboge, obtained from the Oarcinia moreUa. Galbanum, from the galbanum officinale. My rrh,an exudation of the Bahamodendronnvyrrha. BALSAMS. Benzoin, obtained from incisions of the bark of . Styrax benzoin. Balsam of Pern, from the Myroxylon Pereirce. Balsam of Toln, obtained from incisions of the bark of Myroxylon tuluifera. Caoutchouc is the hardened juice of M O, ethyl or common alcohol. II. On two molecules of water : H [ O3, ethylene alcohol or glycol. }03,gly cerine and thus on. ^2 I III. On three molecules of water : CaH,'" H, They may be defined as bodies built on the type of one or more molecules of water having one-half of the hydrogen replaced by a hydrocarbide radicle. MONATOMIO ALCOHOLS, or those formed on the type of one molecule of water, ' Ji-JU^j^iuiiiffl li ; ALCOHOLS. 45 >die8 as issential as to . There zed. scule of type of 'of the of which ordinary alcohol is the best studied, are characterized by the fact that they contain one atom of oxygen only, and that by reaction with the mono- basic acids they form but a single ether. They may be obtained synthetically, as well as by various indirect processes. Subjoined is a classified list of the more important monatomic alcohols: water, FIRST 8KBIE8, 0„H2„+,0. • Methyl alcohol (wood spirit), C H4 Ethyl alcohol, (spirit of wine G, H, Propyl alcohol CaHgO Butyl alcohol, C4 H,oO Amyl alcohol, c, ii„o Setyl alcohol C,H,4 Octyl alcohol CgHisO Sexdecyl alcohol ■ 0„H84O Ceryl alcohol C„H«0 Myricyl alcohol - OaoHoO. SEOOm) SERIES, C„Hj„0. -■'' Vinyl alcohol O8H4O AUyl alcohol OsHjO. THIRD SERIES, C„H2„_20. ■ Bomeol alcohol C,„Hi«0. 1^ ML, 46 OBOANIO CHEMISTRY. FOURTH SERIES, C„H, Benzyl alcohol Xylyl alcohol Cumol alcohol Oymol alcohol FIJTM SERIES, Cinnyl alcohol Cholesteryl alcohol C, II9 O Cg HiqO C, H,aO OioHuO. Cj HloO MoNATxaiio Alcohols havino the General Formula, CnHjn+jO. METHYL ALCOHOL, OR WOOD-flPIRIT. CH40 = ^2«}0. This sabstance is found in the liqnid obtained on distilling wood. The distillate contains in addition, water, acetic acid, tar, and varions oils. In order to extract the methyl alcohol, it is again distilled and that portion which passes over at 90° is collected ; this is diluted with water, the oil which precipitates sepa- rated, and the liqnid agitated for a considerable time with olive oil. Thisjoil is then removed, the liquid redistilled several times and only that portion collected which passes over above 70"*. On being again ALCOHOLS. 41 9BHULA, ined on iddition, jrder to lied and 3d; this les sepa- )le time Q liquid joUected I again distilled with calcium chloride ik furnishea methyl al- cohol, nearly pure, boiling at 66.5°. There are other methods of rectif 'ng besides the one here given. This body possesses most of the general properties of ordinary alcohol. Under the action of the oxides it furniahes an aldehyd and formic acid. "Wwi the acids it produces ethers; viz., with hydrochloric acid, methyl chloride, CHjCl— ^pf» [ ; with acetic acid, methyl acetic ether, Cja,0,— ^ ^q 1 0. Chlobofobm, OHClg . Methyl chloride produces with chlorine a regular series of products of substitution. One of these terms, CHClg, is the very important body, cMorofomif die- covered in 1831 by Soubeiran and Liebig. To prepare this compound, 40 litres of water, ,5 kilos of recently slacked lime, and 10 kilos of chloride of lime are heated to 40°; 1600 grams of 90 per cent, alcohol are then added and the retort luted with clay. It is now heated for a moment to the boiling point and the lire then at once slackened. The ebullition having ceased there will be found two, layers in the receiver. The upper layer is formed of water and alcohol, the lower one is chloroform nearly pure. The latter is washed with water, agitated with a dilute solution of potassium carbonate, or with fused r-w- gMthh^irtiak^u^asaiaa^^ r ,^ ^HMMIB 48 OROANIO OHEMISTRT. calcium chloride for twenty-four hours, and distilled to four-fifths. Chlorofonn is a colorless liquid. When first pre- pared it has a sweetish penetrating taste, and an agree- able, ethereal odor. Its density is 1.-1-8; it boils at 60.6°, is soluble in alcohol and ether and difficultly so in water. It bums, though not readily; its fianio having a green margin. It dissolves iodine, sulphur, phos- phorus, fatty substances and resins. An alcoholic solution of potassa decomposes it into chloride and formiate : CHClg + 4KH0 -= 3KC1 + CHKO, + 2H,0. Physioloqioal Aotion. Chloroform is at present very generally used as an anesthetic. Opinions as to its manner of acting are divided. Formerly it was thought that the insensi- bility produced was the commencement of asphyxia. Since then it has been ascertained that the heart, in case of poisoning by chloroform, immediately loses all power of contraction, and it is now generally admitted that paralysis of the muscles and nerves of the heart is produced. . As the vapor of chloroform is very dense, care should be taken that in it&.use, access of air to the lungs be not wholly prevented, or serious conbequenoes may re- sult. Probably the fatal accidents that have occurred MM« ALCOHOLS. 49 may, in Bome instanced at least, bo attributed to lack of care in this regard. It is of great importance that the chloroform used should be quite pure. In some cases it Ims been found to have undergone spontaneous decomposition after exposure to a strong light It ought to communicate no color to oil of vitriol when agitated with it. The liquid itself should be free from color or any chlorous odor. When a few drops are allowed to evaporate on the hand no unpleasant odor should remain. Shuttleworth (100, 4, 339) states that partially de- composed chloroform can be rectified by agitating it with a solution of sodium hypo-sulphite. a OEDINARY ALCOHOL. Ethylio, or Vimo Alcohol. Formula: OaHgO. Density of vapor 28. Density .81. Boils at 78.40. Cannot be solidiflod. It is prepared by the fermentation of saccharine liquids at a temperature of 26° to 30°, in-the presence of a small quantity of a ferment. Oane sugar does not directly become alcohol under the influence of a ferment. It is first transformed into two other sugars, glucose and levulose. I ■I :-iw^a^BBKgaa^^SSaS5!taiiaAi»^^^ 50 ORGANIC 0HEMI8TET. CuHbO„+ H2O=C8HiA+06H„O,. Qlnoose. Levuloae. In its final fermentation nearly all the sugar is changed into alcohol and carbon dioxide, OeH20o=2C2H«0+4CO.a. This equation accounts for the transformation of 94 to 96 per cent, of the sugar employed, but besides alcohol and carbon dioxide, succinic acid is always formed as well as glycerine, and in most cases " fusel oil," consisting chiefly of amyl alcohol. Fermentation is a phenomenon correlative with the development and growth of cells of the fungus Myoo- derma (Torula) oereviaim which constitutes yeast. Sometimes the sugar is furnished as a natural product by fruits ; often glucose is produced from the starch of cereals, potatoes, etc., and then changed into alcohol afterwards. Corn is the leading original source in this country. Alcohol obtained by fermentation is concentrated by distillation. This operation is performed in retorts, the construction of which is based upon a principle developed by A. de Montpellier, and improved by Derosne, Dubrunfaut and others. The object is to prevent the distilling over of the water with the alco- hol, and is quite weH accomplished by the improved methods now employed. The details are not suited to the scope of this work. The application of this rational method of distilling •ms^^-. in ALCOHOLS. 61 admits of obtaining liquids containing up to 90 per cent, of alcohol, but it is difficult to go beyond that point of concentration. In order to prepare alcohol more concentrated, sub- stances having a great avidity for water must be used. Calcium chloride is not suitable, as it unites with the alcohol. Anhydrous sulphate of copper, carbon- ate of potassium or quicklime do not produce absolute ■ alcohol. But it is very rpro that porfectlv anhydrous alcohol is required. Alcohol of 97 per cent, is obtained in treating alcohol of 86 per cent, during two days with lime, or better, with a sixth or seventh part of its weight of dry potassium carbonate, and then distilling. If it is desired to procure absolute alcohol, very concen- trated alcohol is treated with caustic baryta until the liquid is colored yellow and then distilled. Alcohol in fresh bread made with yeast has been found by Bolas (8-27-2Y1) to the amount of .814 per cent. Slices of bread a week old contained .12 to .13 per cent. Absolute alcohol is a colorless liquid, more limpid than water, of an agreeable odor and a burning taste. It boils at 78.4°, is neutral, combustible and burns with a flame but little luminous. It heats on coming in contact with water, and attracts the moisture of the air very rapidly. It contracts upon mixing with water; the max- imum of contraction takes place at a temperature of 15° when 62.3 vol. of absolute alcohol are mixed with 47.7 vol. ofvvat.,r; instead "DO vol. one obtains ff^-gj^-SiSKsswaBisaiaBaiRs^asjigEv .^ 52 OiiOANlO CUKMISTKY 96.8 vol. At the moment of admixture numerous air bubbles escape and the mixture becomes heated. The alcoholic strength of the liquids consumed as beverages varies considerably. Madeira wines, about (( 20 per cent 14 to 16 (( 15 to 12 « 10 to 12 (( 10 to 16 (( 2 to 7 u Ito 8 C( Malaga Bordeaux Rhine California Cider Beer Spirita are distilled from fermented liquids; brandy from wine ; whisky from a mash of com or rye ; rum from molasses, etc. They contain about 50 per cent, of alcohol. The terra, proof apirita was originally given to al- cohol sufficiently strong to fire gmipowder when lighted. The strength of proof spirits now varies in difierent localities, and it would be well were this ambiguous designation no longer employed. Alcohol dissolves the caustic alkalies, certain m'- trates, chlorides and other salts, also various gases. "With some of these, genuine chemical combinations are produced, and not mere solutions; this is the case with calcium chloride and magnesium nitrate. Alcohol can be mixed with ether in all proportions; it dissolves the resins, essential oils, and a great num- ber of other organic bodies. The chemical properties of alcohol are very inter- mmmmm. ALOOHOLS. sa aumerous heated, isuined as mt. is; hrandr/ rye ; rum ) per cent. riven to al- ^der when iV varies in 1 were this d. certain ni- ious gases. >inbinations ) is the case m nitrate, jroportions; great num- very inter- itm^ esting. Vapor of alcohol is decomposed on passing through a tube heated to redness; hydrogen, marsh- gas, oxide of carbon, small quantities of naphthalin, benzol, and phenol are formed. In presence of air and water it slowly oxidizes and yields acid com- pounds. This action is rapid, if a hot spiral of plati- num is placed in the alcoholic vapor. ExPEBiKESTT. — ^Place a small platinum spiral in the ' wick of an alcohol lamp, light and then blow out the flame. It will be seen that the spiral remains incan- descent. Spongy platinum acts still more energetically; if very concentrated alcohol is poured drop by drop into a capsule containing spongy platinum, or platinum black, it will be seen to redden, fumes are produced and an acid liquid is formed containing chiefly aldehyd and acetic acid. The same oxidation occurs if diluted alcohol is exposed to the air in the presence of mother of vinegar, a cryptogamic plant, {Mycoderma aceti). In fact, this is the basis of the manufacture of wine-vin- egar and alcohol. Fuming nitric acid reacts upon alcohol with ex- plosive energy. Aldehyd is formed, also acetic ether, nitrous ether and acetic, formic, glycollic, oxalic and carbonic acids. Alkaline hydrates attack alcohol even in the cold potassium acetate being the chief product formed. If alcoholic vapor is made to pass over lime heated to 250°, hydrogen gas and calcium acetate are produced; the latter is decomposed at a more elevated temperature into marsh gas and water. If silver or mercury is dissolved in nitric acid, and 90 per cent, alcohol added to the cooled solutions, a ^ 64 OBOANIO CHEMISTRY. lively ebullition results, and a crystalline precipitate is deposited which explodes at 185°, or by percussion. This body is the fulminate of silver or mercury, re- spectively, which is considered as derived from methyl cyanide, CHgCy, by the substitution of 1 molecule of nitryl, and of 1 atom of mercury, or 2 of silver for 3 atoms of hydrogen. The formulae are C(NOg)HgCy; C(NOg)Ag,Cy. Potassium attacks absolute alcohol, and is dissolved liberating hydrogen; on cooling, potassium ethylate is deposited. Sodium acts in the same manner. These compounds, if brought in contact with water, regenerate alcohol and the respective alkaline hydrates. Acids attack alcohol and furnish compound ethers, which we will study later. Ozone, according to A. W. Wright, (80 — L3]7 — 184) oxydizes alcohol to acetic acid. Physiological Aorioif of Alcohol. Uses op Al- ' OOHOL. — Alcohol coagulates the blood; injected into the veins it produces instantaneous death. It is a very powerful poison, as are all alcohols of the series CnH2m30. Rabuteau (9—81—631) has shown that they are more poisonous in proportion as their mole- cules are complex. Cases have been observed where a large dose of alcohol has caused death in half an hour. The worse than worthless character of distilled liquors as beverages is no longer an open question. With regard to their value as food or medicine, a more authoritative or competent expression of opinion can- not be desired than that of the International Medical Congress, which at its session in Philadelphia in 1876, said: [La %:. ALCOHOLS. 55 I itate is lussion. try, re- methyl cule of 3r for 3 HgCy; issolved lylate ia These generate 1 ethers, ;o A. W. etic acid. J OF Al- . into the 9 a very he series }wn that sir mole- 1 where a Ein hour, distilled question, le, a more inion can- ,1 Medical a in 1876, "1. Alcohol is not shown to have a deuniie food value by any of tb g usual methods of chemical analy- sis or physiological investigation. '' 2. Its use as a medicine is chiefly that of a cardiac stimulant, and often admits of substitution. " 3. As a medicine, it is not well fitted for self-pre- scription by the laity, and the medical profession is not accountable for such administration, or for the enormous evils arising therefrom. " 4. The purity of alcoholic liquors is, in general, not as well assured as that of articles used for medicine should be. The various mixtures when used as medi- cine, should have definite and known composition, and should not be interchanged promiscuously." The dissolving power of alcohol renders it very ser- viceable in the arts. Solutions in this menstruum are called aZcoJwUo tinctures. Only the purest alcohol ought to be used in pharmacy, though of course, various strengths are requisite, as it should be of a degree to suit the nature of the matter to be dissolved. If the substance to be treated is a resin, or some substance absolutely insoluble in water, a very concentrated alco- hol is preferable. A weaker alcohol is made use of, if the matter is one that is soluble, both in alcohol and water. Alcohol acts not only as a solvent, but also as a pre- ventative of decay. This i i property which renders it especially valuable in the preparation of remedies. i '. tmmmmm. i I jjg^ 56 OROANIO OHKMISTUV t AMYL ALCOHOL. C5H12O CbHii ) p. H \^' Synonyms: Fousel (ob Fusbl) Oil, Potato Spirit. The amylio compounds derive their name from Amylum^ starch, the chief constituent of the potato. Tiiey are formed in some proportion in almost every in- stance of alcoholic fermentation of sugar. Amylic alcohol is usually prepared on fractionally redistilling the oil which remains when the alcohol, prepared from potatoes, barley, corn, etc., is distilled. The pro- duct which comes over at 132°, is that collected. Cahours and Balard first established the analogy, in constitution and properties, of this compound with ordinary alcohol. It is a monatomic alcohol, giving with oxidizing re-agents, valeric acid. CsHi^O+O, = C»H,oOa+HaO, Amyllo alcohol. Valeric acid. and with acids, compound etherfi, as Chloride of amyl, C5H.11CL C H ) Acetate of amyl or amyl-acetic ether, n'jT^o [ ^ I m o Spirit. itne from he potato, t every in- Amylic edistiiling prepared The pro- collected, ^ualogy, in ound with hoi, giving CsRuOl. ALCOHOLS. 57 MONATOMIC ALCOHOLS. Having the general Formula CnH^O. Allylio Aloohol, CjHeO — C^Hb ) /-| H ["• This is a body giving the same reactions as ordinary alcohol. The radicle it contains is the same as that in the triatomic alcohol, glycerine. Among its deriva- tives there are two which are of considerable impor- tance: Allyl sulphide, Sulpho-cyanide, CgHj OaH, C«H« bHj) o ON r- The former is oil of garlic; the latter oil of mustard. Oil of oablio is prepared by the following method: allylic alcohol is treated with phosphorus iodide which furnishes allyl iodide CsHbI. This iodide is afterwards mixed with an alcoholic solution of potassium sulphide and the whole is distilled; the product which passes over is identical with the essential oil obtained in dis- tilling garlic,onions, assafoetida, etc. , with water. oil of musiaed, or sulpho-otanidk of allyl. This body is prepared by causing iodide of allyl to CN ) react upon potassium sulpho-cyanide, jr r S, and may ON ) be regarded as sulpho-cyanic acid, tj r S, ha>ang the 1 •^ i n unl f 68 OROANIO OHEMISTRY. hydrogen replaced by the radicle of allyl alcohol, CsHb. The product which distills over is an irritating liquid which boils at 145°, like the oil prepared from mus- tard directly. This substance may also be '»* cained by the action of allylic alcohol upon potassium sul- pho-cyanide. It is likewise obtained by the fermenta- tion of mustard seeds. Sulpho-cyanide of allyl does not exist already formed in black mustard {Sinapia nigra), but according to Bussy, its formation is due to a particular ferment. Oil of mustard combines directly with ammonia, forming a crystalline substance culled thiosinnamine, C4HgN2S, which, in contact with mercuric oxide, changes into an alkaloid called ainnamine, of which the composition is C4H6N2 . It reacts upon lead oxide producing a substance called dnapoUne whose formula is CTHiaNjO. BOKNEO CAMPHOR, OH BORNEOL CioHisO. This body exudes from the Dryobalanopa oamphora (Borneo). It is crystalline and has an odor between that of camphor and pepper. It fuses at 195°, and boils at about 220°. It is dextrogyrate. Heated with nitric acid it ftirnishes common camphor CioHuO. ' DIATOinO ALCOHOLS OE GLYCOLS. CnHgn+gOg- Ordinary Glycol, (CgHJ — Og— H8=C2H,0, Propyl " (C3H,) -Og-H,=C3H,02 ALCOHOLS. 59 Butyl Glycol, (C^Hg) -0,-U,=G^T{, oO, Amyl " (C5H,o)-0,-H,=C,H,,0, Hexyl " (C.H„)-0,-H,=C,H,,0, Octyl " (CaH,,)-0,-H,=C8Ht808 TRIATOMIO ALOOHOL8. Glycerine, (CsH5)-03-H3=C3HaOs. • TETEATOMIO ALCOHOLS. Erythrite, (C^H,)— 0^— H«=C4H,o04. * OTHEB COMPLEX ALCOHOLS. Glucose and its i3omerides,(C9Hg) — Og — H,=CjH,j08. Mannite, - - (C,H8)-08-H,=CeH,,0,. Dulcite, - - - (C,He)-Oe— H,=C,H„Oa. ORDINABT GLYCOL. C,HeO,=(^g^)^}Q The discovery of the glycols was an event of great importance. It was achieved by "Wurtz in 1866, and the glycol of which we are treating was the first discovered. In a flask surmounted by a condenser, two parts of potassium or sodium acetate, are dissolv ' in weak alcohol and one part of ethylene bromide added. This I :i ff 60 ORGANIC 0HBMI8TRT. Mil mixture i i heated in a water bath as long as the pre- cipitate of alkaline bromide continues to form, care being taken at the same time to keep the worm well cooled, in order that the vapors of alcohol may contin- ually flow back into the flask. The alcohol is distilled off in a water bath, and the residue afterwards also distilled at a higher toiuperature, and that part col- lected which passes over between 140** and 200° . This portion which contains monacetic glycol, is heated with a saturated solution of baryta until the liquid acquires a strong alkaline reaction. The excess of baryta is removed bv passing carbon dioxide through the solution which is then filtered and evaporated. The barium acetate is precipitated completely by strong alcohol, and the alcohol subsequently removed by dis- tillation. The retort is now heated in an oil bath, and that portion set aside which boils above 150° . This is redistilled and the distillate between 190° and 198" is the product sought. Zeller and Huefner have lately (18, 10,270) obtained the purest glycol by simply hea^ ing a solution of potassium carbonate with ethylene bromide. Glycol is a colorless, odorless liquid, somewhat viscid and having a sweetish taste. Its density is 1.12; water and alcohol dissolve it in all proportions. Ether dissolves it with diflSculty. It is not oxydized in the air under ordinary con- ditions, but if dilute glycol be made to fall on plati- num black, it becomes heated and is transformed into glyoolio acid. Itsequivalenceis shown by the follow- mfmmiteKit MMN MMMM ALCOHOLS. ei Ing: glycol attacks sodium forming two Bodium glycols; NaH ("»' Na,J"»- These glycols furnish two ethyl glycols on being heated with ethyl iodide. Sthyl-Eljrcol. (0,H.), \ ^*- OlethyUglycol. With hydrogen bromide it furnishes two different products according to the number of molecules of HBr taken. 0,HA+ HBr = OaHjBrO + HjO. ^ » ' Monobromhjdrie eUier. CaHjOj + 2HBr=C3H4Bift- 2HaO. V ^ / Bthylens bromide. It is evident tlut mixed ethers may be obtained by treating glycol not with two molecules of the same acid, but with two molecules of different acids. Thus C H ) aceto-chlorhydric glycol is formed (q u.q\oI f ^* ^ 62 OKGANIO OIIEMISTRY. These ethers in the presence of alkalies, are re- formed into their respective acids and glycol, in the same manner in which ethers of ordinary alcohol regenerate alcohol. Monochlorhydric and aceto-chlorhydric glycol form an exception to this rule ; they form oxide of ethylene in presence of alkalies. OXIDK OF ETHYLENE, OaH40, a polymer of (CaH4)20a, is related to glycol as ordinary ether to alcohol. It is not obtained like the latter by the action of hydrogen sulphate on the alcoholic compound, but is produced by the action of potassa on mono- chlorhj'dric glycol. A solution of potassa is gradually poiired into chlorhydric glycol placed in a glass, or a tubulated retort. KHO + CgH.ClO = KCl + HgO + CgH^O. The oxide of ethylene distills over with the water; the latter is absorbed by causing the vapors to pass through a flask containing anhydrous calcium chloride, and the oxide is condensed in a receptacle placed in a refrigerating mixture. It is a colorless, ethereal, fragrant liquid; boiling at 13". Its density is 0.89. Ethylene oxide is very solu- ble in water, alcohol and ether. It burns with a lumin- ous flame and reduces siiver salts. It has the compo- sition but not the properties of aldehyd, of which it is an isomeride. IMIII ■TSFiMr'T^r p »y7«i.v f SEjffif'^ ater; pass ride, in a igat BOlu- min- mpo itis ALCOHOLS. 63 Oxide of ethylene is a very remarkable body. It combines directly with oxygen, hydrogen, chlorine and bromine, also combines directly with acids, often even with tiie disengagement of heat, forming the ethers of glycol and polyethylenic alcohols. This body is there- fore a true uoii-uitrogeuous basic oxide. ^ 64 ORGANIC CHEMISTRY. TEIATOMIO ALCOHOLS OR GLYCERINES. Obdinaet Glycebinb, CsHgOa CsHs '- H3 }0, Tills body, discovered by Seheele, in 1Y79, and called by him, on account of its sweet taste, the sweet principle ofoil8,has been specially studied by Chevreul and by Pelonze. Berthelot discovered its real nature and proved it to be a triatomic alcohol. Glycerine is prepared by decomposing neutral fatty bodies, in the soap and candle industry by alka- lies, or better still by superheated steam. {Tilghman'a process.) It is obtained in pharmacy, whenever lead plaster is prepared and remains in the water with which the latter is washed. It is much employed in pharmacy and perftimery and as a solvent for many substances. Crude glycer- ine may be puriiied by boiling with animal charcoal and filtering before being evaporated to the required consistency. The best process consists in distilling the crude condensed glycerine in a current of steam. Pas- teur has shown that glycerine is produced in a very small quantity in alcoholic fermentation. "We owe to "Wurtz, a remarkable synthetical reproduction of glycer- ine. Propylene CsHg furnishes an iodide OgHsI, called iodide of allyl. This body produces with bromine the 'p^fm^-'^ ^ ES. I, and sweet evreul aature lentral r alka- man^s r lead with imery jlycer- larcoal quired ing the Pas- a very owe to glycer- called no the ALCOHOLS. 65 compound CgHsBrg which, treated with potassa, or oxide of silver, yields glycerine. CaHsBrs+SKHO =■ 3 KBr. +C3H8O3 . (ilycerine. Glycerine is a syrnpy liquid, colorless, of a sweet '» taste and destitute of odor; its density is 1.28 at 16°. Sarg has obtained crystals of glycerine, whose angles have been measured by Victor Lang (2-152-637). They are rhombic in form and very deliquescent. Glyc- erine is soluble in alcohol and water in all propor- tions; it is not dissolved by ether. It dissolves alka- lies, alkaline sulphates, chlorides and nitrates, copper sulphate, silver nitrate and many other salts. Glycerine distills at 280°, but is thereby partially decomposed. It may, however, be distilled in a vacuum without change. It is decomposed at a tem- perature above 300°, and oils, inflammable gases, carbon dioxide, and a product very irritating to the eyes, called acrolein, acrylic aldehyd, are formed; this last substance may be obtained pure by distilling glycerine with sulphuric, or phosphoric acid. The formula of acrolein is CgHiO,;; it is also produced in the dry distillation of all fatty bodies which contain glycerine. If glycerine be made to fall drop by drop upon platinum black, it unites, like alcohol and glycol, with Oa and glyceric acid is formed. CaHgOs + Oa=CsHe04 + H2O. The oxidation of the glycerine does not stop here; i -mmm IMW Qg 66 ORGANIC CHEMISTRY. there is subsequently forined, acetic, formic, and car- bonic, but chiefLy oxalic acid. The action of acids on glycerine demonstrates two facts; first, that glycerine is an alcohol; second, that it is a triatomic alcohol. On treating glycerine with hydrochloric acid the first reaction is similar to that between alcohol and this acid, HCl+CsH808=C3H,C102+H20. Monochlorbydrio ether, or MoDOchlorhjrdrin. The continued action of phosphorous perchloride upon glycerine, or the dichlorhydrate of glycerine, effects the elimination of additional molecules of water and the fonnation of trichlorhydrin. 8HCl+03H808=C8H5Cla + 3(H.,0). Trichlorhydrin. Berthelot has studied the acetines, bntyrines (tri- butyrine exists in butter), valerines, and many other ethers of glycerine. If glycerine is u. ...- with cold nitric acid, and sulphuric acid added drop by drop, an oily substance separates out which is trinitroglyoerine, C3H5(NOi)308. This body detonates with great vio- lence. It acts very energetically on the systeni. A few drops placed on the tongue pro*luce violent me- grim. Glycerire forms compounds, with lime anal- ogous to those formed by sugar, according to P. Car- les, (1-174-87). ALCOHOLS. 67 nd car- icids on ycerine alcohol. ;he first od this shloride yrcerine, >f water nes (tri- j other th cold Jrop, an lyoerine, eat vio- ;eiri. A lent me- 18 anal- . P. Oar- Uses. — The uses of glycerine in the arts, and especially in pharmacy, are numerous and important, many of which are based upon the solvent power of this compound. Henry "Wurtz (31-195-58) has made valuable suggestions as to its economical applications. -TABLE BHOWINO THB SOLUBILITT OF 80MII CHKMIOAI.S IN OLTCEniNB, (FROII KLBTBB.) OHB UUNDKED PABTS OF QLTOERINB DIgSOLVB THB AMNBXED (QUANTITIES or TBB I«LLOWI»a OHBMIOALS; Arsenoux oxide, 20.00 Ai'Bcuic oxide, 20.00 Acid, benzoic, 10.00 " oxalic, 1B.0O " tannic. CO.OO Alnm, 40.00 Ammoninm carbonate, 20.00 " cliloride. 20.00 Antimony and potosBinm tartrate, B.60 Atropia, 8.00 Atropia sniphate. 38.00 Barium chloride. 10.00 Brncla, S.26 Cincbonia, . 0.B0 " sniphate. 6.70 Copper acetate, 10.00 " so'phalo, 80.00 Iron and potasBlnm tartrate. 8.00 " lactate. 16.00 " sulphate. 26.00 Mercuric chloride. 7.50 Mercuroas chloride, iW.O0 Iodine, 1.90 Morphia, 0.4G Morphia acetate. 20.00 " cblorhydrato. 20.00 Fhosphorns, 0.20 Plumbic acetate, 20.00 Potassium arsenate. 60.00 " chlorate, 8.60 " bromide. 25.00 " cyanide. 82.00 iodide. 40.6b i^ninia, 0.50 " tannate. 0.J5 i;;Vi:<,^vi;:i' Bodlnm argennte, ■' bicarbonate, " borate, " carbon'te, " chlorute, Sulphur, Strychnia, " nitrate, " aulphate, Urea, Veratrla, Zinc chloride, " iodide, " lulphate. On O, may be regarded as the oxides respectively of methyl and ethyl. They bear the same relation to alcohols that oxides of the metals do to the hjdrftt*>B, Potassium hydrate KOH. Ethyl hydrate, or ethyl alcohol CjHsOH. Potassium oxide Ethyl oxide or ethyl ether K K CjH, The simple ethers are mostly liquid. They are very slightly soluble in water, wliile they are readily soluble in alcohol. Expo.5ed to the action of alkaline solu- tions they regenerate alcohol. C4H80a+KHO = CaHsO+KCaHsOg." "TO ORGANIC CHEMISTRY. BTHYL ETHEB. Bjfnonym* : Vinic ether, sulphuric ether, common ether. Density .736. Density of vapor, 87. Specific gravity of vapor, 2.586. Boiling point, 85.6°. To prepare this compound, sulphuric acid is heated with alcohol in a retort, placed in a sand-bath. The ether distills, its vapor being received in a well cooled condenser, provided with a long tube which conducts the Tincondensed vapor into a chimney. The cork adapted to the tubulure of the retort is provided with two openings; in one is fixed a ther- mometer, through the other a tube passes which fur- nishes the supply of alcohol. All the connections should close perfectly. When the apparatus is arranged . in this manner, pour 700 grams of 86 percent, or 90 per cent, alcohol into the retort, and add, little by little, 100 grams suli)huric acid of 1. 84 sp. gr., then heat. When the thermometer attains 130°, cause the alcohol to flow from the upper vessel at a rate sufficient to keep the temperature between 130° and liO". The weight of alcohol capable of being transformed into ether is from 13 to 16 times the weight of the mixture first in- troduced into the retOrt. The distilled liquid is mixed ETHERS. 71 with 12 parts, to every 100 of its weight, of a solution of soda having a specific gravity of 1.32, and agitated from time to time, during 48 hours. The ether is decanted by means of a glass siphon,, redistilled and four-fifths of the liquid collected. The remainder may serve for a future operation. This furnishes ordinary etlier. To further purify, wash with water, decant and treat for two dayswith equal parts of quick lime and fused calcium chloride. Wil- liamson has clearly shown that etherification takes place in two stages or successive reactions as follows: OaHeO+HaS04-HjO + (C,H5)HSO«. ' Btbylialphuric acid. (03H5)HSO4 + CaHjO = C4H,oO + HjSO^. This explains how a small quantity of sulphuric acid etherizes a large amount of alcohol, eince sul- phuric acid is constantly regenerated. This is con- firmed by the following experiment. Iodide of ethyl is made to react upon potassium alcohol ; ether is obtained as indicated by the reaction; CHJ H- C^HsOK - C4H,oO + KI. Ether is a neutral, volatile liquid, colorless, having a burning taste and a strong agreeable odor. When agitated with water it rises to the surface, but the water dissolves about one ninth of its ovfn weight of the ether. It is miscible with alcohol in all proper- riP" 78 OROANIO 0HEM18TKY. tionsand with wood spirit. Ether ia frequently adul- terated with the latter substance. 'Next to alcohol it is the most generally employed solvent for organic substances. It dissolves resin, oils and most com- pounds rich in carbon and hydrogen. Bromine, iodine, chloride of gold and corrosive sub- limate are soluble in tliis liquid. It dissolves phos- phorus and sulphur in small quantity. W. Skey (8 — Au^. 3, '77,) has shown that contrary to the usual statement in standard works, ether dissolves notable quantities of the alkalies. At a red heat it is decomposed and furnishes carbon monoxide, water, marsh gas and acetylene. It is exceedingly inflammable, and bums with a bright flame. Its extreme volatility, the density of its vapor, its insolubility in water and its great inflammability render its use dangerous, and explosions caused by it are of frequent occurrence. It should never be brought near a fire or light in open vessels. In case ether inflames, it is best, if possible, to at once close the vessel con- taining it, and thus avoid the more serious conse- quences ensuing from an explosion. Exposed to the air it experiences a slow combustion as in the case of alcohol, and the same compounds are the result. Chlorine acts violently upon it; in moderating the action, the whole or a part of the hydrogen may be replaced atom for atom by chlorine. Uses. — It is used in pharmacy in preparing etherial '^m ■WW BTHSB8. 73 tinctures, a;id as an antispaBmodio and stimulant in the well-known Hoffmann's anodyne. Its most impor- tant use in medicine is as an anesthetic, than which none is safer or more reliable in efficient hands. It is extensively employed in the laboratory and in photography. COMPOUND BTHEES are bodies built up on the type of water, having one half the hydrogen replaced by a hydrooarbide and the other half by a compound radicle containing oxygen, or, in other words, by the radicle of an acid. (C2H5) I n A0ETI0KrHEK,J(.^'jj»^Q^fO. To prepare this ether 8 parts of very concentrated alcohol are distilled with 7 parts of sulphuric acid and 10 parts of anhydrous sodium acetate, which may be replaced by 20 parts of dry lead acetate. The distil- late is agitated with a solution of calcium chloride containing milk of lime, decanted, dried over calcium chloride and finally distilled. Seven parts of water dissolve one part of this body. Alcohol and ether dissolve it in all proportions. It is a solvent for many organic bodies. It is easily de- composed on contact with water. Potassa also effects this decomposition very readily. A prolonged action of ammonia transforms it into acetanude and alcohol. I I 74 OROANIO CHEMISTRY. OXALIC ETHERS. Oxalic acid, being a bibasic acid, furnishec with alcohol two combinations, one being acid and capable of combining ' ith bases ; the other is neutral, CgH,o04. Only the latter is of interest. It may be prepared by introducing four parts of 90 per cent, alcohol and four parts of oxalic acid into a retort, adding to this mixture three to six parts of sulpnuric acid and then rapidly distilling ; the product is washed several times, dried, then redistilled, collecting only the liquid which passes over at 184°. This ether is aromatic, oily, and gradually decomposes in water. Potassium changes it into carbonic ether. If oxalic ether is agitated with ammonia, a white powder, oxamide, and ethyl alcohol are produced. (OA)' 21 ((C^g»)|0)+Njgf^^' H, Oxamide may be considered as derived from two molecules of ammonia, and belongs to a class of bodies called diamides. ^ It is a white substance, insoluble in cold water and alcohol. Heated with mercuric oxide it is transformed into carbon dioxide and urea. (Williamson.) ETHERS. 76 z With lapable ,Hio04. epared lol and to this d then . times, which ly, and white ;ed. 3m two ' bodies ter and iformed Oxalic ether treated with ammonia in solution in alcohol fumishea oxamio ether. In this connection tho compounds of the organic radicles with the haloid elements are usually studied: they iM-e not unfrequently denominated ethers of the hydrauds. Their type is a molecule of hydrogen, g- | . CULOBIDK OF BTHTL OB OULOBHYDBIO ETHEB. C,H,Cl=CjH %\\ This body is formed in small quantity when ethy- lene is made to react upon hydrochloric acid. To prepare it, alcohol contained in a flask sur- rounded by cold water, is saturated with hydrochloric acid gas and the mixture then distilled. C8HeO+HCl=CaHsCl+H40. It is also obtained by pouring into a flask contain- ing 2 parts common salt, a mixture of 1 part alcohol, and 1 part sulphuric acid : it is then gently heated and the ether collected as previously shown. It is a liquid of an agreeable odor, and very volatile, having a boiling point of 12° and a vapor density of 64". A red heat decomposes it into ethylene and hydrochloric acid gas. It is combustible and burns with a green, smoky flame; water dissolves the fif- tifeth part of its volume, alcohol dissolves it completely. s \ T« OUQANIO 0HBMI8TBY. With chlorine it fumishea a complete and regular Bcries of products of substitution which are not iden- tical, but isomeric with the chlorine products of ethene. Their formulsB are: GtH4Cl| GgHgClg CgH)Gl4 C,H CI, C, CI,. IODIDE OF ETHYL OB HYDEOIODIO ETHEE. C,ll,l = ^'^^{ I is obtained on causing alcohol to react upon iodide of phosphorus; the action is violent with white phos- phorus, considerably less so with red phosphorus. Six hundred grams of concentrated alcohol are intro- duced into a retort with 140 grains of amorphous phosphorus, and to this mixture 450 grams of iodine are added. The distilling is carried nearly to dryness. The product, condensed in the receiver, is washed with water containing a little potassa ; afterwards with pure water. It is then dried over calcium chloride and again distilled. Iodide of ethyl is a colorless liquid. Its density is 1.975. It becomes colored on exposure to light, being slightly decomposed ; it is again rendered colorless on agitating it with an alkaline solution, which absorbs the BTHER8. 77 acid formed. Itbnma with a green flame, leaving a resi- due of iodine. Ammonium compounds in alcoholic, or aqueous solution, furnish ethyhiraine. This amino can be attacked in its turn by iodide of ethyl and yields diethylamino and oxide of tetrethylammonium. The knowledge of these reactions and their application to other iodides are the basis of a general mode for the preparation of organic bases originated by Hoffmann." Iodide of ethyl, unlike the chloride, is readily decom- posed by solutions of silver nitrate, giving a precipi- tate of silver iodide. CJlsH-AgNOa = (CA) NOs+Agl. CYANIDE OF E'niYL, OB CYANHYDRIO ETHEB. This ether is obtained on distilling in an oil-bath 1 part of potassium cyanide, with 1-5 part of an alkaline sulpho-viuate. To the product, redistilled in a bath of salt-water, nitric acid is slowly added in excess ; it is then subjected to another distillation. Finally, it is dried over calcium chloride, and that which passes over from 195" to 200° is collected on redistillation. Cyanide of ethyl is a colorless liquid of an alliaceous odor, boiling at 97?. Cyanide of ethyl is decomposed by potassium hy- drate; ammonia is produced, and the acid obtaiucd corresponds with a higher homologous alcohol. 78 ORGANIC CHEMISTRY. ONCOaHs) + 2H2O = NH3 + CsHeOa. Propionic acid. M. Meyer observed some yeairf ago, that if cyanide of silver is treated with iodide of ethyl, a liquid is formed, boiling at 82", of an odor -which is not that of ordinary cyanhydric ether. Gautier has shown that this is an isomeric body, and that there are two isomeric series of cyanhydric ethers. Hoffmann has given a dis- tinctive character to these bodies: under ♦•'le influence of the alkalies they produce a fixed suostance, but this is formic acid and not ammonia, and a volatile substance which is a compound ammonia. CNCCjHs) + 2HjO= CH2O2 + C2H5 )■ N. Formic acid. Ethylamine. Oegano-metallto Compounds. Iodide of ethyl attacks the metals and fumishes a class of bodies called organo-metallio radicles. None of these bodies are found in nature. They are formed from the iodohydrie ethers by the substitution of a metal for the iodine; . . Zn + 2(0^1) =(C2H5)2Zn+ZnIj, 2Sn + 2(0aB[aI) = (CaH5)2Sn + Snl^. Practically these metallic radicles are obtained by various reactions: ORGANO-METALLIO COMPOUNDS. 79 1. By the action of the metal upon the iodide, for example; 2C2H5l+Zn2=(C2H5)aZn+ZnIj. \ In certara oases, wiUi tin for instance, the reaction is not as distinct, and there is formed in addition to stan- nethyl iodide, stannethyl iodides variously condensed. 2d. T':e metal is treated with another radicle; thus sodium-ethyl is prepared by the action of sodium upon zinc ethyl, (C2H5)2Zn + Na,= Zn + 2C2HsNa. 3d. On decomposing a metalloid compound radicle •with a metallic chloride, 3ZnClj +2(C2H5)aP= 3(C2H5)Zn + 2PC18. 4th. Stannethyl is obtained by plunging a plate of zinc into a soluble salt of this radicle: the radicle is precipitated in the form of an oily liquid. Cacodyl, ^8(CHs)3 was the first discovered of this class of bodies. It was obtained by Bunsen on distilling arsenous acid with potassium acetate. The organic radicles combine with metalloids with more or less energy ; zinc-ethyl and cacodyl take fire in the air ; they also decompose water. The products of oxida- tion vary with the nature of the compounds employed; zinc-ethyl furnishes the body, C-^HsZuO, zinc-ethyl- ate, which, in contact with water, produces alcohol and oxide of zinc. The metals which are less readily oxy- 80 OBOAinO 0HBMI8TBT. dized, such as tin, lead and aercury, give oxides which play the parts of bases, and these latter com- port themselves like the oxides of the metals they con- tain. Finally, the radicles formed by the elements, phosphorus, arsenic, and antimony, give, with oxy- gen, compounds which generally have the character of acids. Some of the organic derivatives containing phos- phorus are very complex. For instance, J. Ananoi? (60-"r5-493) has obtained a body he denominates, vnethyldiethylphoaphoniumphenyloxidehydrate! •Xo prepare zinc-ethyl, we introduce into a flask connected with a condenser inclined in such a manner that the vapors find their way back into the flask, 100 grams iodide of ethyl, 75 grams of zinc, and 6 to 7 grams of an alloy of zinc aad sodium, and haat in the water bath until the zinc is dissolved ; then the condenser is inclined as usual, and the distilling is effected over a direct fire, collecting the liquid pro- duct in a flask filled with dry carbon dioxide. Finally it is again distilled in this gas, and that col- lected which passes over from 116° to 120°. All the vessels and all the substances should be absolutely dry, and it should always be collected and distilled m vacuo, or in carbon dioxide. It is a colorless liquid, whose density is 1.182, boiling at 118°, inflammable on exposure to the air. With sodium this body fhrnishes sodium-ethyl, and with chloride of phosphorus or arsenic, it furnishes triethyl phosphine, P(02H5)8, and triethyl arsine. As (CjHjV ETHERS. 81 Mercury-methyl, treated with iodine, famishes a hydrocarbide which has the formula of methyl, CHs. Pi-ofessors Crafts and Friedel (72-[4]19-334) have prepared a large number of compounds of silicon with compound radicles, from which they have deduced valuable theoretical considerations. MISCELLANEOUS ETHERS. Formic, butyric, valerianic ether, and other ethers of the fatty series are prepared in the same manner as acetic ether, and have the general properties of this ether. The odor of these ethers is agreeable. Bu- tyric ether has the odor of pine-apple, and valerianic ether that of pears ; oenanthylic ether has the aroma of wine, etc. They are used in the manufacture of syrups, flavoring extracts, and for imparting an odor to liquors. If the difference between the points of ebullition of these ethers is examined it will be seen that the addition of the elements. CH2 causes an elevation of about 20° in the point of ebullition. Kopp has shown that this fact is a general one and applies to the alcohols, and acids of the same series, and to the homologous bodies in genera) Point of ebullition. Difference. Formic ether, - - 66° Acetic " - - 74:° Propionic « - - 96° Butyric « - - 119° Valerianic" - - 133° 19° 21° 24° 14° ^2 OBGANIO CHEMISTRY. The boiling point of one of these bodies may accord- ingly be predicted, if that of one of its homologous substances is known. There is a certain close relation between the point of ebullition of an ether and that of the acid whose radicle it contains: Point of ebullition. Differejice. Formic acid, - ' - 105° ) « ether, - - 66° f 60» Acetic acid . - - 118°) " ether, - - 74° f M» Propionic acid, - -140°) « ether, - - 95° j" . ^^^ Butyric acid, - - 163° ) " ether, - - - 119° J 44* The solubility in water of the ether formed by homologous acids varies with the molecular weight ; thus formic ether is quite soluble, acetic ether is less soluble, butyric ether is but slightly so, and valerianic ether, which follows it, is nearly insoluble. MEKCAPTAN8 AND THEIB ETHEES. On substituting sulphur, selenium, or tellurium for oxygen in the alcohols of different atomicity, sulphur, selenium, or tellurium alcohols are obtained, which are designated as mercaptans, selenium mercaptans, and tellurium mercaptans. Ethers proper correspond to these as to ordinary al- cohols. These ethers are derived either by the substi- ETHERS. 88 tution of an alcohol radicle for the typical hydrogen, as happens with monatomic mercaptans, or by the elimination of HaS, as is the case with biatomic mer- captans. One only of each of these two classes will be alluded to here. Ethyl snlphide, or hydrosulphn- 1 r) jj g ^CzHg ) g ric ether, j * ^° C2H5 | Ethyl mercaptan, C,H. C4H6S=-^g«|s. To prepare the sulphide a current of ethyl chloride, is passed into an alcoholic solution of potassium sulphide. The mercaptan is prepared by the action of potass- ium hydro-sulphide on ethyl sulphide. In either case potassium chloride is formed. K^S +2CjH^]=-C4H,oS+2KCl KHS-hOgHsCl-CsHs S + KCl. These bodies are afterwards separated by distillation. Like all the sulphur derivatives of alcohol, they have a nauseous odor. The sulphide boils at 91° the mer- captan at 36°. MIXED ETHEBS eontaining two dijfferent radicles, are obtained by act- 84 ORGANIC CHEMISTRY. ing, for instance, with ethyl iodide upon potassium methylate, thus : C.H J + CH" ii'[o-Ki + g^lo- ethyl iodide, potasstnm potassinm methyl-ethyl methylate. iodide. ether. PIT ) or by acting on hydric methyl sulphate j^ ,• SO4 with ethyl alcohol. The following is a list of some of the more important mixed ethers of the monatoinic Beries; TABLE OP AQXEO ETHEfiB. Methyl-etliyl ether 031180= ^^ I O Methyl-amyl ether C6Hi40 =q^^^ \ O Ethyl-butyl ether CeHi40= ^^^^ | O Ethyl-amyl ether C^HaeO = q^^^J^ I O Ethyl-hexyl ether CsHigO = ^^^ | O BOILING POINT. + 11" ALDEHYD8. 86 ALDEHYDS. .. The following are the principal aldehyds, arranged | in seriee: OnHa„0. Formic aldehyd - - - C HjO Ethylic aldehyd - - CaH4 Propylic aldehyd - - - Cs Hj Butylic aldehyd - - - CiHsO Valeric aldehyd - - C5H10O (Enaathylic aldehyd - - C,!!!*© Caprylic aldehyd - - - Cg HigO Caproic aldehyd - - CiqHjoO Kutie aldehyd - - CnHaO Ethalic aldehyd - - OieHajO C„H2„.aO. A Hylic aldehyd (acrolem) - Cs H^O OnHjn^O. Campholic aldehyd {camphor) CioHwO t » ^'ijisS^fe^' ■£:.B< 86 OBGANIO CHEMISTRY. Benzoic aldehyd {oil of hitter aJmonda) Q^ Hj O Toluic aldehyd - - - - CsHaO Cuminic aldehyd ... - CioIIi^O Sycocerylic aldehyd ... C18K23O CnHun-loO. Cinnamic aldehyd {oil of cinncmion) - OgHgO. Aldehyde may be regarded as bodies built upon the type of one or more molecules of hydrogen, in which one half the hydrogen atoms are replaced by one or more molecules of an oxidized carbohydride. The formation of aldehyd, (afcohol (?My ^^tjw '. ,U'ji" !' y ' .wiw.y : "tf.iJ. ' .iiTj|»i|V ' MW!/.J^ ' . ii -/W"^ ' "-'"«*" ' «-"! *' w'-!" ' V^.v■■ ■ '■' ' \ CnH2n-^0g. . . Oa4Ha804. Carballylic acid CeHaOe. ' ' ' ■ ' - ' CnHijn-eOj. •■ ■: C,oHe04 C12H10O4. Aconitic acid CjHflOe. .,.-„ ,-,.... CnH2n_ioOs. POMS OF OXYGEN. r ^ ;, ; , .■ '■■•.:,-■■■ Chelidonic acid CnH2n_io07. C,H4 0« CsHA C4HA. Meconic acid C7H4O, Citric acid CeHg O7 Mucic (( CeHioOg. m CaHA 8J-L2V^5. t nwiwijiUg Organic acids are bodies built upon the type of one or more molecules of water, having one half tJic hy- drogen replaced hy an organic compound radicle con- ^ 96 OBOANIO OUBHISTBY. taining oxygen. There are some acids whose compo- sition is not definitely fixed. We shall first examine the monatomic acids, and study the other series in the order of their atomicity. . The organic acids possess the general properties of the mineral acids. Many among them, like aceticacid, have a very decided action upon litmus. Generally, they are solid and crystallizable; however, formic, pro- pionic, butyric acids, etc., are liquid. Acids whose molecules are comparatively simple, are ordinarily sol- uble in water — the others are little, or not at all, soluble in this solvent. The monobasic acids are volatile, at least where their molecules are not very complex. The polybasic acids are decomposed by heat. Their salts are ordinarily crystallizable. METHODS OF PREPARATION. * % ■ - ' • I. The acids of the so-called fatty series are ob- tained by the oxidation of the corresponding alcohol, or aldehyd, which latter is the first product of oxida- tion of the respective alcohol. X, CijHeO-HO =C2H4O-hHj0. Acetic aldehyd. C2H40 + 0=C2H40,. Acetic acid. II. These acids are also produced by the action of alkalies upon the cyanide of the radicle appertaining to the homologous inferior alcohol. whose corapo- l first examine er series in the al properties of like acetic acid, lis. Generally, ver, formic, pro- Acids whose e ordinarily sol- lot at all, soluble are volatile, at complex. The jat. Their salts N. ■ y series are ob- jonding alcohol, roduct of oxida- :.o. by the action of icle appertaining ORGANIO AOIDS. 97 (CH8)CN + KHO + HjO==NH3 + KC^HaOj. Methyl cyanide. PotaiBlam acetate. III. Acids are likewise formed by the imion of the elements of carbon monoxide and carbon dioxide with hydrogen carbides and water. The remarkable syn- thesis of formic acid by Berthelot is, according to this method: /.■-■.. '■■,■■ C0+H20=CHA. Pelouze has shown that heat, carefully applied to polyatomic acids, causes them to part with a certain number of rxiolecules of water, of carbon dioxide, or of both, and furnishes acids more simple and of a lower equivalence, which he designates by the name oipyro- acids. 2C4He08=GiH804 + 2H20 + 3C0a. Tartaric acid. Pyro-tartaric acid. Of all tlie series of acids, the most numerous and the most important are those of the so-called fatty series- We shall presently indicate the methods by which they are obtained. Their boiling point increases from 15° to 20" with each addition of CHj to their molecule. Certain of their salts, those of calcium, for instance, are decom- posed by heat, furnishing compounds called acetones. ■If*""" 98 ORGANIC 0FV.MI8TET. Ca(CjH802)2=CaCO,+C,IIflO. vr > / Calcium acetatj. Ordlnaty acetone. FORMIC ACID. CHA=CHO|o. , Red ants made to pass over moistened blue litmus paper produce red stains. The acid secreted by these insects was first obtained by Gelilen, and has re- ceived the name oi formio acid. I. Berthelot has obtained it from carbon mon- oxide by synthesis. II It is prepared by distilling a mixture of 10 parts of starch, 30 parts of sulphuric acid, 20 parts of water, and 37 parts of manganese binoxide in a large retort connected with a condenser. The mass swells considerably, and at first must be heated but gently. The formic acid is distilled over and saturated with lead carbonate. The Ibrmiate of load is caused to crystallize in boiling water, then placed in a retort and decomposed by a current of hy- drogen sulphide and thereupon heated; the formic acid is then distilled off. Ill One kilo of glycerine, 150 to 200 grams of water and 1 kilo, of oxalic acid are introduced into a retort and heated for 15 hours at a temperature of about 100°. The oxalic acid is decomi-osed, but only carbon di- oxide is disengaged. Water is added from time to iiili^i'iiiiaagM AOETIO ACID. 99 I blue litmus secreted by Q, and has re- carbon mon- nixture of 10 d, 20 parts of ide in a large , first must be distilled over ;ie Ibriniate of g water, then current of hy- the formic acid grams of water i into a retort s of about 100°. ,nly carbon di- from time to ■■ti-W"'i''"'''' "•'•'' ''""T"iti'i: time, and the mixture then distilled until 8 litres have passed over. The glycerine remains unchanged in the retort, and can ag-^in be used. Formic acid is a colorless liquid, of a very acid re- action, a pungent odor and crystallizing at about 0° and boiling at lO-i". It reduces oxide of mercury, furnishing mercury, as a brown powder, also carbon dioxide and water. Its salts are usually soluble, though that of lead is very little soluble in cold water, but q^uite soluble in boil- ing water. On lieating with sulphivric acid, carbon monoxide and water are formed. ExPKEiMKNT.— introduce into a test-tube a small qtiantity of foi-mic acid or a formiate. Add sulphuric acid and heat; a regular liberation of a gas takes place, which may be ignited, producing a blue flame. CH.O^ CO+HA ACETIC ACID. C2H402=02H30 H O. Bp. Gr. 1.08. Density, of vapor 80. Glacial acetic acid melts at 17o; boils at 118°. This is the acid of vinegar, and of which it forms the essential part. It is found in the juices of many plants and in certain fluids of the body. It is formed by synthesis from methyl, sodium, or potassium for- 100 ORGANIC CHEMISTRY. miate, and by the oxidation of acetylene; also by the action of nitric acid upon fatty substaTices, and by tlie reaction of potassa upon tartaric, malic and citric acids. It is further produced : I. By the oxidation of alcohol in the following way: Wine in vats, or casks, is placed in a cellar main- tained at a temperature of about 30»; every sixth or eighth day several litres of vinegar are withdrawn and replaced by an equal quantity of w.ne. Pasteur has established that the oxydation of alco- hol is produced by a minute plant, the Myoodeima aceti. In fact, acetification commenceB only when this plant has been formed in the liquid. If its development is interrupted the oxydation stops; it renders the service of taking oxygen from the air and transferring it to the alcohol. Thi 8 process is very slow. It may be rendered more rapid by pouring dilute alcohol on beach-wood shav- ings placed in barrels. The air penetrates through openings made in the lower portion. The alcohol, after having been passed over the shavings four times, will be tound sufficiently acetified, if the temperature is maintained at about 25°. II. DisnLLA-nori of wood. Pyholignbous acid. Wood is distilled in retorts , yielding vapors and gases. The former are condensed by causing them to pass through a condenser ; the gases are conducted under the retorts, wheje they are burned, and the heat util- ized in the distillation of the wood. The condensed liquids are water, acetic acid, wood ■X* ilso by the and by the sitric acids. owing way: iellar main- )ry BJxth or hdrawii and [' ion of alco- MyGodei ma only when liquid. If ion stops; it the air and sndered more i-wood shav- atea through The alcohol, ;b four times, inperature is 1NB0XI8 ACID. ors and gasss. ;hem to pass ducted under the heat util- tic acid, wood J AOETIO AOID. 101 spirit and tar ; thtj greuter portion of the tar is mo- dianiciilly reitmved and the roinaining liquid distilled in a water bath. The wood spirit, which boils at 63° passes into the receiver. The water and acetic acid<- remaining in the retort are saturated with sodium carbonate, the product is evaporated to dryness and heatod from 250° to 360°; this temperature, while not effecting the decomposition of the sodium acetate is sufficient to carbonise the tarry substance remaining in solution. The mass is thereupon dissolved in water, filtered, and the acetate allowed to crystallize. If it is desired to obtain the acetic acid uncombined, the solu- tion of the salt is distilled with a slight excess of sul- phuric acid. The acetic acid which distils over contains a large amount of water. Normal, or anhydrous acid may be obtained froiri it by saturating half of the liquid with sodium carbonate, then adding the remainder to this solution; acid sodium acetate is thereby produced, which is evaporated to dryness and distilled with sul- phuric acid. This liquid, cooled with ice, gives crystals of normal acetic acid, which can be separated on de- canting the liquid, furnishing the so-called glacial acetic acid. ^ Acetic acid is liquid above 17°; below that it crys- tallizes in handsome plates. It is a strong acid, has a pronounced odor, and is very caustic, producing blis- ters on the skin. It is soluble in water, alcohol and ether in all proportions. It dissolves rosin and cam- phor, also fibrin and coagulated albumen. On uniting 'H ii ^m 102 ORGANIC CHEMISTRY. with water it contracts in volume. A red heat de- stroys it, many products being formed; methane, acetylene, acetone, benzol, naphthalin, etc., alsocar- ■' bon, wliich remains in the retort. If a flask containing chlorine gas and a small qnan- ihy of acetic acid, is exposed to the sunlight, trichlor- C CI O ) acetic acid is fonned, ^ ^jj ^ O. This experi- ment of Dumas served as a basis for the theory of substitution. Le Blanc has also obtained monochlor- acetic acid CaHjClO [ ^y rpj^^g^ chlorine products are reduced to the state of acetic acid by reducing agents, such as sodium amalgam in presence of water, (H,)8-fC2HCls05.=3HCl+C2Tl40.. In the same manner as acetic acid, heated with an excess of a base, furnishes marsh gas, trichlor, acetic acid produces trichlorinr.ted mai'sh gas, which is chloroform, C2H402+BaO=BaC03 -H CH4 C^HClsOj-f BaO=BaC03 + CHCI3. Perchloride of phosphorus, in the hands of Gerhardt, !ia8 become the means of an important discovery, that of acetic anhydride and in general of the anhydrides of the monobasic acids. If dry sodium acetate (3 parts) is mixed with the perchloride, or better, with oxy- ^*"'*w^ I I heat de- methaTie, !., also car- mall quan- it, trichlor- his experi- e theory of inonochlor- )roduct8 are jing agents, atei", ted with an 18, trichlor, 1 gas, which Cla. of Gerhardt, scovery, that 8 anliydrides in acetate (3 ;ter,withoxy- VINEGAR. 103 chloride of phosphorns, (1 part), and then distilled, a chloride is obtained called acetyl chloride, C,H30C1=C,H,0 CI }• acetyl being the radicle of acetic aci"' . This chloride, subjected to the action of an excess of sodium acetate, is decomposed and furnishes acetic anhydride, C,H30P' (also called acetate of acetyl) or acetic oxide, which boils at 139°. Water destroys it, acetic acid being produced. Chloride of acetyl is an irritating liquid, boiling at about 158°, decomposable by water into acetic and hydrochloric acids. A derivative of acetic acid of considerable theoretical importance is cyanacetic acid CsH3N02=C2H3O ) ^ CNf'-'' a crystalline body forming salts with the metals, which have been studied by T. Menies. On acting with sul- phuric acid and zinc on cyanacetic acid, the author [82-67-69] obtained formic and acetic acids and am- monia. Vinegar. This name is given to the mixture which is obtained by the acetification of wine, whiskey, infu- sion of malt, etc. Good acetic vinegar is of an agree- able taste and aroma. Wood vinegar has a very strong disagreeable taste and odor. It is frequently 104 ORGANIC CHEMISTRY. adulterated with sulphuric acid. An addition of ^^^-^ of its weight of this acid is, however, not considered fraudulent, as its presence is regarded necessary to prevent moulding. A ready method of detecting mineral acids, pro- posed by M. Witz (77-75-268), is based upon the use of methyl-aniline, which undergoes no change in con- tact with acptif, acid, but promptly changes to a green- ish-blue in presence of the least trace of mineral acid. Vinegar and concentrated acetic acid are employed in medicine us stimulants. An acetate, or acetic acid, can be recognized by heat- ing it slightly with sulphuric acid and alcohol ; a fragrant odor, characteristic of acetic ether, is observed. Heated with sulphuiic acid alone, the acetates liberate a vapor which has the odor of vinegar. The following reaction permits of the detection of mere traces of acetic acid; it is saturated with potas- sium carbonate and heated with arsenous oxide in a test tube; fumes and a nauseating odor are given off. The author finds that one of the simplest tests for acetic acid, is to direct a fine, yet powerfiil stream of water into a test-tube, containing a few drops of the liquid to be tested. The very fine, white efferves- cence resulting is entirely characteristic of this acid, none of the other ordinary acids producing the same effect. Alcohol should not be present, as it causes a similar effervesence. If-the acetic acid is combined it should be set free with a strong mineral acid. By this test, ••w^ J ACETATES. 105 ion of 1 ^T7 , considered ecessary to acids, pro- >on tlie use mge in coii- to a greeii- lineral acid. B employed zed by heat- alcoliol ; a is observed. ;e8 liberate a detection of with potas- oxide in a given oflF. est tests for al stream of drops of the ite efferves- Df this acid, ig the same ses a similar 3d it should By this teat, perhaps more physical than chemical, acetic acid, di- luted with 1000 parts of water, can be readily recog- nized, and with practice, one part in ISf" ACETATES. Acetic acid is monobasic; there are, however, alka- line biacetates and some basic acetates of copper and lead. POTASSHTM AOETATB. KCjHsOa^CaHsO ^0. This salt, distilled with its weight of arsenous oxide, furnishes a very inflammable liquid, formerly called the "liquor of Cadet," and in which Bunsen has found a radicle spontaneously inflammable, cacodyl^ C4II12AS2. Potassium acetate fonns, as well as sodium acetate, an acid acetate when treated with acetic acid. It is a very deliquescent salt, difficultly crystallizable. AMMONITTH AOKTATB, NHAHsOa, Is prepared by saturating ammonium carbon- ate with acetic acid. Its solution constitutes the spirit of Mindererua ; treated with phosphoric oxide it forms cyanide of methyl. There is also an acid salt, KH4CgH802.C2H403. In compounds of this character, 106 ORGANIC CHEMISTRY. acetic ao^d must be considered as acting the same part as the water of crystallization in salts. SODIUM ACETATE. NaCaHsOj+SIljO. This is used in preparing marsh gas and concentrated acetic acid. It is recommended by Tommase (62-72- 23), as a solvent for plumbic iodide, of which two grams are readily dissolved in 0.5 c. c. of a strong solution of sodium acetate. CALCIUM ACETATE. CaCCjIIsOaV This salt, subjected to distillatioi, furnishes a Hq^oid containing a large proportion of aoet n CsHjO- ALUMINUM ACETATE. AlCCaHaOa)^. This body is employed at present by dyers, as a mor- dant. It is prepared by causing aluminum sulphate to react upon lead acetate. Lead sulphate, which is insoluble, is separated on filtering the liquid. FEERIO ACETATE. This salt {pyrolignite) has been, and is still, somewhat employed for the preservation of wood. m— iMJ— g -'i W i Mw w mvmm ACETATES. 107 same part COPPER ACETATES. >ncentrated fise (52-72- i two grams ' solution of lies a Kquid •8, as a mor- m sulphate te, which is id. ,n.d is still) >f wood. Normal acetate Cn(C2H302)} is called verditer. It forms beautiful green crystals {crystals of Venus), which, subjected to distillation, furnish acetic acid mixed with acetone. During this operation, a white sublimate is formed, which deposits in the neck of the retort. This latter is cuprous acetate, and is car- ried over into the receiver, oxydizes, and changes into cupric acetate, which colors the distillate blue. There remains in the retort, after this decomposition, very finely divided copper which takes tire when slightly heated in the air. Solutions of this acetate reduce the salts of the oxide, CuO, and serve to prepare the sub- oxide, CujO. A basic acetate, designated by the name oiverdigris, is obtained by exposing to the air sheets of copper moistened with vinegar, or surrounded by the marG of grapes. The metal becomes covered with a greenish incrustation whose formula is, Cu(C2H302>j,CuO+6H20. LEAD ACETATE. The normal acetate Pb(C2H302)2 is prepared by treat- ing litharge with acetic acid in slight excess. This salt, known by the name of sugar of lead, crystallizes in oblique rhombic prisms, soluble in two parts of water and eight parts of 95 per cent, alcohol. It has a sweet taste, and is very poisonous. It is employed as a re- 108 ORGANIC CHEMISTRY. agent, also to prepare aluminum acetate and lead chro- iiiate. In digesting acetic acid with an excess of litharge, it furnishes a hexabiieic acetate of lead. If ten parts of normal acetate, with seven parts of litharge are taken and this mixture digested with 30 parts of water, there are formed minute needles of a tribasic salt Pb(C2H302)2, Pl)02, IIjO. Finally this salt, dissolved in normal ace- tate, gives a sesquibasic acetate, which is deposited in crystals, 2(Pb2C2ll30.,),PbO,IIA Goulard's bxtkaot is a solution containing a mix- ture of normal and of sesquibasic acetate of lead, which is prepared by boiling 80 parts of water, 7 parts of litharge and 6 parts of normal acetate of lead. BUTYRIC ACID. C^HaOa AH.O|o. It is usnally prepared as follows: a mixture of 10 parts of sugar, 1 part of white cheese, 10 parts of chalk, and some water, is maintained at a temperature of 30" to 36°. First, lactate of lime is formed, which causes the mass to thicken, then that salt changes into buty- rate, disengaging hydrogen and carbon dioxide. When the mixture has become clear, the liquor is evaporated and the butyrate separated with a skimmer. This salt is decomposed by concentrated hydrochloric acid which separates the butyric acid in the form of an oil, which is distilled off. It boils at 163°. It is of a fetid odor, and soluble in water, alcohol and etiier. VALEBIO AOID. 109 I lead chro- ' litharge, it ;en parts of re taken and r, there are bCCAOj),, normal ace- leposited in tiing a tnix- ;e of lead, iter, 7 parts lead. mixture of irts of chalk, atureofSO" hich causes s into buty- iide. When I evaporated mer. This ichloric acid tn of an oil, It is of a md ether. Valerianic, or Valeric Acid CbHioOj == * ^ij I O. It can be obtained by oxydizing amylic alcohol by a mixture of potassium bichromate and sulphuric acid or by distilling valerian root with water acidulated with sulphuric acid. The best method is to boil por- poise oil with water and lime. The oil saponifies and the valerianate of calcium alone is dissolved. This liquid is concentrated and liydrochloric acid added in excess. The valerianic acid separates out in the form of an oil which is distilled, and that portion collected which passes over at 175°. Pierre and Puchot have lately devised a process for preparing valericacid fromamylalcohol. (3-[3]5-40.) BENZOIC ACID, CrHgO. , v^7ij.gv/2. Density, 61. Density of its vapor compared with air, 4.27. Melts at 120°; boils at 250°. It is obtained by a dry, as also by a wet process. To prepare it by the former method, equal weights of sand and gum benzoin are placed in an earthen ves- sel, the mixture covered with a sheet of filter paper, which is pasted down round the edge, and a long cone of white cardboard placed over the whole. The earthen vessel is then heated over a slow fire for two hours, and when cool the cone is removed. The ben- zoic acid is found to have condensed on the interior of the cone in handsome blades, or needles. 110 OROANIO CHEMIHTRT. It is obtained in the wet way, by pulverizing gum benzoin, mixing it with half its weight of lime, and boiling for liiilf an hour in a cast-iron kettle, with six times its weight of water, care being ttxken to agitate the mixture. It is thrown upon a piece of linen and the residue treated twice with water. The liquids are reduced in volume to two-thirds that of the water used during the first treatment, then saturated with hydro- chloric acid. The benzoic acid separates out, and is recrystallized from a solution in boiling water. It is also procured from the urine of herbivorous animals. This secretion, evaporated to a small bulk and treated with hydrochloric acid, yields a deposit of hippuric acid, which, on being heated with dilute sul- phuric acid, is transformed into benzoic acid. Benzoic acid is also produced on a large scale from naphtlialin. Benzoic acid crystallizes in lustrous blades, or need- les, is little soluble in cold water, quite soluble iii boiling water, and still more so in alcohol and ether. On passing its vapors through a tube heated to redness, it is decomposed into benzol and carbon dioxide, CiHgOj = CBlIe+CO,}. Chlorine, bromine and nitric acid transform it into substitution products, Chlorbenzoic acid, C7H5CIO. Dinitrobenzoic " C7li4(NO-,)20.a. Ammonium benzoate furnishes, on distillation, berir izonitrile C,NHfl6a = C7H5N" -f 2HoO. The alkaline benzoates heated with chloride, or ,— j '» j ' a i'y.r J. ' J 7g » *y«T«a'-r'nwgy^.':y7r~. ■ BENZOIC ACID. m izing gum lime, and ;, with six 1 to agitate linen and liquida are water used ith hydro- ont, and is ter. icrbivorous small bulk , deposit of dilute 8ul- i. scale from 68, or need- e in boiling ether. On • redness, it n dioxide, and nitric llution, hen- jhloride, or oxychloride of phosphorus, furnish benzyl chloride, which, submitted to the action of potassium benzoate- in excess, gives benzoic anhydride, 3(KC,H80j)+POCl8 - 3(C,H50C1) + KbPO*. 1 Chloride of benz;!, C^HsOCl + KC^HA = C.JI.oOa + KCl. Benzoic anhytiride. The rational formula of benzoic anhydride is, Calcium benzoate heated to a high temperature furnishes henzone, Ca(C:n502)a= CaC03+CO(CeIl5)2. Calcium. benzoate. Benzene. Benzoic acid is monobasic, and the benzoates pre generally soluble. Benzoic acid taken into the stom- ach, ip transformed into hippuric acid. Kolbe and von Meyer have observed that benzoic acid has antiseptic power, though less than salicylic acid, (18-[2J12-133). ciNNAMio ACID. In Certain balsams there exists an acid called omnamio acid, whose formula is CjHgOj. It exists in the balsams of Peru, benzoin, tolu and in liquid storax. It fuses at 129° and boils at 290°. It 113 ORGANIC CHEMISTRY. has striking features of n semblance to benzoic aeid, and is produced like the latter by the oxydation of an aldehyd. This aldehyd is the essence of cinnamon prepared by distilling cinnamon with water. POLYATOMIC ACIDS. • OXALIC ACID. 0,HA-^§;|0,. Pbepakation. In the burdock and sorrel is found an aoid salt, commonly called salt of sorrel, which is a mixture of binoxalate and quadroxalate of potas- sium. Sodium oxalate is found in several marine plants, calcium oxalate in the roots of the gentian and rhuborb, and in certain lichens. Salt of sorrel is extracted from the burdock {Pruntus), in Switzerland, and in the Black Forest of Q-ermany, by expressing the plant, clarifying the expressed liquid by boiling with clay, and evaporating ; crystals of salt of sorrel are deposited. The oxalic acid may be obtained free by decompos- ing a solution of these crystals with lead acetate; the oxalate of lead which precipitates is treated with a suitable quantity of sulphuric acid ; the lead is com- pletely precipitated as lead sulphate; this is filteied off, and the liquid evaporated and allowed to crys- tallize. At present this acid is chiefly prepared by the action of oxydizing agents upon certain organic substances^ the substances best suited for this purpose are those v^tNBfr zoic acid, ion of an cinnamon 1 is found , which is of potas- ,1 marine ) gentian sorrel is itzerland, xpressing iquid by of salt of leconipos- acetate; ;ed with a id is corn- is filtered I to crys- the action bstances^ are tliose OXALIC ACID. which contain oxygen and hydrogen in the proportion to form water. One part of starch, o"" sugar, is boiled with eight parts of nitric acid diluted with ten parts of water, until nitrous vapors cease to be disen- gaged, and the liquid then evaporated. The crys- tals of oxalic acid which separate out are freed from the excess of nitric acid, by being several times re- crystallized in water. It is also obtained on a large scale by the action, at a high temperature, of potass- ium or sodium hydrate on saw dust. Oxalic acid has been obtained synthetically, by Drechel, on passing carbon dioxide over sodium heated to 320°. 2C0j+Naa=Na,CA- Properties. — Oxalic acid crystallizes in prisms, which efhoresce in the air, and which are very sohible in water and alcohol. It fumes at 98°; at lYO" to 180" it is partially sub- limed, but the greater portion is decomposed into car- bon monoxide, carbon dioxide, formic acid and water. 2(CjH A)=CO + 2CO,+Cn.,Oi+HaO. Chlorine, hypochlorous acid, fuming nitric acid and hydrogen peroxide, convert oxalic acid into carbon dioxide. Sulphuric acid causes it to split up into carbon mon- irfwwnf.Aiwjinxr ■ 114 ORGANIO C1IKMI8TRY. oxide and carbon dioxide, and this reaction in made use of in preparing the former gas. Oxalic acid is bibasic. Normal i)otaB8ium oxalate, Ka=Oa=OjO». Acid potasbium oxalate, KIl=02=Ca()8. Uses.— Oxalic acid is employed in removing ink spots from cloth, and in cleaning copper. It owes these properties to the fact that it forms with iron and copper soluble salts, hence it is also employed in calico-works for removing colors. Toxio action of oxalic acid. On account of the use of oxalic acid in tho arts, and its ])hysical resemblance to certain salts, particularly to magnesium sulphate, poisoning with it has often occurred, either through design or imprudence. It acts powerfully upon the system. Tardieu men- tions the case of a young man, sixteen years of age, who was poisoned by two grams of this substance. Tlie symptoms observed are similar to those pro- duced by other corrosive agents; great jjrostr.tion fol- lowed by unconsciousness and a persistent numbness in the lower extremities. The blood of the patient be- comes abnormally red. In cases of poisoning, the acid should be removed from the stomach with promptness, and milk of lime, or magnesium, or ferric hydrate administered. Lime is to be ])referred, as it forms a salt completely insol- uble in vegetable acids. iMMM tnade use ,0,. >,. ving ink vvea those lid copper lico-wcrks of the use semblance sulphate, • through lien men- rs of age, tanco. ;ho8e pro- i.tion fol- nurabness patient be- i removed k of lime, 3d. Lime 3tely insol- j 8UCCINIO AOID. 116 ' ' flCUCINIO AOID. CJIA"CJIA)n n, )"»• Tills ncid is produced by the >x3'dntion of butyric acid, and by subjecting aiiibor, swxinum, to dry distil- lation or by the action of iodhydric {icid on malic or tartaric acids. Succinic acid crystallizes in rhomboidal prisms whicli melt at 180" and boil at about 235", ut a higher tem- perature they are decomposed into water and succinic anhydride iXJl^Oa. It is soluble in 6 times its weight of cold water, soluble in ether and V3ry soluble in alco- hol. It is used in the artificial preparation of malic and tartaric acids. Succinic acid lias been tbund in the fluid of the hydrocele and ot certain hydatids. • ■ MALIC AOID. ' C4H802 ) ^ This acid, discovered by Scheele in sour apples, is found in many plants; in the berries of the service- tree, in cherries, raspberries, gooseberries, rhubarb, to- bacco, etc. Malic acid is levogyrate, deliquescent and crystallizable; it is soluble in alcohol and fuses at about 100". At a temperature above 130°, it is decomposed into 116 ORGANIC CHKM18TKV. various acids and es\iec\A\\y par amalic acid, C4II4O4, which is identical with the acid of the furaaria. It is bibasic like oxalic acid, but triatomic aud is dis- tinguished from this acid by not producing a turbid- ity with calcium compounds. TARTARIC ACID. C4H,02 h:!:^^- This acid, obtained from wine tartar by Scheele, in 17T0, occurs free and combined with potassium in many vegetable products; in the sorrel, berries of the service-tree and tamarind, in the gherkin, potato, Jerusalem artichoke, etc. The grape is the chief original source of this acid. One method of preparing tartaric acid is to purify crude tartar by dissolving and clarifying with clay, which throws down the coloring matters: then filter- ing and adding calcium carbonate, which precipitates half of the tartaric acid as a calcium salt. 2KHC4H4O8+CaCO3=CaC4H4O6+K2C4H4O8+CO2+Hj0 Hvdro-potassic Calcium Calcium tartrate. Potassium tTTtrate. carbonate. tartrate. Tlie solution which contains the potassium tartrate, is filtered and calchim chloride added : the remainder of the tartaric acid is thus precipitated as a tartrate and added to the preceding. mMmssiiJumm muetfp^-'^ ^MiM , C4II404, aria. It id is dis- a turbid- jcheele, in assiuin in ties of the 1, potato, the chief I to purify with clay, hen filter- recipitates -CO,+H,0 tn tartrate, remainder a tartrate TARTARIC AOID. K8C4H4O, + CaCla=CaC4H40« + 2 KCl. Potassiam tartrate Calclam tartrate. These precipitates are wa d a,nd decomposed with sulphuric acid, the calcium sulphate is filtered off, and the liquid evaporated to the point of crystallization. This acid is also called right tartaric, or dextroracemicy as it turns the plane of polarization to the right. Kistner has obtained from certain tartrates a tartaric acid which is optically inactive. This acid, called jjar-fl^- ta/rtario or racemio acid, is somewhat less soluble than dextrotartaric acid, while the reverse is the case with its salts. It contains, moreover, one molecule of water of crystallization, but does not crystallize, as does the dextrogyrate acid, in hemihedral crystals. Levogyrate tartaric acid is prepared by evaporating a solution of racemate of cinchonia; the levogyrate tartrate precipitates while the dextrogyrate remains in solution; or a solution of racemic acid is allowed to stand with a small quantity of calfeium phosphate, and a few spores of the Pencilium, glauaum; fermenta- tion sets in, which destroys the dextroracemic acid. Dextrotartaric acid crystallizes in beautiful r lique prisms with a rhombic base. Cold water dissolves twice its weight of this acid; alcohol dissolves it with equal facility. It is insoluble in ether. Tartaric acid melts at about 180°; and furnishes dif- ferent pyrogenous acids, chiefly: TartaHo anhydride, or Tartrelic acid, C4H4OB, and Pyrotartario aoid^ C5H8O4. .s^MMmA 118 ORGANIC CHEMISTRY. Simpson synthesized pyrotartaric acid and LebedefF has recently (60-75-100) shown that this acid is iden- tical with *hat obtained by heating tartaric acid. Tartaric acid does not precipitate calcium salts. It produces a turbidity with lime water, but an excess of acid dissolves it; by these reactions it may be distin- guished from malic and oxalic acids. Tartkatks. Tartaric acid is bibasic. The two tartrates of potassium are : Normal potassium tartrate, K2C4H406 Hydro " " KO4H5O6. This latter salt is obtained by purifying the tartar of wine casks, and is called cream qftarta r. It is used in the preparation of black flux, white flux, potassium carbonate, and tartaric acid, also largely in baking powders. EocHELLE Salt. KNaC4H,08+4aq. This salt is a double tartrate of potassium and sodium, which vvas formerly much used as a purgative. It may be pre- pared by mixing in a porcelain dish, 3500 grams of water and 1000 grams of cream of tartar, this is brought to boiling and sodium carbonate added ^ j long as ef- fervescence is produced. This solution is then filtered and evaijorated until it has a density of 1.38. The salt crystallizes in regular rhomboidal prisms; it. is soluble in 2.J- times its weight of water, but in- soluble in alcohol. Tabtab emetic. Tartaric acid forms, with bases, a MMMHMnn Lebedeff 1 is iden- !id. salts. It excess of 36 distin- The two the tartai* It is used )0tas3ium n baking s salt is /hich was ly be pro- grams of s brought )ng as ef- en filtered il prisms; ', but in- h bases, a EMETICS. 119 a class of salts called emetiaa, the type upon which they are formed being that of tartar emetic. The ordinary tartar emetic has been generally assigned *^'^ formula (SbO)'K=Oa=CiH404, in which the m > radicle stihyl takes the place of one of the basic hyu. . . gen atoms. It is prepared by boiling for an hour in 100 parts of water, 12 parts of cream of taitar, and 10 parts of antimony oxide. This mixture is then filtered, evapoi-ated and allowed to crystallize. This salt crystallizes in rhombic octahedrons ; it has a me- tallic taste, a slight acidity, and is soluble in Imparts of cold, and about 2 parts of boiling water. Crystals of tariar emetic effloresce on exposure to the air. A strip of tin precipitates the antimony as a brown powder. Tannin, and most astringents, precipitate the antimony, hence tartar emetic should not be ad- ministered in connection with this class of bodies. This salt is the most used ofthe antimony compounds. Febeo- POTASSIUM TARTRATE. — Cream of tartar is di- gested with ferrous hydrate for two hours at a tem- perature of 60". For every 100 pai-ts of cream of tar- tar, a quantity of hydrate should be used containing 43 parts of ferrous oxide. The product is filtered, the liquid received in shallow plates, and kept at a temperature of about 45"^; the salt thus crystallizes in brilliant scales of a garnet red color. It dissolves in water, but is insoluble in strong alcohol. Tartaric acid is often adulterated with alum, potassium bisulphate and cream of tartar ; these substances may 'nmmmmmmmam 120 ORGANIC CHEMISTRY. all be detected by means of alcohol, in which they are not soluble. Tartaric acid is used in making effervescing drinks, and as a discharge by calico printers. Tartaric acid produces the same toxical effects as oxalic acid, though requiring much larger doses. The blood of the poisoned person becomes red and very fluid. OITEIO ACID. n TT n =Cl6H403 ) r^ This acid is found associated with oxalic and tartaric acids in many plants. It occurs in cherries, currants, raspberries, oranges and lemons. It is ordinarily extracted from the juice of lemons. This juice is allowed to stand until fermentation com- mences, then filtered and treated with chalk and milk of limo ; an insoluble citrate of calcium is formed, which is decomposed by sulphuric acid; the calcium sul- phate is filtered off and the filtrate evaporated and left to crystallize. Citric acid crystallizes in regular rhombic prisms; it is soluble in three fourths its weight of cold water; this solution, in time, becomes covered with mould. Citric acid is soluble in alcohol and ether. Heated to about 175° it furnishes aconitio acid, CaH^O.^^" C«H« O, 3 '-'8 H, [Oa, OITBIO ACID. 121 they are » drinks, effects as 168. The and very d tartaric currantb, f lemons, tioii com- aiid milk ed, which 3ium sul- i and left [ regular mrths its , becomes Heated losing HjO on increasing the temperature. Another pyrogenous acid, itaconio acid C5Ha04 is formed, which, if heated, is transformed into citraconio add isomeric with the last mentioned. Oxydizing bodies destroy citric acid, carbon dioxide, acetone, etc., being produced. Fused caustic potassa resolves it into acetic and oxalic acids. OeHA + HaO=C2HA + 2C2H A . Oxalic acid. Acetic acid. . Citric acid is tetratomic and tribasic. It may be distinguished from oxalic and tartaric acids by its ac- tion on lime water, which it does not precipitate in the cold, but if boiled with an excess of lime water, a pre- cipitate of basic calcium citrate is obtained. Magnesium crrEATE. — This salt is prepared by treat- ing magnesium carbonate with a strong solution of citric acid and precipitating tliis salt with alcohol. It is much used in medicine as a purgative. Citrate of ikon. — Hydra ted ferric oxide is dissolved in a luke-warm solution of citric acid, and the liquid evaporated to dryness. This body varies in its composition; it occurs in brilliant amorphous scales, of a garnet-red color. Ammonia orrEATE of iron. — One hundred grams citric acid are digested for some time with a quantity of ferric hydrate, representing 53 grams of iron, and 16 to 20 grams of aqua ammonia. The liquid is then filtered and evaporated to the consistency of a syrup. ■ W iaai M i aa iBKwagejBBtMPF**''" ^ 132 OROANIO CHEMISTRY. and transferred to very Bhallow vessels which are placed in drying ovens. This substance solidifies in scale?, if the temperature at which it is dried is not too high and the layers of liquid are extremely thin. LACnO ACID. CsHeOg. This acid was discovered by Scheele, who extracted it from sour milk. It exists in many products after fermentation, as sauerkraut, beet juice, and various vegetables, also nux vomica. It is found in many ani- mal fluids, in the blood and in the fluids which per- meate the muscular tissues. It is to this body that the acid reaction of sour milk is due. Lactic acid extracted , from flesh forms, with certain bases, salts which diifer in solubility, etc., from those formed with ordinary lactic acid, hence this acid is sonietimes caMed paralao- tio aoid, also sarko-lctotio acid, from ffapxo? flesh. Lactic acid may be prepared by dissolving sugar of milk in butter-milk, adding chalk to the mixture, and allowing it to stand for eight or ten days at a tem- perature of 30° to 35" The sugar of milk is sometimes replaced by glucose, or cane sugar and fermentation favored by the addi- tion of cheese. A special ferment (Jactio ferment) is developed which is transformed into sugar and lactic acid, but the fermentation is arrested as soon as the liquid Ba^ssr^KSKSSsaaBWKSMWBBa-t^^ LAOTIO ACID. 123 hich are lidifies in is not too hin. extracted acts alter cl variou(| many ani- 'hich per- y that the extracted lich differ ordinary \paralao- lei-h. J sugar of icture, and at a tem- ly glucose, the addi- ieveloped acid, but ;he liquid S«51ia»i5S»SCS»S3'nsSSl becomes acid, and it is in order to prevent this acidity that an excess of calcium carbonate or sodium bicar- bonate is always maintained. Wurtz has produced this acid artificially by the action of platinum black on propylglycol. O., + C3Tl80.,=C8He03 + H,0. Propylglycol. Lactic acid is a colorless, syrupy liquid ; at about 130° it is changed into the anhydride of lactic acid, CfiHioOs, and at about 250° it furnishes a crystalline body called laotide whose formula is C3H4O2. Lactic acid posseses the property of dissolving cal- cium phosphate. The lactates are soluble in water. Lactate of iron, (CsH503)2Fe, is employed in medicine. URIC OR LITHIC ACID, O6H4N4O3. Discovered in 1776, by Scheele. This acid exists in human excretions, and in those of the carnivora. In the excretions of herbivora, the uric acid is replaced by hippuric acid. Uric acid is present in normal human urine only in small quantity. The urine of sedentary persons, and of those whose food is very nitrogenous and quite substantial, contains more of this substance than that of individuals who lead an active life, and whose diet is less nourishing. In the latter case the uric acid is oxydized and converted into urea, hence, the proportion of the acid decreases as the quantity of urea increaBes : whereas calculi of 124 ORGANIC OHEMISTRf. uric acid are frequently formed in persons whose diet is very nourishing, and whose occupation necessitates bnt little muscular exertion. The excreta of birds contains a large proportion of uric acid, and that of snakes is formed almost exclusively of this body. This acid may be prepared hy boiling a dilute al- kaline solution with guano, excreta of the boa con- strictor, or uric calculi finely pulverized. The liquid is filtered and the filtrate supersaturated with hydrochloric acid ; the uric acid precipitates in flakes, which become crystalline on standing. The author having had occasion in 1858 to prepare large quantities of uric acid from guano, found that in order to obtain the purest product, as free from color- ing matter as possible, it was preferable to use sod- dium hydrate as a solvent, and carbon dioxide as a pre- cipitant, the latter in sufficient excess to transform the hydrate into bicarbonate. . Crystals of uric acid are colorless and odorless. They are nearly insoluble in ether and alcohol. About 1500 parts of boiling water are necessary to dissolve one art of the acid. • On distillation uric acid yields urea and other cy- anic compounds. Uric acid heated with water and lead dioxide furnishes urea and a substance called al- lantom, which has been found in the urine of sucking calves. Its formula is C4H6N4OS. The same derivative of uric acid was obtained by the author in 1858f also parabanic acid, on heating uric acid with manganese dioxide and sulphuric acid. (80-[2]44-218.) 'WlM I W i URIO ACID. 125 hose diet icessitates , of birds l1 tiiat of >o(ly. dilute al- boa coa- psaturated ipitates in to prepare nd thatiu *om color- 3 use Bod- B as a pre- isform the odorless, i alcohol, icessary to other cy- water and called al- )f sucking ttained by sating uric luric acid. If 1 part of uric acid be added to 4 times its weight of nitric acid of a specific gravity of 1.45, the solution being kept cool, small crystals of a substance called aUoaan separate out. whose formula is C4H4NA+3II,0. Woehler and Liebig obtained from this body a num- ber of very interesting derivations, alloxantin, al- loxanio acid, parabanio acid, thionurio acid, dia- lurio acid, and finally a magnificent purple crystalline body, murexide. A large number of various deriva- tives have also been obtained by other chemists, especially Bayer. The rich color, murexide, is made use of in detecting uric acid. For this purpose, traces of uric acid are heated in a watch glass for a few minutes, \7ith one or two drops of nitric acid ; the ex- cess of acid is evaporated, and the dry residue exposed to the vapors of ammonia, when a purple, or very beautiful rose color, will appear. HIPPCRIO ACID. CsH^NOj. The urine of herbivora contains a large percentage of this acid, which also exists in a small quantity in human urine. A frugivorous diet augments the pro- portion of this body. It is prepared by boiling the fresh urine of the horse (hence the name, from I'mro?, a horse), or better from that of a cow, with milk of ORGANIC OHEJIISTRT. lime, which is then filtered and evaporated to one- tenth its volume; this is mixed with a large excess of hydrochloric acid and left to stand JO or 12 hours. The impure hippuric acid which precipitates is re-dis- Bolvod in soda and ro-precipitated with hydrochloric acid. Animal charcoal may be added to the saline bo- lution if the brown color still reniains. Putrid urine yields only benzoic acid. Dessaignes has prepared this acid artificially by causing zincic glycocol to act on benzoyl chloride. Zn(C»Il4NOa)2+ 207H50C1= Z.iCU + 2C,H3[NI1(0,H50J0.,. Hippuric acid crystallizes in colorless crystals, which require 600 parts of cold water for their solution, but are very soluble in hot water and alcohol. It ifj decomposed at 240°, benzoic and cyanhydric acids being found among the products of distillation. Under the action of oxydizing agents it fumishes ben- zoic compounds; with nitrous acid it yields benzo-gly- colic acid. mmmBsmm ALKALOIDS. ALKALOIDS. ARTIFICIAL BASES OK ALKALOIDS. TKIMAKY. OJI^+sN. Methylaraine Ethylaraine Propylamine Butylamine Amylamine Caprylamine Acetylamine AUylamine CnHon + iN CnHan-S N. Plienylamine, aniline - Toluidine Xylidine - . . Cumidine CH,N CJl.N C3II9N O^IInN CbII,3N C3H7N. CeH^N CgHnN C,HiaN. C„H,„_,K Phtalidamine CsHbN. m OROANIO OHEMISTBr. CJI,„_..N. Naphthalamine - CioHjN. 8KC0NDAEY. Diraethylamine - • Methylethylamine - Diethylamine 1 0,H; N Call. N O4 HuN. TERNARY. Trim ethyl amine Dimethylethylamine Methylethylamylamine OsiljN CJI„N OgH,N. niospuiNEa Methylphosphine Dimethylphosphine Trimethylphosphine - OH,P ■ CjH.P 0,H.P. ARSINEB. Triethylarsine OeHisAfl. BTIBINES. Triethylstibine C.HisSb. NATURAL AJ.KAL0ID8. PRINCIPAL NATURAL ALKALOIDS. OF THK CINCHONAS. Qtiiriia,Quiniciaaiid Qiiiniditt(VIjjN.^Oi Cinchonia and Cinchonidia Call^iNaO OF OPIUM. Morphia Codeia Thebaia Narcotina Papaverine Narceia C,tH„N08 C,8ll2iN Oa C,9lI,,N03 C«Hj3N O, (VIjiNO, O38H29NO,. OP THE STRY0HN08. Strychnia Brucia C21H22NJO2 - CsaH^NA. OP THE SOLANAOEiE. Nicotina Atropia - Hyosciamine Solania • OP THE HEMLOCK. Conylia CioH^Na Cnllj^N O3 CnHjsN Oa CisHnN 0,,. CaE^N. 120 mri 130 ORGANIC CHEMISTRY. OF PEPPER. Piperidine MISCELLANEOUS. Aconitina Veratria Theobromine Caffeia C,H„N. C„H4oN O C'3aH52N208 C^HgNA CbHioNA- The first organic base isolated was u-orphia, obtained in 1816, by Sertuemer. In 1819, Pelletier and Ca- venton extracted quinia from cinchona bark, and showed that the very active plants used in pharmacy owed their energy tocompoundacapableof uniting with the acids, and of forming with them definite crystallizable salts. From that epoch, the number of organic alkaloids has become very considerably augmented ; and methods have been discovered by which many of the alkaloids are prepared artificially. It was Fritsche who, in 1840, obtained the first artificial alkaloid on distilling indigo with potassa ; he named it aniline. Gerhardt by similar methods prepared quinoleim, Cahours piperidine, and Chantard toluidine. The distillation of organic matter also furnishes al- kaloids. Thus several of them have been obtained from a product of the distillation of bones, the oil of Dippel ; also as products of the distillation of various other organic compounds. i ^"''' i'M^-i^'i}:^ ^:^J^O'U''t,-T-^ ^srsiiMiililia '"mmmmm COMPOUND AMMONIAS. 131 A very general method is due to Zinin, which con- sists in causing a reducing substance to act upon nitrous compounds as nitrobenzol, for example. The nitrous compound is introduced into an alcoholic solu- tion of iimmoniura sulphide, and the mixture allowed to stand ; sulphur is soon deposited, and the hydrogen of the hydrogen sulphide combines with the oxygen of the nitrous compound. Example: CeHgN O, + 3HaS=2Il20 + 3S + CJI,^. Aniline. V Nitrobenzol. For this mode of reduction, as it is not very prac- tical, and is tedious in execution, there is at present substituted the action of i»-on upon acetic acir", or that of zinc or tin, on hydrochloric acid. Wurtz has given a very interesting method, which has led to the discovery of alkaloids much resembling ammonia, for that reason called compound ammonias. It consists in causing potassa to react upon the cyanic ethers, these bodies being decomposed much like cy- anic acid. Thus methylamine is obtained by the action of potassium hydrate upon cyanate of methyl : CO I CH„ CH, y^+2KHO=K,C03+ H [if. V" ' Cyanate of mothyl. PotaBBium carbonate. Hetbyl- amiue. Hofmann made known, very shortly afler the pub- r»~ ''''8^^^^,p^?;^!^^f^SfJlS!j<5ijSOi*?S»«SW». 132 ORGANIC ClIKMISTUY. lication of "Wurtz' process, a method for the pi-epara- tion of the compound ammonias, by which not only a simple equivalent of hydrogen is replaced by the radicles (CHs), (CJij), etc., but all the hydrogen of the ammonia, Hofmann's method consists in causing ammonia to react upon hydrochloric as well as brom- hydric or iodhydric ethers, particularly the latter. Let us take, as an example, iodide of ethyl in con- nection with the study of KTUTLAMINB. Ten to 15 grams of iodide of ethyl and 50 grams of aqua ammonia are heated in sealed tubes of green glass jjlaced in a water bath. The following reaction occurs: OaH8H-NH8=C,H8NI. When the liquid has become homogeneous it is allowed to cool, then decomposed by a solution of po- tassium hydrate, the vapors being collected in water, containing hydrochloric acid. The hydrochloric acid solution is evaporated to dryness, and the residue treated with pure alcohol, which dissolves the chlorhydride of ethylatrune and leaves in an insoluble state the ammo- nium chloride derived from the excess of ammonia used. The solution of chlorhydride of ethylamineis evaporated to dryness, and the deliquescent crystals obtaJneddecomposedby potassium hydrate, with the aid of a gentle heat. The volatilized product is con- densed in a cooled receiver. In this reaction there is CLASSIFICATION OF THE ALKALOIDS. 133 also formed diethylamine, triethylamine and oxide of tetrethylatnnioiiiiim from which the ethylamine is separated by distillation. It may be obtained more readily by first distilling 1 part potassium cyanate with 2 parts potassium tulphovinate, then by decomposing the cyanic ether obtained with a boiling solution of potassium hydrate contained in a flask connected with a cool receiver. Ethylamine is a limpid liquid, with a strong odor resembling that of ammonia. It has not been solidi- fied. It boils at 18. 7°, and dissolves in water, producing a very caustic solution. Ethylamine is equally soluble in alcohol and ether. It is combustible, burning with a blue flame, yellow at the margin. It displaces ammonia from its combinations. Its solutions give reactions similar to those of ammonia; for instance, with salts of copper it gives a bluish white precipitate, which is dissolved in an excess producing a deep-blue solution. It differs from ammonia in the following reaction: ethylamine precipitates alumina from its salts, and the precipitate is soluble in an excess of ethylamine, which is not the case with ammonia. CLASSIFICATION OP THE ALKALOIDS, OK OKGANIO BA8 '. Amines. — Hofmann has given the names oi primary amines, or monamines, to ethylamine, which we have just studied, and the compound ammonias in which a single atom of hydrogen has been replaced by a radicle. ^ 134 ORGANIC OHBMISTRT. The same cliemist, having prepared ethylamine by the action of ethyl iodide upon ammonia, subse- quently succeeded in obtaining diethylamine by similar means. The reaction is the following : ( C2H5 ( an, (H (H This hydroiodide obtained, treated with potassium hydrati; t lime, furnishes a second base, which is biethylammonia, or diethylamine ; Diethylamine C4H,iN=N"-^ C2H5. A similar compound is, Ethylaniline C8H,iN=nJ CjH*. These bases have been given the name of secondary amines or imidea. The secondary ammonias are attacked by ethyl iodide and other ethers, and a reaction takes place, iden- tical with that which gives rise to the primary and secondary amines and tertiary aminea, also called nitrite bases, are thus obtained. Mill wm nam -^ AMINES. 135 Snch bodies are: TriethylamineaHi5N=N-^ C^Hs. rcH, Methylethylplienylamine C9Hi3N=N -i CjHj. These bases are related to the alcohols in the same manner as the primary amines. Thus diethylamine is derived from the action of 2 molecules of alcohol on 1 molecule of ammonia and the elimination of 2 mole- cules of water: 2{Cj,TI,0) + NH3-2H20=C4HnN. In like manner the ternary amines may be consid- ered as derived from 3 molecules of alcohol and 1 mole- cule of ammonia with the elimination of 3 molecules of water. There are also bodies built upon the type of two and three condensed molecules of ammonia, and are denominated, respectively, di-amines and tri-amines; as Secondary ethylene diamine N. Ternary ethylene diamine N. |f Ha (CaH,)' AY m m ansa dlVBIiiWiJiWl i Mllg ■'-'•—^'■■'^-- ■ ■ 136 ORGANIC CHKMISTUY. Triethylainine attacks hydroiodic ether, and there is formed the compound C8Ha8NI=N(08Hs)4l. This body treated with oxide of silver, furnishes an oxy- genated qvuternary base, CsHaoNI + Ag 110^ Ag I + CgHjiNO. This substance is very caustic, soluble in water and acts as an inorganic alkaline base like potassium hydrate, with which body it is also unalagous in com- position. l\o (C,H.).Njo Amides, Alkalamides. — The amides are bodies built upon the type of ammonia, in which one or more of the hydrogen atoms are replaced by an acid compound radicle; thus, ( C,H30 acetaraide N -( H . <^ There are also mixed combinations of amides and amines, called alkalamides, as ( CeH, acetanilide N" \ CaHgO. H f-i.-'/Srii' ;t,^E*i3^^5v5P7?s>ss!?^tH^*:'^P«ii^?^^ ALKALOIDS. 137 KATURAL ALKALOIDS. Many of the natural alkaloids appear to possess a composition analogous to that of the compound am- monias. Some are not attacked by iodide of ethyl, and should be classified among the ammoniums, bodies having the same relation to the compound ammonias as does ordinary ammonium hydrate to ammonia. Others are acted upon by iodide of ethyl, and, from the number of bases furnished, it may be ascertained whether they belong to the primary, secondary or ter. nary compound ammonias. The properties of the natural alkaloids in general, resemble those of the artilicial bases or alkaloids. They contain niti-ogen; those that do not contain oxy- gen are ordinarily volatile, while those with oxygen are non- volatile; they are very soluble in alcohol, ether 'and chloroform. Certain ones are dissolved by the hydrocarbides, which are now considerably used in the preparation of the alkaloids. Water does not dissolve any of the artificial alkaloids, except those having a very low molecular weight, like ethylamine; this liquid, how- ever, dissolves cod eia and narceia quite readily. With the exception of quinia and cinchonia, they turn the plane of a polarized ray of light to the left. They react like ammonia, or potassa, with vegetable ^ss3s^Bsn;s'is®iSi55^«5«SBS^SifflRra 138 ORGAinO CHEMI8TBT. colors, and furnish, with platinum bichloride, crystal- lizable double chlorides, little soluble and yellow in color. They combine equally well with auric and mer- curic chlorides. The natural alkaloids have ordinarily a bitter taste. Among their salts the sulphates, nitrates, chlorides and acetates are mostly soluble, while the oxalates^ tartrates and taijnates are insoluble. The harmless character of tannic acid, and the in- solubility of the compounds formed by it, with the al- kaloids, render tannin and astringent vegetable sub- stances generally very efficacious antidotes. The precipitates they produce are soluble in acid and alkaline liquids. The alkaloids are partially precipitated from their solutions by potassa, soda and ammonia. Iodine water and solutions of iodine in jjotassium iodide, precipitate them completely. According to Schultze, the liquid obtained by add- ing antimony perchloride to a solution of phosphoric acid, is a re-agent which precipitates most of the or- ganic bases. A delicate re-agent for the alkaloids is the double iodide potassium and mercury. According to Meyer, the best proportions are 49 grams of potassium iodide and lc)5 grams of mercury dichloride, to 1 litre of water. It is best to add the re-agent to the solution of the alkaloid, which may be neutral, acid, or even feebly alka' >. It must oe borne in mind that the presence of I e, crystal- yellow in c and mer- tter taste. chlorides 3 oxalates^ ind the in- ?ith the al- 3table Bub- in acid and from their )dine water precipitate sd by add- phosphoric of the or- the double f to Meyer, liiini iodide 1 litre of le solution id, or even )re8ence of NIOOTINA. 139 sugar, tartaric acid and of albumen may mask the reac- tions of a number of alkaloids. NIOOTINA OB NIOOTYLIA. Nicotina is obtained from tobacco {Nicotina tdba- owm.) For this purpose a decoction of tobacco is made, and the liquor evaporated to a syrup. The extract is treated with twice its volume of 85 per cent, alcohol, which precipitates the salts present and certain organ- ic substances. The alcoholic solution is distilled and the residue submitted to a second similar treatment. The alco- holic extract thus obtained, is mixed with a concen- trated solution of potassium hydrate, and the nicotina liberated is re-dissolved in ether. This ethereal solu- tion is evaporated in a water bath, and the residue distilled in an oil bath, in an atmosphere of hydrogen. Nicotina is a colorless liquid when pure, remaining liquid at -10°, boiling at about 245°, with decomposi- tion. It has the odor of an old pipe. Exposed to the air it becomes brown, then resinous; water, alcohol and ether dissolve it; its solutions are strongly levogyrate. Nicotina is a powerful base; it fumes when a rod moistened with hydrochloric acid is brought near it ; it precipitates the metallic oxides. Nicotina requires two molecules of a monobasic acid for saturation. The chloride, CioIIuNj'-inCl, is crystallizable, though '^Sgate^^^SgBteiiiSiiiife^^^ 140 OBGANIO OHKMISTKY. deliquescent. The hydrogen it contains is not replace- able by methyl, ethyl, etc. It may be considered as having the rational formula, ^M(C.H,)"'; (C5H7)' ' ' being the compound radicle niootyl. Proportion of nlcotina in different tobaccos : Havana, Maryland, Virginia, Lothringen, 2.0 per ct. 2.3 « 6.9 « 8.0 « (Schloesing.) TOISONING BY TOBACCO OB BY NICOTINA. The injection of a concentrated decoction of tobacco, causes serious results in a few minutes : intense head- ache is produced, with nausea and vomiting, violent pain in the abdomen, pallor, and, finally, extreme prostration. An infiision of tea, unroasted coffee, or any astring- ent substance (pulverized nut-galls, or oak-bark) are the only antidotes known, and they are far from being wholly reliable. The pure nicotina is one of the most dangerous poisons. It manifests itself immediately on being taken, since it is entirely soluble in water. The nervous system is especially affected. Two or three drops suffice to cause death. not replace- nsidered aa cos: er ct. iloesing.) INA. I of tobacco, itense head- ing, violent ly, extreme my astring- ik-bark) are from being dangerous y on being d. Two or CONIA. Ul Two drops introduced into the throat of a dog will almost instantaneously cause the following series of symptoms: respiration becomes difficult, the animal titaggers, falls without the power of rising again, throws the head back and, in a few moments, is perfect ly paralyzed, and death ensues. PIPERIDINE. C.H„N. There has been obtained from the pepper ( Piper longum, Piper nigrum, or Piper oaudatum)^ a body crystallizing in colorless prisms called jp^pmn«, whose fortnula is CnHijNOa. It is a neutral substance. Wlien distilled with three times its weight of soda- lime it furnishes piperidine, a limpid liquid having the taste of pepper, and also its odor, soluble in water and alcohol, boiling at 106°. This body is alkaline and saturates acids. It con- tains a single atom of hydrogen replaceable by methyl, ethyl, etc. OONIA, OONYLIA, OR CONINE. Cen„K This body is obtained from hemlock {Convum moo- vlatum); the crushed seeds are distilled in a large glass retort, with a solution of potassa, orsoda, whereupon an alkaline distillate is obtained. The distilled product is treated with a mixture of two parts of alcohol and one 7i38BsiaiaMMW8etags^n3B-. t=.,^^^ 142 ORGANIC CHEMISTRY. part of ether, which dissolvcH tho sulphate of conia and leaves the insoluble sulphate of ammuuium. The ethe- real alcohol is separated by distillation, potassa is added to the residue, and the mixture diHtilled. Water and conia pass over; the latter is dehydrated with po- tassa, and rectified in vacuo, or in a current of hydro- guu gas. Conia is a colorless, oily liquid; emitting an odor of hemlock. Water dissolves it but little, and this better when cold than warm. It is very soluble in al- cohol and ether. It boils at about 210°, yet emits va- pors even when cold, for if a glass rod, moistened with hydrochloric acid, is brought near it, white fumes are produced. It is a monacidic base, veiy tilkaline, and forms crystalHzable salts. One of its atoms of hydro- gen is replaceable by ethyl or methyl. This base is very poisonous. According to Christi- ason, ten centigrams would suffice to cause death. It is classified among the narcotics; its action is charac- terized particularly b^' its effect on the organs of respi- ration and the left ventricle of the heart. ALKALOIDS OF THE PAPAVEBAOB^. The poppy-seed capsules ( Papaver aomnif-^t'vm) yield, on incision, a milky sap, which dries up in a day or two ; thir «ap, when solidified, constitutes opivm,. There are '^' iding varieties of opium : I. ^ , Smyrna is found irt small cakes of 100 ' uiis, frequently distorted and agglutinated togt -y reason of their soft nature, and contain 7 fconiaand The ethe- sa is added Wuter and i with po- t of hydro- ig an odor I, and this uble in al- b emits va- tenodwith fumes are caline, and i of hydro- to Christi- ifttli. It is is charac- QB of respi- ip hi a day es opiitm. 11 cakes of :glutinated I contain 7 OPIUM. 143 to 10 per cent, of water. The surface ib brown but the interior has a fawn color. Sometimes it is found to contain 14 to 15 per cent, of niorphiii, but in ctlior in- stances only 6 to 6. Good Smyrna opium should con- tain not loss than 10 per c(;nt. II. The opium of Constantinople is drier than the preceding. It a[)j)ear8 in commerce in flattened, irreg- ular cakes, almost always surrounded with poppy- leaves. It contains 5 to 10 per cent, of morphia. III. The opium of Egypt is still dryer ; it is rarely enveloped in leaves. Its odor is feeble, and it contains no more than 2 to 7 per cent, of moi])hia. Recontly, attempts have been made to cultivate the poppy in Europe, especially in FraJice. Opium contains the alkaloids morphia, codeia, the- baia, papaverine, opianino, narcotine and narceia, an acid combined with these alkaloids called meoonio acid (from /itfxoov, a poppy), a crystallized neutral substance called meconine, which, according to Berthelot, la a complex alcohol, and finally, various gummy and resin- ous compounds. MORPHIA OR MORPHINE. ChHibNOs, HA Preparation. Ten kilos, of opium are treated re- peatedly with water, and the liquors evaporated to the consistency of a syrup. The mass is redissolved in water, filtered, and again evaporated. To the lukewarm liquid are added 1200 .lJ..- 144 ORGANIC CHEMISTRY. grams of anhydrous calcium chloride, dissolved in twice its weight of water. A complex precipitate is formed, con tai' r resins, coloring matters, and ' sul- phate and mf <;o> ate of calcium, which is thrown upon a filter. The filtered lie is evaporated over a water-bath. During the concentration, a fresh quantity of meconate of calcium is separated by filtering, and the liquid Evaporated to the consistency of syrup. The liquid is then acidulated with a small quantity of hydrochloric acid, and set aside in a cool place. At the end of a few days, it contains brown crystals of the double chlorhydrate of morphia and codeia, con- taminated with a blackish liquid ; these crystals are drained, pressed, and again dissolved in as little boil- ing water as possible. The chlorhydrate, on cooling, .deposits crystals, which are again dissolved in hot water and decolored with animal charcoal. After heating to 80° or 85°, the solution is filtered, and the liquid, on being concentrated, deposits the double chlor- hydrate in pure white crystals. This salt is again dissolved in boiling water, and the hot liquid treated with ammonia ; the codeia remains in solution, while the morphia is precipitated. This deposit is thrown upon a filter washed with cold water, dried, and dissolved in boiling alcohol ; the morphia separates out in crystals on cooling. It frequently contains some narcotina, from which it is freed by washfng once or twice with ether, or chloroform, which dissolves the narcotina, and does not afiect the morphia. mmmm i isolved in cipitate is , and ' 8ul- own upon ater-bath. meconate ;he liquid 3 liquid is irochloric n crystals deia, con- ystals are little boil- n cooling, ed in hot al. After 1, and the ible chlor- sr, and the a remains ed. This old water, ) morphia 3ra which ether, or and does mm »m^^mirf^ MORPHIA. 145 Pure morphia, (from Morphem, in allusion to its nar- cotic qualities,) crystallizes in regular prisms with a rhombic base, is colorless, soluble in 500 parts of boil- ing water, scarcely soluble in cold. Forty to forty-five parts of cold 90 per cent, alcohol are required to dis- solve one part of morphia; it is insoluble in ether. Solutions of morphia are very bitter. Morphia is little soluble in ammonia, while it is dis- solved very readily by alkaline solutions, and even by lime water. Under the action of heat, it fuses in its water of crystallization, the latter escaping, and the alkaloid re- crystallizes on cooling. Morphine is an energetic reducing agent, reducing gold and silver salts, setting free the respective metals. It separates the iodine from solutions of iodic acid. If a solution of starch is poured into a test-tube, and a solution of iodic acid and traces of morphia added, the blue color of iodide of starch appears. If morphia is put into a few drops of a concentrated and slightly acid solution of a ferric salt, a beautiful blue color is produced, which subsequently changes to green. Morphia, moistened with nitric acid, is colored orange-red, which rapidly changes to yellow. These four reactions are characteristic of morphia. If iodine and morphia are mixed in equal propor- tions and the mixture treated with boiling water, a brown liquid is formed which deposits a reddish-brown powder called iodomorpMa. Morphia fased with al. 146 ORGANIC OHEMISTBY. kalies yields methylamine. (p. 127). It is attacked by ethyl iodide at 100°, a single molecule of ethyl entering into the group. Morphia forms crystallizable salts, from the solutions of which it is precipitated by the fixed alkalies. Chloehydbate of morphia, CnHiaNOaHCl+SHaO. To prepare this salt, 100 parts of pulverized morphia are treated with a little warm water, then hydrochloric acid is added in sufficient quantity to dissolve the al- kaloid. The solution is afterwards evaporated in a water bath until it crystallizes. This salt is soluble in 20 parts of cold water, very soluble in alcohol. It is the salt of morphia most used, and contains Y6 per cent, of morphia. Sxn.PHATE OF MORPHIA, (Ci7Hi9¥Os)2H2S04+6H20 is prepared like the preceding salt, which it resembles in appearance as well as in properties. Morphia and its salts are used in very small doses, as in larger doses they are energetic poisons. CoDEiA, CisHaNOsjHaO. Discovered in 1832 by Robiquet. This base, whose name is derived from kojiJ?/, poppy head, exists in the ammoniacal solution obtained in the preparation of morphia. On evaporation the ammonia is driven off and the codeia is precipitated by potassa. The codeia is at first precipitated in the form of a sticky mass which soon becomes pulverescent. It is washed with and dissolved in hydrochloric acid. The liquid is then boiled with washed animal charcoal, and the codeia precipitated with potassa. tacked by of ethyl polutions ies. n+SHaO. , morphia irochloric. m the al- ated in a ater, very )hia most O4+5H2O resembles aall doses, ase, whose ists in the laration of driven off rhe codeia ticky mass ished with aid is then the codeia NAROOTINA. 147 Codeia is crystalline, very soluble in alcohol and ether. It dissolves in 80 parts of cold and in 20 parts of boiling water. Codeia is very soluble in ammonia, and nearly in- soluble in potassa. With chlorine, bromine and ni- tric acid it forms products of substitution. With iodine it fiiruishes ruby-red crystals, whose formula is CjsH^jNOsI. Codeia is somewhat used as an anodyne. It is easily distinguished from morphia, since: I. Codeia is soluble in ether and ammonia, II. It is insoluble in solutions of potassa. III. It does not reduce iodic acid or ferric salts. IV. Mtric acid does not impart to it any color. !N"akcotina, CiBjHjaNO,. iffarcotina crystallizes in rhombic prisms. It is al- most insoluble in cold water, somewhat soluble in alcohol, quite so in ether. It fuses at 170°, and is decomposed before reaching 200°. Dilute nitric acid transforms it into various products of oxydation, the most important of which are meconme, ootarnine and opianio acid Narcotina unites with acids, but the compounds are decomposed on evaporation. It is distinguished from morphia in that it does not reduce iodic acid and ferric salts, and from codeia in giving with nitric acid a blood red coloration. This substance is also insoluble in potassa and ammonia. It is not as poisonous as morphia. ■!^»^sis^''&S3Bffi®a«JaJseste^&"iKv*Ka!iM«gB^,\s^^ r 148 ORGANIC CHEMISTRY. THEBAIA. This alkaloid, sometimes called parctmorphia, is the most poisonous of the bases of opium. It is crystallizable, insoluble in water, soluble in alcohol and ether. Fuming nitric acid attacks it in the cold, and a yellow liquid is obtained, which be- comes brown on contact with alkalies, and which dis- engages an alkaline vapor. Concentrated sulphuric acid gives it a red hue. PAPAVEBINB. CaoHaKO*. This body is crystallizable, insoluble in water, quite soluble in boiling alcohol and ether. It forms crystal- line salts. Under the action of strong sulphuric acid it as- sumes a deep blue color, though Hesse and Drag- endorff have recently ascertained that when absolutely pure no color is obtained, the ordinary article found in trade not being pure. NABOEIA. C28H29NO9. This alkaloid crystallizes in silky needles, insoluble in ether, soluble in alcohol and boiling water, little soluble in cold water. It forms crystallizable salts. OPIUM. 149 d, is the luble in ks it in iiichi be- hich dis- ulphuric Narceia flises at 96°, and commences to decompose at about 1 1 0°. It is attacked in the cold by concentrated sulphuric acid, a red liquid being produced which rapidly becomes green, especially if slightly heated. The best means of distinguishing narceia is to cause a solution of iodine to act upon the pulverized substance. According to Roussin, the operation is most easily per- formed with one part of iodine and two parts of potas- sium iodide dissolved in ten parts of water. A blue color is produced, which disappears on coming in con- tact with alkalies, or on heating. ;er, quite 3 crystal- jid it as- id Drag- bsolutely e found insoluble ;er, little salts. PHYSIOLOGICAL AOTION OF OPIUM. NARCXOTO POISONS, Opium in small doses is a very highly-prized ano- dyne. Continued use of this substance produces a peculiar state of inebriation, an excited sleep and hal- lucinations of various sorts. The bodies of opium-eaters are lean and cadaverous, their eyes are lustrous, their forms bent; their appe- tite diminishes, and they exist only by increasing the dose of the poison which destroys them. In larger doses it is highly poisonous, and acts in a different manner from that of the poisons already studied. Tt may be considered as the type of the narcotic poist ,3. It is not nnfrequently used for criminal pui-poses, and the imprudent administration of laudanum and other solutions of this substance often causes serious effects. Claude Bernard has made a careful study of the ac- tion of the various alkaloids of opium upon the system, uiriiftiMfrnTiTTiTmnr'""-'-'^-"''-'''"-''^^''-"'''""'"^-"'"''-''''''-^"^ 150 OBOANIO CHEMISTRY and has tabulated their soporific, toxic, and convulsive actions as follows : Toxic. CODTuUTe. Soporific Thebaia, Thebaia, Naneia, Codeia, Papaverine, Morphia, Papaverine, Narcotina, Codeia. Narceia, Codeia, with- Morphia, Morphia, out Narcotina. Narceia. Those at the head of each column are the moat marked in the respective characteristic action. Subjoined are tabulated the principal chemical characteristics of the opium alkaloids : WATIB. AI.00H0L. XTBHt. AXXOKIA. Horphla. Bat little sol- uble. Quite soluble. Almost insol- uble. Nearly insol- uble. Codels. Soluble. Very soluble. Very soluble. Soluble. Narcotina. Insoluble. Soluble. Soluble. Insoluble. ThebaU. luBoluble. Soluble. Soluble. Insoluble. PapaTerlne. Insoluble. " Soluble. Soluble. Insoluble. Natcela. Slightly Bon)le Soluble. Insoluble. Insoluble. Nearly insol' able. Solable. Insolnble. Ineolable. iDBolnble. llnBolnWe. , _-.^.TiES#^" . QUINIA. 161 QUINIA OR QUININB. CaoHMNaOa,3HjO. This alkaloid was discovered in 1820 by Pelletier and Caventou. The following is the modern process by which it is prepared. Yellow Peruvian bark is carefully pulverized and thoroughly mixed with 80 per cent, of its weight of lime, previously slacked. The mass is then lixiviated three or four times with refined petroleum (petroleum ether) or amylic alcohol, (wood spirit) which dissolves the alkaloids. FOTASBA. Solnble. Newly Iniolnble. Iniolnble. Ineolable. Inaolnble. Inaolnble. NTTBia AOID. Orani;e-red color atlon. Orange-red color- ation, Blood -red color- ation. Yellow coloration. BtrLPUDBIO ACID. Colored violet on heatine with di- lute acid. Colored violet on beating with di- lute acid. Yellow coloration. Red coloration. Dark-blue color- ation. Red color, which becomea green IODIC AOID. Reduced. Is not reduced. Is not reduced. 3«MBiBa»rJaBaiaagi»gi'««ia»a^ WM mm s^Ptssmit 16|2 ORGANIC CHEMISTRY. The united extracts are agitated with water, acidu- lated with sulphuric acid, making the liquid only slightly acid. When the solution is completed, animal cliarcoal is added, and the liquid brought to boiling, filtered while still hot, and allowed to cool. The quinia sulphate which is formed, 2(O.MH24Na02). Il2S04+7aq., being but slightly soluble, is deposited on cooling. After being allowed to stand 24 hours, the sulphate is collected, expressed and redissolved in as small a quantity of water as possible, containing a few drops of sulphuric acid. The liquid on cooling, deposits crystals, which are dried at 35°. The mother liquors are treated with ammonia, or sodium carbonate, which precipitates a certain quantity of the alkaloid. The precipitate is lightly washed with water, redissolved in dilute sul- phuric acid, boiled with washed animal charcoal, and allowed to cool. A second crop of crystals of quinia sulphate is thus obtained. The mother liquor contains cinchonia sulphate. This sulphate is dissolved in 30 times its weight of boiling water, allowed to cool, and a slight excess of ammonia added. The cinchonia which is precipitated is collected on a filter, and washed with lukewarm water until the filti-Hte no longer gives with barium chloride a white precipitate insoluble in acids; it is then dried at a temperature of 30° to 40°. Quinia is whitef amorphous and very friable. It SULPHATES OF QUINIA. 153 !r, acidu- iiid only larcoal is red while sulphate q., being Bulphate } small a Few drops vhicb are ited with ipitates a jipitate is lilute Bul- rcoal, and of quinia r coniains ved in 30 cool, and lected on nutil the e a white ,ried at a ■iable. It may be obtained in a crystalline condition, by adding an excess of ammonia to a dilute solution of quinia sulphate, and allowing the solution to stand. This crystallized quinia melts at 57°, losing it« water of crystallization, solidifies and remelts at 176°. It requires 250 parts of boiling and 460 parts of cold water for its solution. It dissolves in 2 parts of boiling absolute alcohol, 2 parts of chloroform or 50 to 60 parts of ether. Its solutions are very bitter, levogyrate, and for the most part fluorescent. Heated on platinum foil, quinia swells up and in- flames, leaving a deposit of carbon. Heated with po- tassa it produces hydrogen and quinoleine,' (cinchon- . lein); it also furnishes a brown compound on being triturated with iodine. Quinia is recognized by the following reactions. It is first saturated with very dilute sulphuric acid and chlorine water; then an excess of ammonia is added, whereupon a green color is obtained. On adding powdered potassium ferrocyanide before the aqua ammonia a rose coloration is produced, which afterwards becomes dark red. Quinia has a basic reaction; it forms with acids crystallizable salts from which the alkalies precipitate quinia. It is a base which saturates two molecules of a monobasic acid. Sulphates of Quinia. Two sulphates of quinia are known; that obtained by the process we have above 164 OROANIO 0HKMI8TRT. ih' deacribf-d, is the neutral siilphate, though generally known as the basic sulphate. Its formula is 2C„H„NaOa.IIaS04+7Il20. This salt contains 74.3 per cent, of quinir. It crystallizes in very delicate needles belonging to the clinorhombic cysteui, and which effloresce in dry air. It dissolves in 30 parts of boiling and 740 parts of cold water; also in 60 parts of cold absolute alco- hol. It is very nearly insoluble in etlier. Its solu- tions are extremely bitter. It becomes phosphorescent on being heated, and subsequently fuses. Heated in the air it burns, leaving a carbonaceous residue. . On adding quinia to water acidulated with sulphuric acid, it rapidly dissolves and another sulphate, often called the acid sulphate, is formed, whose formula is C«,Ha4N.aOa,H2S04 + 7HjO. It is on account of the difficult solubility of the pre- ceding salt, and the great solubility of this latter one, that we cautioned against the employment of an excess of sulphuric acid in the preparation of quinia. This salt dissolves in 11 parts of water at 12°, and in 9 parts at 18°. Sulphate of quinia, heated to 130* with acidulated water for several hours, is transfornaed into an isomeric dextrogyrate base called quinioine^ which is likewise a febrifuge. Medicinal sulphate of quinia always contains sulphate generally mging to ;e in dry 740 parts Inte al co- Its 8olu- borescent bonaceous sulphuric late, often rraula is i>f the pre- latter one, f an exct'SB lia. it 12°, and ed to 130'' ■ansformed quinioiney as Sulphate QUINIA. of dnchonia, and its presence is not considered frandu- lent, even when ii contains ? 5 per cent, of the latter substance, as this salt is necejsarily produced in the preparation of quinia. Cinchonia appears to be of little therapeutic value, and is often added to sulphate of quinia. This adulterant is detected by weighing out 0,5 grams of the salt, and adding to it 5 grains of ether. The mixture is agitated and 1.5 grams of concentrated ammonia added. If no cinchonia is present, two liquid layers are obtained ; if it is present, a layer of this al- kaloid is formed directly above the ammonia. Good commercial sulphate of quinia should give only a very thin layer. The amount of quinia may be directly determined by decanting and evaporating the ethereal solution, and weighing the residue. This result may be verified by replacing the ether in another determination, by cliloroform, which dissolves both bases; the residue obtained by the evaporation of this liquid furnishes the weight of the quinia and cinchonia together. Sulphate of quinia sometimes contains sulphate of quinidia; this base is precipitated, together with cin- chonia. by ether. Its presence may be detected by dissolving one gram of the sulphate in 30 grams of boiling water, and adding to the solution ammonium oxalate. Oxalate of quinidia, which is the only soluble oxalate of these bases, remains in solution, and, on fil- tering, a bitter liquid will be obtained, in which the quinidia may be precipitated by ammonium hydrate. Mri 156 ORQANIO OilEMISTRT. In case sulpliate of qiiinia lias been adulterated with calcium sulphate, or other inorganic substance, it may be recognized by a residue which will bo obtained on heating the sulphate to redness on i)latinum foil. Sulphate of quinia should dissolve in 80 per cent, alcohol. If it dissolves in water, but does not dissolve in 56 per cent, to 60 per cent, alcohol, it may be re- garded as not pure. If adulterated with starch, or fatty bodies, a clear solution cannot be obtt.iued, even in very large quanti- ties of water. Should it contain sugar it will emit an odor of caramel on ignition, and blacken in contact with sul- phuric acid. Quinia sulphate to which salicin, a common adulter- ant, has been added, is colored red by sulphuric acid. Quinia sulphate is chiefly employed in cases of in- termittent fevers. omchonia or oinciioninb. CjoHmNjO. Cinchonia was discovered by Duncan in 1803, though first recognized as an organic base by Pelletier and Caventou in 1820. It diflFers from quinia in containing one atom less of oxygen ; it has never been converted into quinia. It is prepared in the same manner as quinia, but ^ CINOHONIA. 167 ed with , it may iiied 00 >il. ter cent. disBoIve y be re- , a clear ) quaoti' odor of vith sul- i adnlter- mlphuric 68 of in- 3, though etier and im less of Ilia, linia, but from the Gray Peruvian Bark. Cinchonia separates out in crystals on the eviiporution of the alcohol with wliich the calcic precipitate 's waslied. The crystals of cinchonia are collected, allowed to drain, and tlio liqnid which runs off will furnish addi- tional crystals on being evaporated. To this mother licjuor sulphuric acid is added in excess, and the sohi- tion slightly evaporated. The first crystals obtained are sulphate of quinia, which is less soluble than sulphate of cinchonia. When nothing remains but a very concentrated mother- liquor, the cinchonia is precipitated by ammonia, and freed from quinia by washing with ether. The quinia dissolve^, while the cinchonia remains insoluble. The latter crystallizes in brilliant colorless crystals, which are insoluble in cold water and ether, soluble in 2,600 parts of boiling water, in 30 parts of boiling 90 per cent, alcohol, and 40 parts of chloroform. Its solutions are very bitter and dextrogyrate. Cinchonia melts at. about 257°; on heating to a slightly higher temperature in a current of nitrogen, or hydrogen, it is completely sublimed. With chlorine and bromine, it furnishes dichloride and dibromide of cinchonia. With iodine, a yel- low crystalline body is obtained, whose formula is Heated with fused potassa, it produces quinoleine. Cinchonia has ar^ alkaline reaction. It unites with acids, forming salts which correspond to the salts of quinia, though generally more solublie. -,*3siWiB» ■ ^-^ PT" i; 158 OBGANIO CHEMISTRY. Cinchonia sulphate, heated to about 135°, furnishes the sulphate of an isomeric alkaloid, oinchonicia or cinchonieine. Cinchonia is employed as a febrifuge in Holland, and a few other countries, but its action is regarded as in- ferior 10 that of quinia. QuiNOiDiNE. — Quinidia is a base obtained from the last mother-liquor in the preparation of quinia, by precipitation with sodium carbonate, It is often min- gled with another alkaloid, cinchonidia or cinchoni- dine, and it is this mixture, containing chiefly quinidia, which is called qumoidme in commerce. Q'linidia is isomeric with quinia ; it melts at 160". It is difficultly soluble in water, very soluble in boil- ing alcohol, and slightly soluble in ether. Its solutions are dextrogyrate. Quinidia acts as a febrifuge. With chlorine and ammonia, it gives the same reactions as quinia, and forms corresponding salts. Quinoidine contains, as we have said, cinchonidia, a subbtance isomeric with cinchonia. This body is crys- talline, fusible at about 160°, almost insoluble in water, slightly' soluble in ether and chloroform ; boiling alco- hol is the best solvent for cinchonidia. m 8TBT0HNIA. 169 iimishes nicia or and, and ed as in- from the uinia, by tten min- yinchoni- quinidia, B at 160°. I in boil- solutions ;e. With actions as Lonidia, a iy is crysr in water, ling alco- ALKALOIDS OF THE STKYCHNOS. The two chief alkaloids are strychnia and brucia. Desnoix extracted from the imx vomica another alka- loid, which he named igasuria', but according to Schutzenberger, this body is a mixture of several bases. These alkaloids are extracted from the fruit of the Btrychnos nux vomica ; from St. Ignatius' beans, fruit of the f'ltryohnoa Ignatii ; from the wood of Ooulevre, root 01 the Strychnoa eoluhrina ; from the upas, the poison of indian arrows, extracted from the Stryohnos tieutS] from the False AngusturaBark, also from the bark of the Strychnoa nux vomica, which contains princi- pally brucia. SIBTOHinA. C2iH!aN20a. Nux vomica is pulverized and boiled with three suc- cessive portions of water containing sulphuric acid, and these decoctions evaporated in a water bath. When the liquid is reduced to a small volume, 126 grams of quicklime slacked to a thin paste are added for each ^yp^ — ■'mutBgBg s^^Sjjhi.Xi^fi^iim»*-^t.-i.itMir i amt>\kuaj-mtJMiK < iaii^^ teo ORGANIC CHEMISTRY. kilo, of nux vomica. The precipitate is. collected on a cloth, washed, dried, and treated with 90 per cent, al- cohol. The alcoholic solution is distilled to three-fourths its volume and left to crystallize. The crystals obtained are chiefly strychnia ; these are allowed to drain, then dissolved in water containing g«5 its weight of nitric acid, and the soluiion concentrated in a water bath. The nitrate of brucia remains dissolved and the nitrate of strychnia crystallizes out. These crystals are re-dissolved in water, animal charcoal added, the solution brought to boiling and then filtered. Ammonia is added to this liquid, the precipitate washed, dried, and dissolved in boiling alcohol, which deposits the alkaloids on cooling. This method is at present very advantageously sup- planted by the process given for the production of quinia, which, briefly stated, consists in treating the sub- stance with lime directly and employing a solvent for the alkaloids, which is insoluble in water, such as petro- leum or amylic alcohol. Strychnia crystallizes in octahedrons or in prisms of the rhombic system ; they are colorless, very bitter, and almost insoluble in water or ether, but readily soluble in ordinary alcohol diluted with 75 per cent, of water. Strychnia treated with potassa furnishes a small quan- tity of quinoleine. Iodide of ethyl produces with this base the compound ;; ted on a cent, al- urthe its obtained liu, then of nitric • bath, and the crystals Ided, the *ecipitate ol, which lusly sup- uction of g the sub- Ivent for as petro- prisms of )itter, and r Boluble of water, lall quan- with this BBUOIA. 161 CaHa(C2H,)NAI. Chlorine gas renders even a dilute solution of this alkaloid turbid and the liquid becomes acid; this reaction is characteristic. Bromine also forms deri- vatives by substitution. Iodine combines directly with the molecule of strychnia. Strychnia dissolves in strong sulphuric acid; the so- lution i.H colorless and becomes dark blue iu contact with poiassium bichromate or lead dioxide. The color rapidly passes to red and finally to a yellow. Strychnia is colored yellow by hydrogen nitrate only when it contains brucia, a trace of which is suf- ficient to produce the change. Strychnia forms with acids crystallizable salts. The nitrate C2iHa2N202,HN03 crystallizes in fine needles very soluble in hot water. Strychnia is among the most powerful poisons, 2 to 3 centigrams being snlRcient to cause death. There is believed to be no reliable antidote for strychnia though F. M. Peirce claims that small doses of prussic acid are efficient for the purpoie. (44-'68-336.) BRUCIA. CasHaeNA-^HjO. To obtain this alkaloid the alcoholic liquids from which strychnia has been removed, are saturated with oxalic acid and evaporated. The crystals of oxal- ate of brucia which are formed, are washed with 95 per \m^^^ iges^P^ 162 OBOANIO CHEMISTRY. cent, alcohol and redissolved in water. The sohition is decomposed by lime, the precipitate collected, dried and dissolved in boiling alcohol; brucia then crystal- lizes out and is pnrified by two recrystallizations. Crystals of brucia are large and of the clinorhombic system; they are solnble in alcohol, insoluble in ether, but soluble in 850 parts of cold, or 500 parts of boil- ing water. Concentrated sulphuric acid strikes a rose color with brucia whicli afterwards changes to green. IJitric acid colors it red, and if heated it gives off nitrous ether, methyl alcohol and carbon dioxide. Brucia is much less poisonous than strychnia. It may be distinguished from strychnia by its reac- tion with nitric acid. A red color is produced by brucia, which passes to violet on the addition of stannous cliloride. This latter coloration does not take place with morphia. Brucia is also one of the best reagents for nitric acid. CuRAEiNA. — From the arrows of the Indians living on the shores of the Amazon and Orinoco, a brown resinous matter is collected, from whicii ciystals of a substance have been obtained v>"^-e poisonous action is exceedingly rapid. Preyer, 1o whom we owe this discovery, I'egards its formula aa CigHigN, and has named it curarina. The Indians of Dutch Guiana poison their arrows with two other substances no less daugeroiis: airari and tikunas. These threo subB*"- ' -^es paralyze the ac- tion of the muscles by destroyinff the motor nerves ?il!PiiWfP jolution d, dried crystal- is. rhombic in ether, of boil- )lor with trie acid as ether, ia. its reac- duced by iition of jii does me of the ns living a brown tals of a us action owe this and has ir arrows is: urari ze the ac- )r nerves VEBATBIA. 163 (Claude Bernard), It appears that urari, though a fa- tal poison when introduced into the blood by a wound, may yet bo swallowed with impunity. DEASno rOISONS. We shall not describe the prejjaration of the follow- ing alkaloids, on account of their minor impoi-tance. The process in general is similar to that by which the ^preceding ones are prepared: The alkaloid is dissolved in an inorganic acid, precipitated by a base, and redia- solved in an apj)iopriate solvent. The roots of the white hellebore ( Veratrum album) and its seeds, furnish an alkaloid called veratria, CsaHs^NjOg. It crystallizes in prisms having a rhom- bic base. They are very bitter, insoluble in water, soluble in alcohol and ether, and melt at 115°. Vera- tria is dissolved by strong nitric acid, the solution be- ing violet. Sulphuric acid colors it first yellow, then red. Three other poisonous bases, adbadilUa, colchinia., and jervia, are found associated with veratria in the Veratrum album. Jervia, C20II46N2O82H2O, (Ger- hardt and Wills' analysis) is white, crystalline and fusible. These bodies are very corrosive poisons, producing great irritation of the alimentary canal. ALKALOIDS OF THE TOISONOUS SOLANACKfi. The belladona, Atrojpa belladona, and the thorn- apple, Datura stramonium., furnish each an alkaloid >'jiww>ft^,j wi f i 'n,jjjujim ii i 164 ORGANIC CHEMISTRY. called, respectively, atropia and daturia, the formula of which is CitlliaNOa. This substance crvstallizes in fine needles, which are fusible at about 90", and are partially sublimed at about 135°. It is difficultly soluble in water, but very soluble in alcohol and ether. Heated with an oxydizing agent, such as potassium bichromate, or sulphuric acid, it disengages essence of bitter almonds, easily recognizable by its odor, and crystals of benzoic acid are sublimed. With sulphuric acid a violet color is produced, accompanied by a fra- grant odor resembling that of a rose. Hydrochloric acid furnishes two acids with atropia, tropic CgHioOg, and atropic CgHgOa. Cases of poisoning by atropia are rare, but instances in which persons are poisoned by the berries of bella- dona are of frequent occurrence. The black henbane, Hyoacyanvut niger^ furnishes silky needles of a substance, hyoaoiamine., which has much resemblance to atropia, but whose action as a poison appears to be less violent. Its physiological action is on the nerves rather than on the muscles. It causes less dilation of the pupil of the eye, and produces a sombre delirium. BoUadona and atropia, the datura, the henbane and hyosciamine, as well as the poisonous solanacese in general, should be classed among the narcotic poisons. Poisoning produced by belladona, and by most of the poisonous solanaceSB, is characterized by great dila- tion of the pupils of the eyes. The patient is also AOONITINA. 166 I formiila which are )limed at but very potassium essence of odor, and sulphuric I by a Ira- ;li atropia, t instances 58 of bella- fumishes which has iction as a ■ather than he pupil of nbane and anacesB in tic poisons. )y most of jreat dila- nt is also seized with vertigo and strange hallucinations followed by a turbulent delirium and convulsions. The face is congested, respiration difficult, and the skin often breaks out in an eruption similar to that in rubeola (measles). No antidote is known for these poisons; an infusion of uiiroasted coffee, tea, or other astringent substances is recommended, but the use of energetic emetics and purgatives is the most eificient method of treatment. The chemical characters of these alkaloids has not been as yet very fully studied. Desfosse has extracted from the woody nightshade, Solanum dulcamara, from the berries of the felon- wort and from the young sprouts of the potato, SolO' numtuherosum^s. substance called aolanine, C43H7iNOig, a highly poisonous alkaloid. On being boiled with acids, it furnishes a stronger base solanidine and glucose. AcomnNA. Aconitina is extracted from the monk's-hood, Aoonitum napellus, as a colorless amorphous, bitter powder, soluble in alcohol, slightly soluble in ether, and almost insoluble in water. It fuses at 120°, and is al- kaline. It is a very active poison. Planta gives its formula as O30H47NO; (?). Duquesnel has extracted from the AoonitujYh napel- 1x18 a crystalline alkaloid, whose formula is C2JH40NO. ■tiglDf0ggiffiBSissi«.i LwaffW»'^iig?^J^ft>saB;aA:fgy:fcreseiit in it from 0.5 this Pub- •77-102.) coffee and dissolved, is treated irate out are pnri- recrystal- matS'pos- e at 178°, ire. These old water, ing water, an should Qon bever- I of many mow, con-. THEOBROMINE. 169 It 18 recognized by boiling with faming nitric acid; a yellow liquid is produced. On being evaporated to dryness, and ammonia added to the residue, a purple coloration is produced, resonibling murexide. (p. 125.) Amalio acid and Cholestrojpimn are products of tJie action of oxidizing agents upon caffeine; bodies link- ing this alkaloid to the uric acid group. THEOBKOMINB. There is extracted from the caco, Theohroma cacao, a principle crystallizing in microscopic crystals, volatile at 296°, soluble in alcohol and ether, and slightly so iji water. It furnishes salts which are decomposed by water. It is called theobromine; its formula is CtHb JN 4O2. WOKOTOXIN. CsHeO,. From the Indian berry, Cocculm Indicus, there is extracted a white crystalline matter of extreme bitter- ness, called picrotoxin, (from mxpos bitter to^ihSv ) This body is neutral, difficultly soluble in water, and easily soluble in alcohol and ether; its solutions are levogyrate. The physiological action of picrotoxin is analo- gous to that of strychnia, but it differs from it in that It renders the action of the heart slower, and produces vomiting. Prof. J. W. Langley. of Pitteburg, has contributed " """Ksa^iKsmf-:- ■^~ -•■Tm>w»i^^ 170 OHOANJO 0HKMI8TRY. "> , ,1 II much to (87-1862) our knowledge of .the chemical character of picrotoxin. POLTATOMIO ALKALOIDS. There are polyatomic bases which are to the mona- tomic bases what polyatomic alcohols are to mouatomic alcoliols. They are built upon the type of several molecules of ammonia, or condensed ammonia, in the same man- ner that polyatomic acids and alcohols are derived from several molecules of water. CIocz obtained the former by the action of ethylene bromide upon potassa dissolved ?" alcohol. HoflEmann established their true formula. They are called polyaminea. EXAMPLE. Ethylenic diamine. Na < II 2 I H, Diethylenic " Triethylenic " N, N. 11/) IT/ f C2H4' C3H4' TJBBA. CH,N,0=N, CO" Ha Ha ^WHMHilHi POLYATOMIC ALKALOIDS. 171 chemical the mona- nonatomic molecules same raan- •e derived if ethylene They are Kouelle, Jr., was tlio first to obtain this body in an impure state from uriiio, Foiircroy and Vanquob'n first obtained it pnre. Woehler, in 1828, prepared it artificially by a remark- able synthesis, the first attempt to form a bod.y syn- thetically. Urea forms the chief constituent of "the urine of mammalia, amounting to nearly one-half of the solid constituent; a small proportion of urea is found in all the fiuids of the body. It is an excretory product, as the hydrogen and carbon whibh have taken tlioirpartin the body, escape mainly in the form of water and carl)on dioxide, so the nitrogen is eliminated from the system chiefly in the form of urea. Urea may be extracted from urine by evaporating this liqnid to one-tenth its volume and adding, after it has become cold, an excess of nitric acid. Brown crystals of nitrate of urea are formed: these are drain- ed, expressed, re-dissolved in water and boiled with animal charcoal. This solution is filtered, and on evaporation it deposits crystals of nitrate of urea. This salt is then dissolved in as small a qiinntity of water as possible, and the solution treated first with barium carbonate, then with a strong solution of potas- sium carbonate; urea is set free and barinm and potas- sium nitrates formed. The above mentioned salts are added as long as effervescence is produced; the liqnid is then evaporated to dryness, and the residue treated with absolute alcohol, which dissolves only the urea. (J. E. Loughlin, 100-5-362.) •«HiSW«*>» 172 ORGANIC 0HEMI8TBT. The synthetic method employed by Woehler, con- sists in preparing cyanate of ammonia, which body ia isomeric with urea. Cyanate of AMMONnnii=H4CN20=NH4-0-CN. This substance changes spontaneously into urea. Heat, upon an earthen plate,' 28 parts of potassium ferrocyanide and 14 parts of manganese dioxide, both finely pulverized, and dry until the mixture becomes pasty; when cold, the mass is pulverized and tpeated with water, and 20 parts of ammonium sulphide added to the liquid, which is now evaporated in a water bath, and the residue treated with boiling alcohol. On evaporating the alcoholic solution, crystals of urea are deposited. Urer , is also obtained as a product of other reactions. It crystallizes in prisms of the tetragonal system; these crystals are colorless, without odor, and have a cooling taste. It is soluble in its own weight of water at 15°, in an equal weight of boiling alcohol, and in 5 parts of cold 80 per cent, alcshol; it is diflBcultly soluble in ether. Its solutions are neutral. Urea fuses at 120°t at about 150° it is decomoosed, yielding ammonium carbonate, ammelide, CgOHgNs, and lluret, C^OaHs^s- Oxydiidng agents decompose urea. Chlorine also decomposes solutions of urea in the following man- ner : _ 3Cla + HjO -F CH4]Sr80=6HCl + N, + CO^ . Jrea heated to 140° with water in sealed tubes, is transformed into ammonia and carbon dioxide: TTBEA. 173 )ehler, con- icli body is -0-CN. ito urea. ,f potassium ioxide, both are becomes and tpeated Iphide added a water bath, ilcohol. On Is of urea are •duct of other lie tetragonal out odor, and at 15", in an jarts of cold ble in ether. decomDOsed, le, CsOHbNb, Chlorine also lowing man- + CO2. saled tubes, is ioxide; HaO+OHAO=C03+2NH3 . Thifj transformation likewise occurs when urea is heated with strong sulphuric acid, or fused with po- tassa, also, spontaneously, in presence of the nitro- genous matters of the urine. Urea does not appear to unite with all acids. It has not ye't been combined with carbonic, chloric, lactic or uric acids. The nitrate, chloride and oxalate of urea are crystalline. Urea forms combinations with mercury, silver, and sodium oxides, also with mercuric and silver nitrates, etc. 174 OEftANIO CHEMISTRY. P ^^?| NATURAL FATS AND OILS. i \ \ The fatty bodies are very widely distributed through- out the vegetable and animal kingdoms. Some are liquid, others are more or less solid. Certain oils re- main liquid exposed to the air, as olive oil; others oxydize and thicken, as linseed oil, poppy oil, and nut oils; the latter are called siccative oils, and are used in the manufacture of varnishes, printers' ink, oil cloth, also ia paints. ! ts and oils are insoluble in water; they are among the -ery few bodies which are wholly insoluble in this menstrum; they are also, in general, difficultly soluble in alcoliol. They generally dissolve in ether, and the liquid hydro-carbons. Their specific gravity is less than that of water. Heat destroys them ; acrolein is usually formed associated with otlier products. Since oil and water repel each other, many other substances may be protected from moisture by simply coating them with oil. Shoe-leather may be rendered water-proof and iron protected from rusting by greas- ing. Wood, saturated with oil, will last for a long time when buried in moist ground. Stearin or Steabine, (from ffreap, suet) C57HnoOe, is prepared by melting suet i\ turpentine; the two other proximate principles present, are precipitated, :i H FATS AND OILS. 176 brough- »me are oils re- ; others oil, and and are ers' ink, © among iluble in ifficultly in ether, p gravity formed ,ny other y simply rendered )v greas- a long 3|i7Hiio06, the two cipitated, "while the stearine remains in solution. It is separated from the liquid by water, and purified by sereral re- crystallizations in ether ; it fuses at 71°, and solidifies at' 50°. Berthelot has reproduced stearine synthetically, by heating 3 parts of stearic acid with oue part of glyc- erine, in a sealed tube. This synthesis, as well as other researches, estab- lishes the fact that the neutral fats are compound ethers of glyceryl, and the fatty acids. Oa account of the heat generated by oxidizable oils when exposed to the air, frequent instances of spontaneous combustion occur when cotton rags, or waste soaked with oil, are allowed to remain in a heap. Fats, especially if mixed with nitrogenous matter, become acid, rancid. The chemical nature of this change is not entirely understood. Olein ok oleine, is the chief constituent of olive oil and fish oil. Berthelot has shown, by the action of oleic acid on glycerine, that natural oleine is a mix- ture of monoleine, dioleine, and trioleine. Oleine heated with a small quantity of mercury nitrate, or any other body capable of fumiphing nitric oxide, be- comes solid, owing to the transformation of the oleine into an isomeric body, elaidine. Siccative oils contain, instead of oleine, another principle called elaine. Neutral fatty bodies and other ethers of glycerine are decom^)osed by alkaline solutions ; a combination with wpter takes place, glycerine and fatty acids are formed. We may take as an example, stearin. hi j; ViBf ■• -■ 17-6 ORGANIC CHEMISTRY. 3KHO+C57Hno06 = 3(KCj8H3502) + C3H808. Alkalies, therefore, react upon the ethers of glycbrine in the same manner as do the ethers of glycol and ordinary alcohol. This reaction is called saponifiGOr tion, and soaps are salts formed by stearic, margaric, and oleic acids, with a metal. SOAPS. STEAEINE CANDLES. • The only soluble soaps are those whose base is potassa or soda. Soda soaps, those ordinarily in use, are hard, while potassa soaps are soft. On adding to an aqueous solution of soap a solution of a metal, a precipitate is formed which is the soap of the metal employed ; thus the precipitate which common water produces in soap is a lime soap. Ordinary soap is made by boiling fats of inferior quality with an alkaline solution. When the oil is completely decomposed the soap is precipitated by salt water, in which soap is insoluble. Stearine candles have hitherto been made by saponi- fying suet or tallow with lirae in the presence of boiling water. At present the amount of lime employed in the saponification is considerably diminished (amount- ing to only 4 per cent.) by operating at a temperature of 150°. The saponification of fats of inferior quality is also effected by means of sulphuric acid instead of lime; this acid forms with the fatty acids, double or conju- ^^db "f^m«im'ilf'!«iiiling nitric acid converts it into saccharic and oxalic acids. Mannite, treated with a small quantity of nitric acid, is changed into a body insoluble in water, called nitro-mannite, >-»tq V > Oe, which may be regarded as a compound ether. Duloite. — Dulcite is very analogous to mannite, but differs from it, in that it furnishes, with nitric acid, mucic acid. .1 ■M 184 OBOAIflO 0UKM18TKY. ,* , * ■ GLaCOSES. C,HuOe. These componnda may be considered as representar ti , carbohydrates. Ordinary glucose (from yXvxv?, sweet,) or grape sugar, is a crystalline substance, and is found in honoy, iigrf, and various other fruits, together with anotlier insoluble gUicose. It has been found in small quantity in the liver and in tno^t of the fluids of the body. It is obtained by the decomposition of salicine, tannin, and other substances, which, for this reason, liave been named glucosidea. Vegetable cellulose, the envelope of many inverte- brates (chitin and tunicin) and the glycogenous princi- ple of the liver furnish glucose on treatment with dilute acids. It is maimfactured on a large scale by the action of starch upon dilute sulphuric acid. Water containing four to eight per cent, of sulphuric acid is placed in vats and "heated to boiling by means of superiieated steam. Before the water boils, starch mixed with water is added, and ebullition maintained as long as a small quantity of the mixture gives a blue reaction with iodine. The sulphuric acid is not changed durmg this transformation: It is then saturated with chalk and the liquid allowed to become clear. It is decolored by passing through ^a IMAGE EVALUATION TEST TARGET (MT-S) 1.0 I.I |50 *"^" u 1.25 ■ 1.4 PhoiDgraphic Sciences Corporation 2A 2.2 IZO 1.6 «' '<> 23 WEST MAIN STREET WEBSTER, N.Y. 14580 (716) 872-4503 PI? ■i_^ CIHM/ICMH Microfiche Series. CIHM/ICMH Collection de microfiches. Canadian Institute for Historical Microreproductions / Institut Canadian de microreproductlons historiques ■Hid GLUCOSES. 185 filters containing animal charcoal and evaporated to a density of 41° Baum^. The glucose crystallizes in compact masses. Often the liquid is evaporated to only 3° B., when a syrup is obtained known as starch symp. Honey treated with cold concentrated alcohol, also furnishes glucose. The crystals of glucose are small, opaque, and ill defined. They are represented by the formula CeHijOj,2H20, but they may be obtained having the composition CeHijOe byprecipitating the glucose in boiling concen- trated alcohol. The water may also be driven off by heating the glucose to about 100°. Glucose is soluble in a little more than its own weight of water. Weak alcohol dissolves it readily. It is slightly soluble in cold concentrated alcohol. Its solutions turn the plane of polarization to the right. This rotatory power is feeble in the cold. Glucose, heated to about 170°, acts in the same man- ner as mannite. Gelis has demonstrated that it loses a molecule of water; the body formed CgHioOs, is called glucosane, CaHi20o=C6Hio05 + H20. It re- produces glucose on being boiled with acidulated water. If glucose is boiled with dilute nitric acid, saccharic and oxalic acids are formed. Fuming nitric acid forms with glucose a very explosive compound. Hydrochloric acid turns it brown. With dilute sul- phuric acid it furnishes a double acid (sulphogliioio acid)] with strong sulphuric a'jid, carbon. Glucose oxydized with care, furnishes saccharic acid. Heated to 100° with butyric, or various other acids, r t.- ^ 186 ORGANIC CHEMISTRY. it loses water, and the glucosane formed reacts upon the acid, forming an ether, saccharide, or dihutyrio ghicoaane, This body, as well as other saccharides, are decom- posed under the action of boiling acidulated water, into an acid and glucose. Glucose combines, with sodium chloride, forming several crystalline compounds; it also forms unstable compounds with the metallic bases, CaCgHioOs BaCgHiiOg, etc. P^ligot has shown that the solutions of these glucos- ates are gradually changed into salts of a special acid called glucio acid, whose formula is C12H18O9. Cupric acetate boiled with glucose is reduced to the state of suboxide. This action, which is very elow with salts of copper with inorganic acids, becomes rapid and complete in presence of alkalies. On adding glucose to a solution of copper sulphate, this salt is not precipitated by potassa. If, however, the liquid is heated, it deposits cuprous oxide. (Trommer's test.) This reaction is more delicate with copper salts, whose acids are ,i ii'tj-^'i^iil id reacts upon s, or dihutyrio les, are decom- idulated water, loride, forming forms unstable of these glucos- f a special acid 3 reduced to tlie salts of copper ,nd complete in 3se to a solution precipitated by ated, it deposits Lhis reaction is ifhose acids are GALACTOSE. 187 organic. A mixture is used of copper sulphate, Rochelle salt and soda (Fehling), or a solution of copper tartrate in potassic hydrate. (Barreswil.) Prof. W. S. Haines has found in glycerine a very desiriible substitute for the tartrate in Fchling's test. The proportions employed by him for qualitative ex- aminations are: cupric sulphate, 30 grains; potassic hydrate, li drachms; pure glycerine, 2 fluid drachms; distilled water, 6 ounces. , . LEVTJLOSE, C6H12O6. This name is given to a variety of glucose, which is found in many fruits. It may be obtained by boil- ing inulin with water, or, better, it can be pi )pared from cane sugar by the action of dilute acids. It differs from the other sugars in that its rotary power diminishes on heating. GAUlOTOBE, CgHuOfl. This body is produced by boiling, for two or three hours, sugar of milk with water acidulated with sulphuric acid. It is soluble in water and insoluble in alcohol; nitric acid transforms it into mv^ic acid. INOSIN, INOSriE OE MUSCLE SUGAE. CsHiaOs + SHaO. This substance is found in many animal organs, and 188 OBaANIO OHEMISTBY. is the chief constituent of the liquid which impreg- nates the muscles. It may be prepared by first extracting the creatin from the muscles, then separating theinosic acid with baryta. To the liquid is then added a quantity of sulphuric acid sufficient to precipitate the whole of the baryta and the liquid treated with ether, which dis- solves the foreign substances. il The aqueous solution is removed and alcohol added to it until a precipitate is formed. Crystals of potas- sium sulphate first separate out, then beautiful crystals of inosile. This substance has a sweet taste. At a temperature of 100° it loses two molecules of water. It dissolves in one-sixth of its weight of water while it is insoluble in ether and strong alcohol. Inosite is without action upon polarized light. It is not converted into glucose by the action of dilute acids, and does not reduce copper salts. Mixed with milk and chalk it undergoes lactic fermentation. (Page 122.) which impreg- .ng the creatin nosic acid with a quantity of he wliole of the her, which dis- i alcohol added rystals of potas- eantiful crystals set taste. At a ecules of water, ►f water while it 1. prized light. It action of dilute ;b. Mixed with c fermentation. r^ J 8A0CHAUOSEB. 189 SACCHAEOSES. Okdinaky Suoab, Ci2H2ijOn. This body exists in a large number of plants, though it is almost exclusively extracted from the sugar-cane and beet-root. The sugar-cane, Arundo saccharif&ra^ contains 17 to 20 pe;' cent, of sugar. To extract, the juice of the cane is first obtained by expressing. This juice repre- sents 60 to 65 per cent, of the total weight of the cane, and would alter rapidly in the air if care were not taken to bring it rapidly to a temperature of 70°, and adding a quantity of lime. The juice soon becomes covered with foam and deposits different albuminoid and other matters, which are precipitated by the lime. It is decanted into pans and rapidly evaporated. The sugar crystallizes out, and the mother liquor is evapo- rated as long as it furnishes crystals. The thick liquid which remains is molasses. The sugar thus obtained is brown sugar, and is subsequently refined. The beet-root most rich in sugar is that of Silesia. It contains about 10 per cent, of sugar. Sugar crys- tallizes in clinorhombic prisms. They may be readily obtained by slowly evaporating a solution of sugar. ;i n !':ii! 190 ORGANIC CHEMISTRY. The crystals of ordinary sugar are very small, as the syrup is made to crystallize quite rapidly. Cold water dissolves three times its weight of sugar; hot water dissolves it in all proportion-i, forming a syrupy liquid. It is not dissolved by cold alcohol or ether. Dilute alcoiiol dissolves it in proportion as it is more or less aqueous. Its solutions are dextrogyrate. Sugar melts at about 180°, and yields a liquid which solidifies to a vitreous, amorphous mass, called harley sugar, which becomes opaque and crystalline after some time. If sugar is heated a little above this point, it is transformed into glucose and levulosane. Levulosane. At about IGO** sugar loses water, becomes brown, and finally furnishes a substance whieli is commonly known as caramel. According to Gelis three pro- ducts of dehydration are formed, Garamelane, oara- melene and oarameline. At a temperature of 230° to 250° sugar is decomposed into carbon monoxide, carbon dioxide, carbohydrides and different empyreu- matic products. Sugar is transformed slowly in the cold, and rapidly at 80°, in contact with dilute acids into inverted sugar, which is thus called on account of its inverted action upon polarized light. On pro- longed ebullition the solution is rendered brown and ulmic products are formed. Sugar reacts with baryta water and lime water, forming different compounds called eiicrates or saooharates. Mril SUGAR OF MILK. 191 7 small, as the y. Cold water gar; hot water , syrupy liquid, ether. Dilute is more or less I. Sugar melts rhich solid i lies barley sugar, ifter some time. bis point, it is ano. lecomes brown, 1 is commonly elis three pro- 'amelane, oara- ^rature of 230° 'bon monoxide, erent empyreu- slowly in the th dilute acids Lied on account light. On pro- ired brown and icts with baryta 'eut compouads The solutions of these sucratos are decv riposed by carbon dioxide : sugar is reformed. Eousseau makes use of this fact in the manufacture of sugar on a very large scale. Sugar does not ferment immediately in contact with beer veast. BUOAB OF MILK, LACTHN OR LAOT06B. C12H22OU + H2O. , It is obtained from mifk, by precipitating the casein with a few drops of dilute sulphuric acid, filtering and evaporating the liquid. Crystals are deposited, which are purified by re- dissolving and treating with animal charcoal. In Switzerland large quantities of sugar of milk are made by evapoi'ating the wkey which remains after the separation of the cheese. The c-ystals of this body are rhombic prisms. This sugar is insoluble in ether and alcohol, aad requires 2 parts of boiling and 6 parts of cold water for its solution. Its solutions are dextrogyrate. At a temperature of about 140° it loses H3O, and becomes brown at 160° to 180°. In presence of sour milk and chalk it undergoes lactic fermentation. Sugar has been found in a sample of a saccharine matter extracted from the sap of a sapodilla ti'ee, the tree furnishing caoutchouc. IB ip 192 ORGANIC OnEMISTBY. Keichardt has obtained from gum arable a sugar distinct from ordinary sugar, a body though having the same formula. He no'nes \tpara-arahin. HONKT. Honey is produced by the domestic bee (Apis mel- lifica), an insect of the order Hymenoptera. It is separated from the wax by exposing the honey- comb to the sua, on wire nets; very pure honey is thus obtained. The mass which remains is expressed, and this prod- uct is a second quality of honey, more colored and of a less agreeable taste and odor than the first. The comb is then heated with water to remove the remain- der of the honey. The wax thus isolated is melted and run into moulds. Honey owes its sweet taste to several sugars. There is found in it a dextroyrgate, crystallizable glucose, and on removing this sugar there remains a viscid uncrystallizable liquid, which contains levnlose. In addition "to these, small quan- tities of ordinary sugar have also been found in honey. GLUCOSIDES. This name is given to certain bodies which have , the property of forming various products by combin- ing with ^ater, among which is glucose, or some other saccharine matter. This change is produced by the action of acids, bases, or by the action of ferments. "We cite the fol- lowing, but shall only study the most important: irabio ihough rabin. a sugar having bee (Apis mel- sra. ing the honey- pure honey is md this prod- 3 colored and le first. The e the remain- ;ed is melted sweet taste to dextroyrgate, ? this sugar liquid, which I, small quan- Bn found in which have 8 by combin- r some other )n of acids, cite the fol- (ortant: GLIT008IDE8. 193 S;ilicin, CialligO,, extracted from the bark of the Willuw. Amygdalin, 0.»H„NO,„ extracted from the Bitter Almond, Amygdalus oommtmia. Orcin, CiHsOj,, extracted from various Lichens. Tannin, 0„HaO,7, extracted from the Oak. Phlorizin, CziHziOio, extracted from the Apple^ Pear, or Cherry tree. Populin, CjoHjjjOg, extracted from Aspen leaves. Arbutin, CisHibOt, extracted from the leaves of the Uva-Ursa. Convolvulin, Q^'R^O,^, extracted from the CoriAJol- vultia orizahemis and sohifideanus. Jalappin, Cs^UseOi^ exti-acted from Convohmha orizahensia and acammonia. Saponin, a white amorphous powder whose solution is very frothy and of which the powder is very sternu- tatory. Dophnin, OwHsjOig, the crystalline matter extracted from the bark of the Ash {Fmxinua excelsior). Cyclamin CaoHjiOio, extracted from the tubercles of the Cyclamen eurcjpceum. Qumovin, CsoIIjsOg, a resinous, bitter matter, solu- ble in alcohol, existing in the bark of the Quina nova and other cinchonas, Solanin, C43H7iNOie. This has abeady been studied, (page 165). Esoulin, OaoHsiOi,, extracted from the bark of the Horse Chestnut. , Qnercitrin, Q^^0„, from the bark of the yellow oak (Quercm tinctoria). V. 194 OROANIO 0HEMI8TKY. Ooniferin, CieHaOg, from the Larix europaea, etc. Vanillin, from the Vanilla bean, and recently ob- tained artificially (60-74-608). SALICIN, CislIiaOT + IIaO. Thia body cryrtallizes in white needles, fusible at 120S Insolable in ether, solublo in alcohol and water. These solutions are levogyrate and very bitter. It is used as a febi'ifugo, but is of little value in well de- fined intermittent fevers. It has as a dibtinguishing chemical character, the property of becoming red with sulphuric acid. Under the action of dilute sulphuric, or hydro, chloric acid, or even with emulsin, salicin is decom- posed. With the latter the reaction is: CisHisOt + H,0=C6H, A + CtH A Glucose. SaUeenin. In contact with cold nitric acid it loses hydrogen, and a body is formed called helicin^ CisHiaO^. When treated with oxydizing agents, it gives off an odor which is identical with that of the essence of meadow sweet {Spirea ulmana). This body if. produced especially when salicin is treated with a mixture of sulphuric acid and potas- sium bichromate, and is also known by the name of hydride qfsalicyl. Its formula is identical with that of benzoic acid, fjHsOa, bui it has not the properties of this acid. . ii'yiKtf^ii 8ALICIN. 196 mropaea, etc. d recently ob- ilcB, fusible at hoi and water. y bitter. It la ue in well de- character, the ic acid. iric, or hydro- licin is decom- loses hydrogen, 3H16O7. !, it gives off an the essence of when salicin is acid and potas- by the name of af benzoic acid, les of this acid. It is an aromatic liquid, boiling at 196°, and hai he property of oxydizing spontaneously, giving rise to an acid called salicylic acid, C7lle08. Salicin, treated with fused potassa, furnishes potas- sium oxalate and salicylate. Cahours has shown that essence of Gauliheria procumbena, a heath of New Jersey, contains, besides, an isomer of the essence of turpentine, a sweet-scented liquid, boiling at 220°, which is salicylic methyl ether, and is re-converted, in contact with, nlkalies, into methyl alcohol and sali- cylic acid : it may be produced artificially by treating wood spirit with a mixture of salicylic and sulphuric acids. Salicylio or oxybemoio acid has been lately pro- duced by Kolbe (56 -'74 -22), by a remarkable syn- thesis in acting on carbolate of sodium with COj. 20.H,0Na + C0,=C,H80 -f- O^H^OaNaa. wK«Maei!^V<*i an lose its oxy- nal excreta are :l8 on exposui'e n a good crop, )gen of the air, jh furnitih not lose which, be- organic com- sccsfeary for its ter there is rc- jium chlorides, ogen, nitrogen,, rariety of com- ih we have not, I research gives tide and water, formic acid he acid. Pasteur le principles of •mentation and ;o fonned under 'e are far from es which nature oith only four is that of the elaborate with let, the fragrant VEGETABLE CHEMISTRY. 203 By combining six atoms of carbon with five atoms of water, nature forms either the woody principle, oel- lulose, or the essential constituent of the potato, ^^aroA. By uniting ten atoms of carbon with sixteen atoms of hydrogen, she produces, in the orange and in tlie pine, two essences or oils very difierent in character. By associating the four organic elements she forms tlie most different substances, the nourishing cereal as well as the most deadly strychnia; and often products as unlike as these are found side by side in the same plant. Thus the plant is a stnicture which decomposes car- bon dioxide, water, and compounds of nitrogen; which forms its substance out of carbon, hydrogen, nitrogen, and a part of the oxygen of these compounds, and which exhales oxygen. Hence, chemically, it would be proper to call tlie plant a rednoAng apparatus. "We should add that the flowers and portions of ^'lants not green, also the buds in developing, produce an exhalation of carbon dioxide, and Ihat during ger- mination, and especially during the time of flowering, a sensible amount of heat is disengaged. As a result of this elevation of temjierature, there is produced in plants some slight oxydation or combustion, as in the respiration of animala. Hence, we must conclude that plants and animals, in many circumstances at least, deport themselves in .a similar manner. Many experimenters, and especially Dutrochet and Gurreau, go further, and say that plants and animals . ^■ 204 ORGANIC 0IIEMI8TRT. respire in an identical manner, and according to their theories all living creatures take up oxygen and exhale carbon dioxide. The experimentH of Garreau especially deserve at- tention. He placed branches, detached or affixed to the plant, in vessels full of air, and exposed them to a diffused light. The volume of the air was known and the oxygen absorbed was determined by a special con- trivance ; the carbon dioxide produced was removed by placing in the vessel an alkaline solution of known weight. Thus the variations of these gases were care- fully stud'ed. As a TLoijlt of his experiments Garreau claimed to have established that both in the dark and in the light, there is an absorption of oxygen and an ex- halation of carbon dioxide, but the amount of car- bon dioxide collected does not represent the amount really exhaled, as the greater part is reduced at the moment of liberation. From these facts it would appear that in all living creatures the same phenome- non of respiration takes place, which consists in a consumption of oxygen and an exhalation of carbon dioxide. This phenomenon is associated with another ; viz., assimilation or nutrition. It is here that the differ- ence, indeed a complete opposition, between the two kingdoms is established. The plant grows by re- ducing, under the inflnence of heat and sunlight j carbon dioxide, water and nitric acid, by accumulating carbon, hydrogen, nitrogen and by exhaling the greater "««99BiSK^|PS^-' iording to their 'gen and exhale illy deserve at- sd or affixed to losed them to a was known and r a special con- l was removed ition of known ases were care- 3au claimed to rk and in the m and an ex- .niount of car- at the amount reduced at the [acts it would same phenorae- i consists in a tion of carbon another ; viz., ;hat the differ- tween the two grows by re- and sunlight j i^ accumulating ing the greatel* "oimmmims^frr' ORGANIZED SUBSTANCES. 205 part of the oxygen. The animal, on the other hand, forms its substance from that of the plant, oxydizing, or consuming, the vegetable products with the oxy- gen of the air exhaled by the plants; it reduces the complex products formed in the vegetable to the state of carbon dioxide, water and ammonia; thus the ani- mals supply the plants with food, receiving in turn nourishment from them. Those desirous of further studying this and other interesting i,opics relating to Vegetable Chemistry, will find very valuable the works of Prof. S. "W. Johnson, « How Crops Grow," and "How Oops Feed"; also Prof. John 0. Draper's article in Am. Jour. Sci. and Arts, Nov. 1872, entitled ''Growth of Seedling Plants." ORGANIZED SUBSTANCES. Among the chemical substances of which we have spoken certain ones participate more in vital phe- nomena, and have more definite physical structure than do others. These are designated as organhed or organizoMe s^ihstancea, the term organio being reserved for the definite compounds studied in organic chemistry. All these substances play an important part in the veget- able kingdom, forming the network of vegetable tis- sue, as cellulose or as starch, etc. CELLUIXBE OB OELLULIN, (CgHio05)n. ' On examining a young plant under the microscope, il 206 ORGANIC 0HEMI8TKY. we observe that it is built \ip of little cells and mi- nute, diaphanous ducts or vessels filled with sap and air. The material of which these tissues are com- posed is called celliiloae. The pith of the elder, cot- ton fibre, and paper are almost exclusively composed of this substance. Cellulose is a carbo-hydrate; CgHjoOs, is the formula, ordinarily given to it, although a multiple formula at least three times as large, or C,8lIaoO,j is necessary to explain certain reactions with nitric acid. ExPEKiMENT. Pure cellulose may be obtained in the following manner; cotton, linen or paper is treated with dilute alkaline solutions, washed and immersed in weak chlorine water; finally it is submitted to the action of various solvents, as water, alcohol, ether and acetic acid until nothing more is dissolved. This substance is solid, white and insoluble. It is destroyed at a red heat, producing carbon and numer- ous carbohydrides, gaseous and liquid, which distil over. "With monohydrated sulphuric acid it produces a colorless, viscid liquid, which contains, at first, an insoluble substance having the properties of starch and yielding a blue color with iodine. If the action of the acid is continued, the whole is dissolved and the same products are obtained as in the case of starch when brought in contact with sulphuric acid, i. e. dextrin and glucose. To separate the latter substance, it is simply necessary to saturate the acid with chalk and evaporate the liquid. Concentrated hydrochloric acid produces the same Munmasuu^f^ e cells and mi- l with sap and issues are com- ' the elder, cot- ively composed ^eHioOs, is the iigh u multiple 1, or CigllfflOis is vith nitric acid, obtained in the r is treated with imersed in weak to the action of ther and acetic nsoluble. It is bon and nurner- d, which distil acid it produces lins, at first, an ;ie8 of starch and the action of the 3d and the same of starch when lid, i. e. dextrin substance, it is with chalk and >duces the same i5*™(.'***w»w«e.wBW v-^^Jj^'CSSSliimuJFY" OELLULOSJfi. 207 effect. If paper bo immersed for an mttant only in sulphuric acid, diluted with half its volume of water, and carefully washed, it acquires the toughness of parchment. Paper thus prepared is frequently employed in experiments on dialysis; it is also much used by pharmacists to cover the stoppers of bottles. It is known in commerce as vegetable parohment. f GUN COTTON OK PYROXYUN. Gun cotton was first made by Schoenbein, in 1846. To prepare it cotton is plunged for two or three minutes into fuming nitric' acid, or, better, into a mix- ture of 1 vol. nitric acid (of a density of 1.5), and 3 vols, of strong sulphuric acid; it is then thoroughly washed and dried at a low temperature. The cotton is not changed in appearance other than becoming somewhat wrinkled. When well prepared it burns completely, leaving no residue. The tem- perature at which it takes fire varies from 100° to 180° according to the manner in which it has been pre- pared. It is cellulose in which from six to nine atoms hydrogen have been replaced by an equivalent quan- tity of the monad radicle NO^ that, having the formula O18H21O159NO2, has the greatest explosive energy. Pyroxylin regenerates cellulose in contact with ferrous chloride. If cellulose be considered a sort of alcohol, as claimed by some, pyroxylin would be a nitric ether of this alcohol. Pyroxylin has the advantage over gunpowder of 208 OKOANIO OUEHISTKY. beiiiff more easily prepared, and of remaining nnaf- fected l)y moiBtiire, but its cost is relatively greater, and its shattbring power rundera its employment dangerous. The term collodion (from xoWa^ ghr^ is given to a preparation obtained by dissolved gu cotton in a mixture of 1 part of alcohol and 4 parts oi ether. Chas. II. Mitchell has made (62-Y4- ii36) a number of experiments, with the view of ascertaining the rela- tive proportions of cotton and acid, together with the proper time of maceration necessary to produce a cotton which should combine the largest yield with the highest explosive power and solubility. The following formula was at length adopted: Raw cotton, - - . , - 2 parts. Potassium carbonate, - - - 1 " Distilled water, - - • 100 " Boil for several hours, adding water to keep up tho measure ; then wash until free from any r^kali, and dry. Then take of — Purified cotton, - - - - 7 oz. av. Nitrous acid (nitric, saturated with nitrous acid), 8. g. 1.42, .... 4 pints, Sulphuric acid, s. g. 1.84, - - - 4 " Mix the acids in a stone jar capable of holding 2 gals., and when cooled to about 80° Fahr., immerse the cot- ton in small portions at a time ; cover the jar and allow to stand 4 days in a moderately cool place (temp. 50° to 70° Fahr.) then wash the cotton in small po:-- i w Kt rt i Wj III iiii if Mwft liiMWTtllimiii I OKI CKLLULOHK. 209 mining nnaf- ivoly greater, employment ^ is given to a -cotton in a 01 ether. 36) a number tiing the rela- :her with the » produce a 3t yield with iopted: 2 parts. 1 « 100 « ) keep up the y r'kali, and 7 oz. av. ous acid), 4 pints - 4 " )lding 2 gals., lerse the cot- p the jar and . place (temp, n small po;-- tions, in hot water, to remove the principal part of the acid; pack in a conical glass percolator, and pour on distilled water until the washingii are not affected by solution of barium, chloride. Collodion, on spontaneonsly evaporating, forms . transparent and impermeable membraneous coating, and is much employed in photography, also somewhat in surgery. Cellulose is attacked by chlorine; the use of solu- tions of chloride of lime, and of chlorine, in large quantities in washings or bleaching, will cause a rapid deterioriitiou of linen or cotton goods. Schweizer has shown that cotton, paper, etc., is very easily dissolved by an anunoniacal solution of copper. Attempts by the author to employ this solution for a *• water-proof " coating of fabrics, as has been suggested, failed to yield a satisfactory result, on account of the liability of the coating to crack and peel off. Pcligot has found in the skin of silk worms, and Schmidt has discovered in the enve^•pes of the Tunicates, a substance, tunioine, which has the com- position and properties of cellulose. Linen^ hemp, cotton, wood and paper are all essen- tially cellulose. itdiiiii uiuk'jHWvQui^HSliyBfiQyQG^'^' 210 ORGANIC CHEMISTRY. AMYLACEOUS SUBSTAT^CES. These Bubatauces are alinost universally present in plants; particularly that known as starch ovfeoula. The p(;tato yields about 20 per cent, of starch. In order to obtain it, this root is grated and the pulp placed upon sieves, arranged one above the other, and through which a strpsim of water iiowa. The grains of starch bfiiiig extremely minute pass through the meshes of the sieve, while the walls of the cells remain behind. The starch is washed, drained, and dried, first at ordinary temperature, afterwards by the application of a moderate heat. Staeoh. ajCCfiHioOs) probably dgHaoOis- Flour contains, besides starch, nitrogenous substances, de- nominated gluten; this gluten is capable of ferment- ing, whereupon it becomes soluble, while (he starch remains unaltered and insoluble. Under these con- ditions the gluten gradually dissolves, disengaging ammoniacal compounds, hydrogen sulphide and other products of putrefaction. At the end of twenty or thirty days, the gluten having become dissolved, the liquid is removed, and the starch, washed and dried, shrinks into columnar fragments, which are readily pulverized by gentle pressure. nOMbal »imiaHSmimmK»stm mum STARCH. )ES. ly present in i ovfeoula. f starch. In md the pulp he other, and minute pass e walls of the shed, drained, ifterwards by aoOig. Flour ibstancea, de- e of ferment- ile (he starch [er these con- disengaging lide and other 8, the gluten removed, and iito columnar )d by gentle A more modern method is that employed in France, which is eosentially the same as the process cited above, as that used in making potato starch here. The water carries away the starch while the gluten remains be- hind in the form of an elastic mass, which is also util- ized. For this purpose it is incorporated with flour poor in gluten, to be made into macaroni, and for the manufacture of a very nutritive preparation, " granu- lated gluten;" it is also employed, according to the recommendation of Bouehardat, in making bread for persons afflicted with diabetes. Starch, examined with a microscope, exhibits flat- tened ovate granules of different size in various plants, but always very small. Those of the Eolian potato have a length of 0.186 mm.; the smallest are those of the Chenqpodium. quinoa whose length is 0.002 mm. When stafch is heated with water to 70°, the gran- ules increase from 20 to 30 times their original volume, and become converted into a tenacious paste. A small nuarttity of the starch passes into solution, and to this the name amidin has been given. Starch paste and the solutioiis of starch have the characteristic property of becoming blue in contact with small quantities of iodine. The liquid becomes colorless at about 70°, but regains its color on cooling. If to this blue liquid a solution of a salt, sodium sulphate for instance, be added, we obtain a dark-blue floculent precipitate. This substance, called starch iodide, is not a chemical com- pound, but a sort of lake, containing variable quanti- ties of iodine diflfiised throughout the starch and solv- i ^ 212 ORGANIC CHKMFSTKT. ejit. This reaction with iodine is a very valuable test for starch, but is open to several fallacies, and apt to mislead in inexperienced hands. Until lately, it has been claimed that starch is insol- uble in water, and that if water in which starch has been boiled gives with iodine the characteristic reaction of this substance, it is due to particles of starch suffi- ciently minute to pass through the pores of the filter. But the results of the experiments of Maschke and Tlienard, show that if starch is heated for some time at 100°, it is partially transformed into a variety solu- ble in water. This substance is colored by iodine; it furnishes, on evaporation, a gummy solid which is pre- cipitated by alcohol as an amorplious powder. If we boil starch for a long time with water it is converted into a substance called dextrin. The pres- ence of a small per centage of sulphuric acid facilitates this change, which is soon followed by the transforma- tion of the dextrin into glucose. The sulphuric acid is not at all altered during the reaction. TliR change of starch into glucose also takes place when water containing starch, and to which germinated bai'ley has been added, is heated to about 70°. This transformation is due to a substance called diastase {irova. diacrrafft?, separation), which is formed in the seed during germination. The proiluction of diastase on the formation of the young shoot, explains how starch becomes soluble and serves as nutriment to the young plant. The piyalin of the saliva, the pancreatic juice, the r»> aluable test and apt to rch is insol- starcli has Stic reaction Btarcli suffi- if the filter, [aschke and some time /^ariety soiu- 7 iodine; it vliich is pre- ier. water it ia The prea- jd facilitates transforma- Iphuric acid ► takes place I germinated 70°. tance called ich is formed roduction of oot, explains autriment to tic juice, the fiTAROH. 213 solnble parts of beer yeast, gluten, and many other sub- stiinces, are capable of producing this transformation of starch into dextrin and jrlucose. It has generally been considered that the molecule of starch, in being transformed into glucose, simply united with one molecule of water directly, thus: C,H,o05 + H,0=CeII,A. Musculus, however, claims to have established that the starch is first transformed into a soluble metamer, and tliis, thereupon, splits up into dextrin aud glucose: CjgHsoOiB + HaO=2CeH,oO, + C,H, A- V Dextrin. Qlucose. By further action, the whole of the dextrine becomes converted into glucose, (2-[3]60-203). Starch, heated simply to alK)ut 160", is also changed into dextrin. It is attacked by dilute nitric acid, nitrous vapors are given off and different substances are produced, chiefly, however, oxalic acid. If starch is agitated with fuming nitric acid, it is dissolved and water precipitates from the solution a nitrous compound which is explosive. The alkalies, in concentrated solutions, when heated with starch disorganize and dissolve it. Solutions con- taining two to three per cent, of alkali, accelerate the formation of starch paste. iniiiiirtiiiiiyif — 214 ORGANIC OHEMISTRY. Starch is employed in the laundry and therapeutic- ally in poultices, injections and baths. Thpioca is the starch of the root of the Jatropa Tnanihot, called cassava or manioc. Sago is obtained from the pith of various sago palms. Arrow-root is the starch of the Maranta arundi- nacecB, and one or two other tropical plants. Salep is obtained trom the Orchw mascula. ImjLiN. There has been found in the roots of the Jerusalem artichoke, of the cliicory, and the bulbs of the dahlia, a substance isomeric with starch, called inulin. LiCHENiN. There is extracted from certain lichens and mosses a substance called lichenln, which has the property of swelling in cold water and of being dis- solved in boiling water. It is prepared by treating Iceland moss with ether, alcohol, a weak solution of potassa, and anally with dilute hydrochloric acid. There exists in the animal organism a variety of starch designated by the name of glycogen. DEXTEIN, OR DEXTRINE. To prepare dextrin, starch may be heated with water containing a small quantity of sulphuric or oxalic acid ; the operation should be arrested when the liquid gives with iodine only a wine-colored re- action. TWBsss^isr.'f ?r-r»sj!- i-i!stiS\>t^'KViVf:c'it>'r-^ni-: tiait bmn {H-mr. ivn i»^ftif' 4 220 ORGANIC 0HKMI8TRY. less easily procured from beans (haricots), in con- sequence of their containing a gummy matter which interteres with its precipitation and with the filtration of the liquids. The cliemical properties of legumin are identical witli those of casein. Liebig supposes that grape-juice and other vegetable juices which are deficient in albumen, derive their fermentation power from soluble legumin. This principle is soluble in tartaric acid, and to its presence he ascribes the tendency of sugar to form alcohol and carbon dioxide instead of mucilage and lactic acid. VEOBTTABLB ALBUMEN. Vegetable albumen is contained in many plant- juices and is deposited in flocculi on applying heat to such liquids. It can also be precipitated by nitric acid, tannin and mercuric diloride precisely like animal albumen. Vegetable albumen is composed of carbon, hydrogen, nitrogen, oxygen and sulphur. There ia no trustworthy formula for this substance. cots), in con- f matter which th the filtratiou are identical other vegetable derive their gnmin. This [ to its presence rm alcohol and L lactic acid. ANIMAL CHEMISTRY, n many pLant- pplying heat to kated by nitric sely like animal losed of carbon, There ia no BUUIIWlWIUU I JI i HIHai ANIM.^L CHEMISTRY. The substances serving us materials to build up the structure of animals are of a varied no' ure ; they may, however, be grouped into four clasBea : I, FARINACEOUS AND SACCHARINE. II. PArrv. III. NITRCIGENOL'S. IV. MINKHAL, We have already studied the first, second, and fourth of these classes ; we will now proceed to examine those of the third. NITROGENOUS SUBSTANCES. It is generally considered that these substances act a different part in the organism from th ^ of the saccharine and fatty bodies, these latter serving ex- clusively as heat producers, and being decompoded and ultimately consumed (oxidized) in the respiratory process, have therefore received the name of respiratory foods. The nitrogenous principles {albumen, casein, fibrin, etc.) serving to form the tissues have, likewise, ^m^msmr* •01k | .,V V ' — ^ >" *r . <" if a..!".! ^ I ) j«y»^^— ..— . ^ - ^^^-..»-.-y^ , — i., . , ■ . "»■• — — ^.^.,.^, --■,-, ,., -.. . .. , ' -m ■,. . . « 224 ANIM\L CHEMISTRY. received the denomination />/rts^Jc foods. The distinc- tion thus made is too restricted, as we shall show later. Dumas and Cahours have proven that the cereals and otlier plants employed as food contain similar principles to those fouud in flesh, and especially that albuminoid matter exists in plants as well as animals. The albumen of the blood and that of wheat are alike. In the gluten of wheat albuminoid substances are found which are hardly distinguishable from animal albumen, fibrin, and casein. These substances are characterized : 1st. By their amorphous structure. The three sub- stances mentioned never crystallize; and as they are also non- volatile, it is difficult to form an idea of their constitution, and represent them by a formula. This formula must necessarily be very complex, as sulphur forms a constituent, though present only in very small quantity. Lieberkuhn represents their composition by the expression Cy^HnAsSO '22- 2nd. By their extreme instability. The apparently most insignificant circumstance causes them to pass from a soluble to an insoluble condition, or vice versd, and produces their transformation. They are decom- posed with great facility under the action of air and water. This very exceptional instability constitutes a property of the greatest interest, as it permits these The distino- we shall show lat the cereals iontain similar especially that rell as atiimuls. ,t of wheat are Qoid substances )le from animal The three sub- ad as they are rm an idea of by a formula. py complex, as present only in epresents their MITEOGENOUS SUBSTANCES. 225 The apparently 3 them to pass n, or vice vend, ^hey are decom- ition of air and ty constitutes a t permits these substances to take part in a wonderful manner in the varied transformations which occur in living organisms, and it might be said that they are the principal agents of development in animals and plants. We shall pre- sently see that, whatever this real albuminoid sub- stance may be, it is transformed in the stomaoh into identical substances — peptones; also, that during the incubation of the egg the albumen is seemingly changed into fibrin. Classification. — The albuminoid substances are very numerous, and may be classed into two groups. Those of the first group contain: Carbon 63.5 Hydrogen 6.9 Nitrogen ..... 15.6 Oxygen 24.0 100.0 They contain, besides, 0.4 to 0.6 per cent, of sulphur, unlike those of the second group, which usually contain no sulphur. In addition, they often contain small quantities of mineral substances. The first are more specieJly designated by the name of albuminoid substanc'es, as albumen is the most characteristic member of the group. They are also known by the name of protein substances, because Mulder claimed they might be considered as formed of a single radical protein, to which are united variable proportions of sulphur, phosphorus, etc. 226 ANIMAL CHEMISTRY. The principal members of this group are : albumen, of which several modifications are recognized — the paralbumen, metalhumen, etc. ; fibrin, of which there are several kinds — the fibrin of the blood, fibrin of the mnscles or myosin ; casein, regarded by some as a com- bination of albumen and alkali ; homoglohin or heinato- crystallin, the colouring matter of the blood, wbicli is distinguished from most other albuminoid substances by its property of crystallizing ; mtellin, the principle of the yolk of an egg ; also, several principles, idhin, icthlin (Ixdvs, a fish), etnydin, the firet two obtained by Valenciennes and Frcmy from fishes' eggs, the latter from the eggs of the turtle. The composition of these substances is identical or very similar; a formula cannot be given with pre- cision. The substances of the second group generally contain less sulphur, often none, and appear to be derived from the first by the addition of nitrogen and oxygen. They contain in per cent. : Carbon . Hydrogen Nitrogen . Oxygen . 50.0 6.3 16.8 26.6 100.0 In this group we find — ossein, the organic substance of bones, which is converted into gelatin by the action of boiling water ; oartUage, a substance very analogous N1TK0GEN0U8 SUBSTANCES. 227 are : albumen, cognized — the hich there are fibrin of the )me as a com- liti or hciiiato- lood, which is )id suhstances the principle noiples, idhin, obtained by gs, the latter 8 identical or en with pre- lerally contain ;o be derived a and oxygen. 50.0 6.3 16.8 26.6 100.0 mio substance L by the action reiy analogous to the latter, and which is transformed by boiling water into chondrin ; various principles concerned in the digestive phenomena, as the ptyaHn of the saliva, the iiepiiin of the gastric juice, the mucin of the mucus, the pyin of pus, etc.; together with differont pro- ducts which result from the action of the gastric juice upon nitrogenous substances, and which are called (tlbuminoses or peptones. General Characteristics.— The substances of these two groups on being heated give off an odour of burnt feathers. On distillation they produce water, empy- reumatic oils, and ammonium carbonate, sulphide, and cyanide. Carbon remains in the retort. The substances of the ^st group, on being heated to 60°— 60° with a solution of potassium hydrate, lose their sulphur and are dissolved. If we add acetic acid to this liquid, dark grey flakes of a substance (protein of Mulder) are thrown down. The substances of the second group do not possess this property. On pro- tracted boiling with a caustic alkali they yield : Tyrosin Leucin Glyoocol C»H„N03 CeHiaNO^ C,H«NO, Some are soluble, others insoluble, in water ; they are, in general, insoluble in alcohol, ether, and chloroform. Hydrochloric acid diluted with 1,000 times its weight of water dissolves some, a few swell up simply ; upon others it has no effect. Hot concentrated hydrochloric AMMAL CHEMISTRY. aoid nttaoks all these substauoes, and the resulting pro- ducts are the same as those which are obtained (and more readily) with sulphuric acid. These products are chiefly glyoocol, leuoin, and tyrosin. Nitric acid colours them yellow (xanthoproteic acid). Ordinary phosphoric and acetic acids do not precipitate the substances of the second group, but redissolve thera even when coagulated. Solutions of albuminoid substances in potassium hydrate do not precipitate copper salts. Heated with oxidizing reagents, as a mixture of potassium bichro- mate and sulphuric acid, they furnish several members of the series of fatty acids, and the aldehyds corre- sponding to these acids, The albimunoid substances are decomposed during the process of respiration in the same manner as when under the action of oxidizing agents. Ammoniaoal solutions of copper dissolve albuminoid substances as they dissolve cellulose, which fact would seem to connect the albuminoid substances with cellu- lose, and to give certain weight to a theory of Hunt, which considers the albuminoid substances as cellulose which has combined with the elements of ammonia and parted with the elements of water. ALBUMEN. This substance is found both in vegetable organisms (cereals) and in animal organisms (serum of the blood, white of egg, lymph, chyle). i SaS i l ii i l Siita i -w i i ian ^ ^ if i ^^ mimm ALBUMBN. 229 resulting pro- obtained (and e products are Nitric acid d). Ordinary •reoipitate the dissolve them in potassium Heated with ssium bichro- ?eral members Idehyds oorre- substances are liration in the 1 of oxidizing ve albuminoid lich fact would ices with cellu- leory of Hunt, ses as cellulose i ammonia and ible organisms a of the blood, Wurtz obtains it by mixing white of eggs with twice its weight of water, straining and precipitating the albumen with a solution of lead acetate. The precipitate is washed with cold water and decomposed with a current of carbon dioxide, which precipitates the lead, while the albumen remains in solution. If this liquid be evaporated at a temperature below 59°, it is deposited in a soluble state ; if a quantity be heated to 63°, a portion of the albumen is coagulated ; but if the temperature is not raised above 74°, four-fifths remain dissolved ; consequently it would seem as though there were several kinds of albumen, but the nature and amount of foreign substances present are the principal causes of these differences. If the solution is very dilute, coagulation will not take place. Heating is not the only mode of producing this change ; alcohol, acids — vnt'a the exception of a few, such as hydrogen phos- phate, H3PO4, hydrogen tartrate and hydrogen acetate — the metallic salts, creosote, tannin, etc., also effect it. The alkalies prevent this action. Gautier obtains albu- men by dialysis. Soluble albumen is without odour, and is more soluble in saline than in pure water. Very dilute hydrogen chloride precipitates solutions of albumen, the precipi- tate being redissolved by an excess of the acid. This solution does not contain albumen, but a substance probably isomeric with it, which is, however, more easily obtained from muscular tissue : . it is called syntonin. Among the products of the putrefaction of albumen, mammf^' 230 ANIMAL CHEMISTRY. Nenoki (18-'78-71) has obtained butyric and vale- rianio aoids. Insoluble albumen heated with water in a sealed tube to 150° or 160°, dissolves, but this modification is not coagulated again by heat. Animal albumen containing 1.5 per cent, of soda may be regarded as a weak acid, and in presence of alkaline solutions it dissolves. A few drops of potassium hydrate are sufficient to form with albumen a gela- tinous compound, called potassium albuminate, which is soluble in water and no longer coagulable by heat. This liquid, diluted with water, is rendered turbid by acetic acid, but the precipitate is redissolved by an excess of jcid. Albumen of the Serum. — This is easily soluble in con- centrated hydrochloric acid, and is not precipitated by ether. Injected into the veins it is absorbed. Egg Albumen. — This is more difficultly soluble in concentrated hydrochloric acid, and is precipitated by ether. Injected into the veins it is absorbed in very minute quantities, and can be found again in the urine. Albuminoid substances (fibrino-plastic substance, fibrinogene) are found in the blood; they have the general characteristics of albumen, but are distinguished from it by being precipitated with carbon dioxide. The soluble matter of the crystalline lens of the eye also possesses this property. The coagulation of albumen by alcohol, tannin, and heat, and the consequent formation of a sort of net- '^^ssmmsm^^^s^mmm!^mmmmmmmmmmnffMemmi!&iis^ssms^;^^mf^- w 1 VIKRIN. 231 work which fills the whole liquid, and which precipi- tates all matters held in suspension, as well as certain substances in solution, explains the employment of white of egg for the clarifying of wine, syrups, also as a mordant, and the use of blood in sugar refining. FIBRIN. The blood of animals coagulates spontaneously shortly after leaving the body. This is due to the solidification of a substance called fibrin, which, on solidifying, forms a sort of net-work, imprisoning the globules of the blood, and gives rise to a gelatinous mass (clot). The researches made to explain this process of coagulation will be mentioned further on. Ether accelerates this coagulation. Sodium sulphate and glycerine retard or even arrest it. Pure fibrin may be obtained by beating fresh blood with twigs. It attaches itself to the twigs, and if then washed with water, and afterwards with alcohol, we obtain a dark-grey filamentous substance, which is insoluble fibrin. It may also be obtained by working clotted blood in water as long as it colours the water. Fibrin is insoluble in water, hot or cold, but if heated with it in close vessels it gradually loses its property of solidifying. It is soluble in alkaline solu- tions, and precipitable again by acids. Lehman has concluded from his analyses that fibrin is oxidized albumen. Smee affirms that if oxygen be passed into dofibrinated serum, heated to about liia 382 ANIMAL CHEMISTRY. 36°, the albumen is gradually transformed into flocks of fibrin. This subject needs further investi- gation. Fibrin of blood swells when treated with water con- taining 1- 1000th part of hydrochloric acid. It is dissolved in stronger hydrochloric acid, and is then converted into syntoniu. Freshly precipitated fibrin ia dissolved at 35° to 40° in water containing certain salts, and notably in that containing potassium nitrate or sodium sulphate ; it decomposes hydrogen peroxide. The albumen in the egg is transformed into fibrin during incubation ; inversely, if fibrin be kept under water, it gradually becomes soluble, and this liquid, like albumen, is coagulated by the action of heat. Vnrictien of Fibrin.— The gluten which constitutes the plastic substance of cereals, has the composition and general properties of fibrin. When well-washed, muscular tissue is macerated with water containing ten parts in 100 of sea salt, it is partially dissolved; if this solution is poured into water a gelatinous mass is obtained on agitation. This substance washed on a filter has received the name of myosin, or mmculin. It is soluble in acids, in dilute alkalies, and in a solution of sea salt ; this last solution coagulates. at about 60°. Myosin, on dissolving in dilute acids, is changed into syntoniu, which, like myosin, is soluble in acids . and alkalies, but from which it is distinguished by its insolubility in salt water. Syntonin is more easily ob- tained by macerating fiesh, which has been completely med into ir investi- water oon- id. It is id is then ted fibrin ag certain im nitrate peroxide, into fibrin Bpt under lis liquid, f heat, lonatitutes imposition macerated sea salt, s poured agitation, eived the a solution 3ut 60°. changed ) in acids . ad by its easily ob- )mpletely CASEIN. 233 deprived of blood by prolonged washing with water, containing 0.01 of hydrogen chloride. The macerated flesh is almost entirely dissolved. This solution is filtered and exactly neutralized with sodiimi carbo- nate ; the syntonin is precipitated in a grey, flocculent form. Blood fibrin contains about : C = 52.6 ; H = 7.0 ; N = 16.6; S = 1.2 to 1.6; = the difference, authors not agreeing very closely as to its exact com- position. CASEIN. Casein is the nitrogenous principle of milk. To extract it, milk is brought to boiling, and a few drops of acetic acid added. An abundant coagulum of casein mixed with butter (caseum) is formed. The pure casein is separated by watthing this coagulum several times with water, alcohol, and ether. Casein is difficultly soluble in water, but is dissolved by alkalies. It forms with the alkalies soluble com- pounds, and with the other bases insoluble salts. Casein has the composition of the albuminates of soda, differing, however, from these by various re- actions, and by the amount of its levogyrate action on the polarized ray of light. Solutions of csisein are not coagulated by heat, they simply become covered with a white film. They are precipitated by acetic aud other organic acids; milk curdles spontaneously, on account of the lactic acid formed in it. 984 ANIMAL CHEMISTRY. Many substances such as tannin, alcohol, plants with acid reaotions and several others, the flowers of the artichoke, of the thistle, of the butterwort {Pinguicula ndyaris), and, above all, rennet from the stomach of a sucking calf, cause coagulation in milk. LHGUMIN, OK VEGETABLE CASEIN. Braoonnot extracted, by means of water, from the seeds of leguminous plants (beans, peas) a substance called kgumin, aud which has a close analogy to casein. vrrELLiN. This substance is prepared by treating boiled yolk of egg with ether, which extracts the fatty matters. There remains a white substance insoluble in water. It can be obtained in a soluble state by mixing fresh yolk of egg with water. The clear liquid coagulates at about 70°, like albumen, of which it possesses the general properties. OSSEIN, GELATIN, CHONDEIN. The compounds of this second group formed of a single substance, whose differently aggregated, and also mixed quantities of mineral substances. They in water, alcohol, and acetic acid ; they and dissolve in hot alkaline solutions. The organic substance of bones {ossein), treated with are probably elements are with variable are insoluble swell in oold 'ms^mmsmmsmmsmmnm-m iloohol, plants 9, the flowore he buttorwort rennet from ooag^ation in BIN. ater, from the b) a substauoe logy to casein. ig boiled yolk fatty matters, uble in water. y mixing fresh uid coagulates \, possesses the I are probably elements are with variable ' are insoluble ' swell in cold ), treated with OSSEIN, OBLATIN, CHONDKIN. 236 ftm^-'- boiling water, fUmishes grlatin. The cartilages, under the same oiroumstanoeB, fumish a product which has most of the properties of gelatin, but which differs from it in being precipitated by acids and by alum ; it is called chondrin. To prepare gelatin, bones are treated with boiling water to remove the grease, then macerated with water acidulated with hydrochloric acid, which dissolves the mineral portious (calcium carbonate and phosphate). The organic portions remain undissolved, retaining the form of the bone, yet flexible and elastic. The solu- tion is poured off and employed in the manufacture of calcium hypophosphite, or of composts. The organic substance, well freed from acid by washing in milk of lime or a weak solution of sodium carbonate, is put into boilers with water, which is gradually raised to the boiling point. The organic matter gradually enters into solution. It is now decanted into a vat heated over a water bath, where various undissolved substances arc deposited, and whence it is drawn into wooden moulds, whore it solidifies. The gela- tin is removed from the moulds, cut into thin slices, dried on nets, and is now the glue of commerce. The tendons, skin, horns, and clippings of hides are also employed for the manufacture of glue ; they axe simply treated with boiling water. Darcet showed in 1817 that gelatin could be made directly from bones by digesting them with steam heated to 104°. The solution obtained has the appearance of soup, and it was hoped to thus pro- 2au ANIUAL 0HEMI8TRY. duoe a very flubstantial nutriment quite cheaply ; but it has been found that the nutritive power of this Bubstanoe is very small, and the use of "gelatine food " has been abandoned. Tlie purest gelatin is the ichthyoool, or isinglaiis. It is made chiefly in Moldavia and on the borders of the Caspian Sea, froin the swimming bladders of the sturgeon and of the acipenseres. Pure gelatin is solid, colourless, and transparent. Boiling water dissolves it in large quantities. The liquid solidifies to a jelly on cooling : one per cent, is sufficient to give water a gelatinous consistency. Continued boiling with water deprives it of the pro- perty of solidifying in the cold, or gelatinizing. Boiled with dilute sulphuric acid, it is transformed into glyooool. '^imi^m^mmi^^mf^s^^ss^iis^&^s^^siifmmm r ^ i^^smf '^ VIQESTIUN. 237 cheaply; but ower of this of "gelatine or isinglms. the borders ; bladders of transparent, ntities. The me per cent. oonsistenoy. k of the pro- gelatinizing. I transformed DIOESTION. An organized being cannot live without nourishment, that is, without obtaining from the bodies which surround it the materials necessary for the formation and the metamorphoses of its tissnes. The food of animals is rarely assimilable in the state in which it is found in nature ; therefore it must undergo a preparation which shall render it absorb- able. Hence the existence of a particular function, digestion. This function is performed by the digestive organs. They vary in complexity with different animals ; they diflFer in form according to the nature of tlie food. In man the digestive apparatus is very complex. If the food is solid it must be dissolved. Every liquid, however, is not immediately assimilable ; it often also must be transformed in chemical and physical charac- ter. We shall now follow the food through the process of digestion, and explain the manner in which each class of aliments becomes soluble and absorbed. SALIVA. In the mouth the food is subjected to mechanical action under the influence of a liquid secreted by glands urn SALIVA. situated in pairs on each side of the mouth (parotid, submaxillary, and sublingual). Tubes have been introduced into the ducts of the parotid and submaxillary glands, and by^ exciting secretion, the products of these glands have been separately examined. The salivas are not alike, and have different digestive properties, their combination, mingled with miicus, constituting " mixed saliva." The parotid secretion is a clear liquid, not viscous, and slightly alkaline, containing 1.0 to 1.6 per cent, of solid substances, among which are alkaline chlorides and phosphates; an organic substance soluble in alcohol and water ; another, ptyalin, which is the most important principle of the saliva ; and finally, prtassium sulphocyanide. Ptyalin contains potassium, sodium, and calcium. It resembles compouuds of albumen with these bases, is, however, gelatinous and not ooagulable by hf ^t or by most metallic salts. It is precipitated by mercury bicMoride, lead acetate, and tannin. The submaxillary glands are dependent upon the chorda tympani nerve, and thtj branches of the great sympathetic nerve. The secretion varies as it is excited by the one or the other of these nerves. The liquid secreted after an excitement of the great sympathetic nerve is thick, alkaline, and rich in solid substances. The liquid obtained by the excitement of the chorda tympani is less concentrated. It is alkaline, and contains epithelial cells, small quantities of albumen, globulin, and a substanoe (mucin) to wmoh n outh (parotid, ducts of the by^ exciting b have been lot alike, and combination, I saliva." i, not viscous, .6 per cent, of line chlorides se soluble in ch is the most lly, prtassium and calcium. 1 these bases, le by hf ^t or i by mercury nt upon the } of the great L8 it is excited ; of the great rich in solid 3xoitement of It is alkaline, quantities of oin) to wmoh SALIVA, 239 its mucilaginous appearance is due, and which is not found in the parotid secretion. The liquid of the sublingual glands has not as yet been obtained pure ; concerning it we know only that it is a viscous solution. Buccal mucus has a slight acid reaction. Mixed saliva is a turbid, ropy, inodorous, tasteless liquid. It deposits ddbris of epithelium. In man its density varies from 1.007 to 1.008. It has an alkaline reaction, and contains from 0.7 to 1.0 per cent, of solid substances, of which about one-third is inorganic, chiefly alkaline carbonates, phosphates, and chlorides. It contains in solution more carbon dioxide than even venous blood. 1,000 parts of saliva contain : — Water Solid substances . Ptyalin Mucus and epithelium Sulphocyanogen . Mitscherlioh. Jacubowitsoh. 984.60 992.16 10.60 6.26 0.06 4.84 1.34 1.62 0.06 According to Longet, potassium sulphocyanide is a normal product of the saliva. It is recognized by placing in the saliva a ferric salt, which is coloured red. This salt does not exist in the blood, perspiration, lacrymal fluid, or pancreatic juice. Its amount is always very small, and its presence in saliva is doubted by Gautier. ANIMAL CHEMISTRY. On boiling saliva it becomes opalescent, on account of the precipitation of albumen. Nitric acid colours it yellow by attacking the albuminoid substances. Alcohol precipitates from it ptyalin, mixed with nitrogenous compounds. > Saliva exposed to the air becomes covered with a film of calcium carbonate, and concretions of this substance are often found in the salivary ducts and on the teeth. An adult can secrete about 1,200 to 1,500 grains of saliva in twenty-four hours ; the actual quantity varies with the dryness of the food. The saliva possesses evident mechanical functions in digestion. It facilitates mastication by impregnating the food ; it lubricates the bolus, and renders degluti- tion possible ; and finally, by virtue of its viscous and frothy consistency, it imprisons air, which passes into the oesophagus with the food. Deglutition is favoured much more by the mucus than by the saliva proper ; this mucus is secreted by glands found in the walls of the mouth and pharynx. It has been contested that the saliva has for a chemical function the saocharifioation of starch, as the food does not remain but for an instant in contact with it, and as the amount of saliva secreted is independent of the amount of starch in the food. The proportion of saliva increases when the food is dry or hard, and diminishes when it is soft, even when it is formed of boiled starch; in short, it seems to vary inversely with the humidity of the food. mm^im^mmM^M'B SAMVA. 241 at, on account aoid oolouTB it inces. Alcohol I nitrogenous ivered with a tions of this ducts and on ,500 grains of uantity varies )I functions in impregnating iders degluti- ts viscous and )h passes into ly the mucus is secreted by id pharynx. ra, has for a starch, as the I contact with Ls independent ) proportion of or hard, and ; is formed of ?ary inversely It has been remarked that salivary glands exist in a rudimentary state in animals which do not masticate their food. Mialhe indicates the following experiment : Chew some unleavened bread, then place it on Berzelius test paper. Eub another portion of the same bread with water, and filter the liquid. The first is not coloured by iodine, and • becomes brown on being boiled with potassa. The second turns blue with iodine. According to the same chemist this action is due to ptyalin, an amorphous substance insoluble in alcohol, of which 1 to 2 per cent, is present in the saliva, and which is able to saccharify as much as 2,000 times its own weight of otaroh ; it also efiocts this change with extreme rapidity. This substance has then the property of vegetable diastase; It has also been shown directly by Messrs. Mialhe, Longet, and Schif, that even if pure gastric juice itself does not have the property of saccharifying starch, this eaccharification by the saliva is not arrested by the acidity of the gastric juice, and consequently the saliva which is carried into the stomach can continue to saccharify the starchy food in this organ. It is then very probable that the saliva performs this service in the process of digestion, though some claim that this ;ii- tion is only on food not yet thoroughly mixed with gas- tric juice. It appears to have no action on sugar, gun), cellulose, or albuminoid compounds. In inflammatory diseases of the mouth, as in the thrush, the saliva becomes acid, and weak alkaline ^ 242 ANIMAL CHEMISTRY. beverages are prescribed. In Bright's disease urea .s found in the saliva. Mercury is also present in cases of mercurial salivation. After the use of preparations containing iodine and bromine, these substances are found in this secretion. The tartar, of the teeth contains, in 100 parts, 25 of organic substances, 75 of inorganic substances, formed chiefly of calcium phosphate; the remainder is calcium carbonate, iron, and silica. GASTRIC JUICE. The gqstrio juice is secreted in the mucous mem- brane of the stomach by an immense number of glandular follicles, though not secreted when the stomach is empty. As soon as food enters the stomach, the mucous membrane swells, assumes a blood-red colour, and the gastric juice is at once secreted. The secretion can also be excited by irritating this membrane by ice, cold water, wine, gall, coffee, bismuth subnitrate, sodium bicarbonate, and alkaline substances in general. According to L. Corvisart, gastric juice secreted by mechanical irritation is most rich in digestive principles. We can easily procure gastric juice, or rather a mixed liquid, formed of this juice, stomachic mucus, and saliva, by making an aperture in the stomach of an animal, and it may be obtained free from saliva by previo-isly ligating the mami^sm)fm«^m retion Is very rmod. pom the liver led glycoyene, us produote, *ge. (l^uinea- jitity of bile i^ht of their lese or other > the biliary in them, r is odoiirless. strong odour, jrms a viscous r varies from le. It is 00- »rmed of t\«ro Eicids. cent, of solid ;he bile of the due js formed with different as essentially id constituents L'UMrosiTlON OF BILE. 261 of the bile are — a neutral organio substanoo called chok'Htirin, a colouring matter, neutral fatty subHtauces and salts ; urea is sometimes found in it. Streoker has extracted a base from bile which he calls cholin. This substance is identical with iwuriii, wliioh has been extracted from the brain and j'olk of egg. Its formula is CjHijNOj. COMPOSITION OF BILE. (Gobup-Bebanez.) » Man of « I Woman of] Man of 08 ^!if*!firf yeani, de- UUyiavB, de- ycBiM, killod/ ,' nAni.otAH nMTtitut^ul llV ft full. . . Wat^r Fatty Bubstanoes SaltM of the bilibry aoids Fat . Cholesterin MucuM, uolouring matters Mineral Baits . . The ash of ox gall contains : — Sodium chloride . 27.70 Sodium phosphate < 16.00 Potassium „ 7.60 Calcium „ 3.02 Magnesium „ 1.62 Ferric oxide 1.52 Silica . 0.36 Small quantities of nitrogen have also been found. rwtawwuiwiWiiw msm 252 ANIMAL CHEMISTRY. and considerable proportions of carbon dioxide ; this last gas may be extracted by a mercury pump. Animal food augments the quantity of carbon dioxide. Acius OF THE Bile. — Human bile contains much ' more taurocholio than glycooholio acid. The former alone exists in the bile of the dog ; it abounds in the bile of serpents and fishes. Glycooholio acid is wanting in carnivorous animals. Both exist abundantly in the bile of the ox. The bile of the pig contains special acids : hyoglyco- cholio acid, and taurohyocholalic acid. In order to obtain tho two acids of the bile, neutral lead acetate is added to ox-gall, which precipitates the glycooholi.c acid as a lead salt. This compound is col- lected, washed, b ".ed with 85 per cent, alcohol, and the boiling liquid filtered. It is then exposed to a current of hydrogen pulphide while yet warm ; the lead sul- phide is thrown on a filter and washed until the liquid becomes turbid. The glycocholio acid precipitates out of the solution, and is purified with boiling water. The alkaline taurocholate is not ])recipitated by the lead acetate. To the first liquor lead subacetate is added until the precipitate takes on a fatty consistency ; this precipitate is collected, washed, and suspended in water. A current of hydrogen sulphide is passed through the water, the liquid filtered and evaporated. The taurocholic acid is deposited as a white powder. Glyc()(;hohc Acid, C2oH43NOg, forms white needles moderately soluble in alcohol. One part is soluble in dioxide ; this iroury pump. J of carbon mtaius muoh ' f the dog; it Glyoooholio . Both exist U : hyoglyco- e bile, neutral recipitates the apound is col- oohol, and the d to a current the lead sul- atil the liquid recipitates out ig water, pitated by the subacetate is y consistency ; suspended in de is passed d evaporated. ite powder. white needles t is soluble in TAUROOHOLIC ACID. 258 100 parts of boiling and 300 parts of cold water. With alkalies and barium it forms soluble crystalline salts. Boiling alkaline solutions and dilute acids, separate it into chol acid and glycoool by combining with water. C^oH^sNOe + H^O = C2,H,oO, + C2H5NO2 Olycocholio add. Water. Cholalio add. Olycocol. On being boiled with concentrated hydrochloric acid or sulphuric acid, it furnishes the following products : Cholonic acid Choloidio . Dyelisin C24H38O4 Tatjrooholic Acid, C20H45NO7S, has not yet been obtained crystalline. It dissolves in alcohol and water, imparting to these an acid reaction. It is partly destroyed by the evaporation of its aqueous solution. It combines with one molecule of water on being boiled with alkaline solutions, choialio acid and taurin being formed. C^sH^NO^S + H2O = C2,H,o06 + C2H7NO3S Tamin. Y Tauioohollo add. Choialio add. The Bile Ferment. — W. Epstein and J. Muller A 254 ANIMAL CHEMISTRY. (60-1875-679) have lately investigated the influence of different substances upon the action of the ferment of the liver. Dilute aqueous solutions of carbolic acid (1 : 300) do not prevent the transforaiation of the glycogen into sugar if brought into contact with fresh, finely -chopped liver; yet this carbolic acid solution protects the liver from putrefaction for a long time. Five per cent, solutions of sodium chloride and sodium sulphate do not prevent or influence the transformation of the glycogen of the liver. Alkalies render the change slovrer, acids prevent it entirely ; even when very dilute they greatly retard it. The action of acids, however, is only tran- sitory ; on neutralizing them the action of the ferment at once begins. Whether carbon dioxide prevents fermentation or not, has not been ascertained with <3ertainty. The "upposition of Tiegel that the change of the glycogen of the liver into sugar is connected with the destruction of the blood -corpuscles was not confirmed by the experiments of Epstein and Miiller. They prepared from liver — moistening it with carbolic acid, drying at 30°, extracting with glycerine, and precif tating with alcohol — a ferment peculiar to liver, which converts glycogen into sugar very rapidly and . easily. Taurtn, C2H7NO3S.— This substance may be pre- pared by boiling ox- gall with an excess of hydrochloric acid for several hours. Filter and add to the liquid five or six times its weight of boiling alcohol, and allow to cool slowly. The taurin, which is almost *^ / L IMAGE EVALUATION TEST TARGET (MT-S) 1.0 I.I [f 1^ IIM ■a IS 112.2 £ lii £ US 12.0 1.8 Photographic Sciences Corporation 1.25 1.4 1.6 .4 6" - ► 'O- .^ ''^f^ ^\. %^ 23 WEST MAIN STREET WEBSTER, N.Y. 14580 (716^ S7i-'<503 ijSSl^jggjjj^iggllP MMm tKHS/tmaaam, wBfttw&mtammafm n iwiiiiiiiiKiwirat % CIHM/ICMH Microfiche Series. CIHM/ICMH Collection de microfiches. Canadian Institute for Historical Microreproductions / Institut Canadian de microreproductions historiques SERUM. 379 the air. Hence it is clear why alkalies and ammonium hydrate, as well as concentrated solutions of certain salts which absorb carbon dioxide, prevent the coagu- lation of blood. Venous serum contains somewhat more water than that of the arteries, the serum of women containing, according to C. Schmidt, more water than that of men. The proportion of water increases in most diseases ; the reverse is seldom observed except in certain fevers and in cholera. The abundance of albumen in the serum and in the blood in general proves that this substance is the prin- cipal constituent of the albuminoid fluids and nitro- genous tissues of the body. Its proportion ranges between 63 and 70 in 1000 parts ; it increases at the moment of digestion. Venous blood contains more albumen than arterial blood. Its quantity generally diminishes in disease ; yet it increases, as does the fibrin from other causes, in inflammatory fevers. The fatty bodies of the serum are often crystallizable, and it was a mixture of these subjtances which was formerly called seroline. There is a small quantity of olein and oleic acid in the serum. There is also found in it stearin, margarin, the two corresponding acids, and cholesterin. The venous blood contains more of this last body than the arterial blood ; the blood of the vena porta contains more than that of any other vessel.* The amount of fatty bodies increases during digc?- tion. They diminish in general during disease, with 280 ANIMAL CHEMISTRY. the exoeption of oholesterin, which often increases. The blood of women contains a little more than that of men. Glucose always exists in the serum ; its proportion is very small ; it increases during digestion if the food is very starchy. The blood of the hepatic veins contains a considerable proportion of this substance, while the blood of the vena porta hardly contains any whatever. The blood of diabetic persons scarcely furnishes 0.06 per cent ; normal blood contains at the most 0.0020 per cent. The blood which is most rich in salts is that of the vena porta ; arterial blood in general contains more than venous blood. A considerable diminution in the quantity of sodium chloride in food affects health seriously. Many other substances have been found in the serum. Some are constantly met with ; these are urea, uric acid, hippuiic acid, creatin, creatinia, casein, acetic acid, dextrin, and glucose, the peptones, sodium and potassium chlorides, sodium carbonate and phos- phate, sodium and potassium sulphates. Neither glycocol, leucin, taurin, nor tyrosin has been found. Prevost and Dumas detected the presence of urea in the blood after the suppression of the urinary secretion. The existence of this body in the blood has been proved by Beohamp and other experimenters. According to Picard, normal blood contain^ 0.017 of urea ; twice as much is found in the renal artery as in the renal vein. THE COAGULUM. 281 Qoreases. ban that portion is tie food is J contains while tlie -whatever, ishes 0.05 ,Bt 0.0020 hat of the tains more uantity of jusly. nd in the these are inifl, casein, nes, sodium and phos- Neither found. ,nce of urea the urinary the hlood perimentera ataini 0.017 renal artery in m Casein exists principally in tuo blood of pregnant women, nurses, and nurslings. In leuoooytheemia the blood contains gelatin, hypo- xanthin, lactic and formic acids : biliary acids in diseases of the liver, ammonium carbonate in persons having cholera. The COAGULUM — crassamentum or cht — is red and somewhat elastic. It is formed principally of fibrin and globules, and incloses about one-fifth of its volume of serum. It seems to form more rapidly in the blood of a child than in that of an adult, in that of women sooner than in that of men ; its com- pactness is in inverse proportion to the rapidity of its formation. In some pathological states the separation of the clot and serum does not take place, and a gelatinous mass remains. In others the blood is rich in fibrin, and a whitish matter called " buff," or huffy coat, is observed on the surface, which is fibrin nearly free from globules. On agitating coagulum in a bag placed in a stream of water the globules and other proximate principles, with the exception of the fibrin, are carried away by the water, and the latter remains in the cloth in the form of greyish filaments. GLf)BULEs. —Blood globules may be obtained by receivirfg fresh blood in a saturated solution of sodium sulphate, then filtering ; the globules remain on the filter mingled with the solution of the salts. The red globules of the blood of mammalia are 282 ANIMAL CHEMISTRY minute circular disks, slightly thickened at the margin. It is generally admitted that they are formed of a colourless membrane ; they would, therefore, be verit- able cells. Yet some observers regard them as an agglomerated gelatinous substance destitute of exterior membrane. This latter view is not probable, for on placing a drop of blood on the slide of a microscope and adding a little water th^^ globules are seen to swell, also the margins become yellow in contact with a solution of iodine. According to Beohamp and Estor, there exists in the blood on leaving the body an immense number of movable granulations of extreme minuteness, capable of development, of uniting and even of changing into bacteria and bacterides. These ;nioro80opio beings- called microcosms— are said to form the globules by their aggregation.(?) These savants aflfirm that they have seen them form new cells, and that the blood-globules in the body are the result of the activity of the microcosms. The blood-globules in fishes, reptiles, and birds have an elliptic form. Milne-Edwards has shown that no connection exists between the size of animals and the size of their blood-globules, but that they are smaller as the organ- ism is more perfect and respiration more active. Globules have a greater density than serum. Placed in contact with water they absorb the same, swell, and become spherical. At the same time a quantity of the colouring liquid of the globules is extravasated and nargin. d of a e Verit- as an sxterior , for on jroscope seen to lot with xists in number capable ing into >eing8 — )ule8 by )m form )ody are The lave an m exists of their orgau- Placed veil, and ,y of the ed and i GLOBULES. 283 colours the water. Change of form exerts a great influence upon their colour. On swelling, they take on a darker tint. On losing water they become clear and red ; this takes place when they come in contact with sugar and alkaline liquids. The globules cannot, therefore, be collected on a filter and washed with water without becoming altered. A solution of sodium sulphate of 18° Baume does not attack them, and if a mixture of one volnme of blood and two volumes of this solution be thrown upon a filter, they may be sepa- rated from the serum without being destroyed. This result is better obtained by adding to defibrinated blood ten times its volume of a concentrated solution of common salt ; the globules are precipitated, and may be washed with salt water. Besides red globules there exist in the blood white corpuscles ; their number is much smaller (about 1 in 400). There appear to be two kinds. The most abundant, the plasmic, lymphatic, and fibrinous globules, have a spherical form. Their border is very well defined ; they contain a viscid matter in which float little nuclei, which refract light strongly. They are larger than the red globulea (diameter=0.0113 millimetre), also lighter than these latter. They ^ay be distinguished from the coloured globules by their different reaotiona Water distends without destroying them, and dissolves them only after a long time. Acetic aoid simply causes them to contract. 1i Wri ■M 284 ANIMAL CHEMISTRY. These globules are not, like the preceding ones, specially characteristic of the blood, for they are found in most of the other fluids of the system. The name glohulines has been given to certain white corpuscles, not numerous, whose diameter is about -^ of a millimetre. They are small spherical nuclei, which are probably derived from the chyle. The number of globules in a cubic millimetre of blood has been estimated at four to* five millions. ANALYSIS OF DRIED GLOBULES. Humaa Blood of a blood. dog. Haemoglobin . 86.79 86.50 Albuminoid -matter . 12.24 12.55 Lecithin 0.72 0.59 Cholesterin . .25 0.36 (Hoppe-Seyler). The albuminoid matters appear to be constituted chiefly, if not wholly, of fibrino-plastic substance. Eed globules treated with water become spherical and distended, the colouring matter and other elements pass into the water, and there remains a gelatinous mass of a pale tint called stroma, which is formed chiefly of albuminoid substances. HiEMOGLOBiN. — This substance is prepared by mixing defibrinated blood with an e^ual volume of HJEMOOLOBIN. 285 ing ones, are found tain white about ^Tsir }al nuclei) limetre of ons. Blood of a dog. 86.50 12.55 0.59 0.36 be-Seyler). constituted stance. me Bpherical her elements a gelatinous 1 is formed prepared hy al volume of water, and adding to tliis liquid one-fourth its volume of 80 per cent, alcohol ; this mixture is allowed to stand twenty -four hours exposed to a temperature of 0°. Crystals then form in the liquid, which are pressed out on a filter and purified hy re-dissolving in water and re-precipitating by adding to the solution one-fourth its volume of alcohol and exposing to a temperature below 0°. It may be easily obtained in an impure state by adding ether, drop by drop, to defibrinated blood. The colour of the blood darkens on account of the destruc- tion of the globules, and the liquid deposits crystals on exposure to a low temperature. This substance is also known as hmmatocrystallin. The hsemoglobin of human blood forms regular rec- tangular prisms ; the same is true of that of the dog, cat, horse, and lion. That of guinea-pigs and mice crystal- lizes in tetrahedrons, and that of squirrels in hexagons. It is insoluble in absolute alcohol, ether, chloroform, carbon bisulphide, and essential oils. Acids decompose it without dissolving. Alkalies dissolve it by altering its nature. It has a slightly acid reaction. It may be preserved after having been dried at a low temperature. In aqueous solutions it is slowly destroyed at ordinary temperatures, and instantly at 100°. It absorbs oxygen at ordinary temperatures, one gramme of hsemoglobin dried at & absorbing more than 1 c.o. In a vacuum nearly the whole of this gas again escapes. Haemoglobin may therefore be considered as that oonstituent of the globules which fixes oxygen. B ^ 286 ANIMAL CHEMISTRY. Htemoglobin contains, besides carbon, hydrogen, oxygen, and nitrogen, small quantities of sul^'^hur and phosphorus, and about 0.5 per cent, of iron. H^.MATiN — H^.MiN. — An aqueous solution of hsorao- globin heated to about 75" or 80" is decomposed into another colouring matter, heematin, and an albuminoid matter which coagulates. This decomposition takes place gradually at ordinary temperatures, in presence of acids or alkalies in solution. Heematin represents only about four per ctnt. by weight of hoemoglobin. If a small quantity of sodium chloride and strong acetic acid is added to hoemoglobin or blood, and after having heated this mixture over a water-bath, it i.s allowed to slowly cool, hydroohlorate of hoeraatiu (hsemin) is precipitated in rhomboidal crystals of a brown «olour J this is also a characteristic test in medico-legal investigations. Virchow, also Robin, have designated as hcematoidin a crystalline matter, containing neither iron, sulphur, nor phosphorus, and which results from the destruction of heematin in sanguinary effusions. This body is, however, now generally recognized as bilirubin. Haemoglobin forms with carbonic oxide a crystalline compound, which may be prepared in the same manner as hoemoglobin, by employing blood previously agitated with carbon oxide. These crystals have the Game form as the hoemoglobulin. F. Hoppe-Seyler (60-1874-1065) has lately care- fully investigated the colouring matter prepared from hoematin, by reducing substances, and proved its IRON IN THE BJ.OOD. 287 ydrogen, pUur and of hoorao- osed into buminoid ion takes presence represents ;lobin. nd strong and after bath, it is hceraatin of a brown adico-legal designated ig neither isults from effusions, agnized as crystalline ne manner previously B have the ately oare- )ared from proved its identity with the urobilin of Sa.\% (;]6-1869-815), and the hydroliliruhin of Maly (36-1872-836). " It should be oliserved that Thudiohum and Kingzett have quite recently (32-76-255) made an analysis of heemin, and finding the same to contain 7.65 per cent, iron, 3.02 chlorine, and 0.60 phosphorus, have come to the conclusion that hoemin is in reality a substance consisting of ha3matin, ohlorhydrate of hoematin, and a crystalline compound containing phosphorus, which they regard as identical with myelin, a body claimed by Virohow as existing in the brain. C. Husson (9-81-477) states that crystalline com- pounds may be formed between hsematin and phenol, oxalic acid, valerianic acid, tartaric acid, citric acid, and silica. Haemoglobin forms crystalline compounds with nitrogen dioxide and oyanhydrio acid. Red globules are not attacked by albumen, gum, or sugar solutions, carbon dioxide, or neutral salts of the alkaline metals. Alum, chlorine, sulphuric acid, and nitric acid cause them to contract ; water, organic, and phosphoric acids, and alkaline solutions dissolve them. Milne-Edwards (9-79-1 268) remarks that the respira- tory power of the blood depends upon the number of red blood- corpuscles present. Iron in the Blood. — Boussingault determined this metal among the elements of ( jw's blood. In 100 parts he obtained : 1 WM&M^^^^&S^:AiB& Mi ^ 288 Dry fibrin Dry albumen Dry globules ANIMAI, CHKMISTKY. Total Mineral Substanoes. . 2.151 grammes . 8.715 „ . 1.325 ,. Iron. 0.0466 grammes 0.0863 „ 0.3500 „ The colouring matfer of the blood owes its colour mainly to the largo proportion of iron in the globules, which, dried, giv^es: 10.760 per cent, ash, containing 9.043 „ ferric oxide, 1.707 „ other mineral substances, formed almost entirely of lime and phosphoric acid. P. Picard (9-79-1266) found the proportion of iron in the blood of dogs to be quite variable and pro- portional to the amount of oxygen the blood was capable of absorbing. In his investigations regarding the amount of iron in the human body, the spleen gave higher proportions than any other organ. Jolly has very lately (61 -'78) made analyses that appear to show that the iron in blood exists as ferrous phosphate. - GASES OF THB BLOOD. Magnus was the first to make, in 1837, an extended study of the gases contained in the blood. A fiask con- taining blood was agitated violently, in order to coagu- late the fibrin. The defibrinated blood was transferred d. on of d pro- d was 1 T*^ 1 n (y igave s that errous tended sk con- ) ooagu- sferred GASES OF THE BLOOl). 289 into a bell glass, filled with mercury. He obtained the following composition of the gases liberated :— Carbon dioxide Oxygen . Nitrogen Veuous Bloud. . 71.6 . 15.3 . 13.1 100.0 Arterial Blood. (J2.3 23.2 14.5 100.0 His methods of collecting the mixed gases were not, however, complete, and later analyses may be regarded as more reliable. C. Bernard determined the amount of oxygen in the blood, profiting from a fact discovered by him that carbon oxide displaces the oxygen. The blood is taken directly from the body by a syringe, and immediately introduced into a graduated tube half-filled with carbon oxide. This is agitated, and kept at a tem- perahire of 40°, after which the amount f oxygen in tile gas is determined. Venous and arterial blood dissolve variable quanti- ties of oxygen. 100 voluL.as of blood from a young dog contained : ^ r In the left ventricle, 23.0 vol. of oxygen. Animal fasting. In the left ventricle, 17.6 vol. of oxygen. Animal digesting. In the right ventricle, 10.0 vol. of oxygen. Animal , fasting. . . .,:.:^ 290 ANIMAL CHEMISTRY. In the right ventricle, 10.2 vol. of oxygen. Animal digesting. The gases from the blood of a dog gave, in 100 parts : Nitrogen. Arterial blood Venous blood fl.6I 12.30 rl.32 11.64 )xygen. Carbon Carbon di- dioxide. oxide combined 20.06 34.8 traces. 22.2 36.3 0.88 12.1 43.6 4.40 11.6 42.8 6.30 When venous blood is agitated with oxygen it takes on the red colour of arterial blood. ? If, on the contrary, arterial blood be agitated with carbon dioxide, hydrogen, or nitrogen, it assumes the dark brown tint of venous blood. P. Bert (9-80-733) found, in his investigations upon the power of blood to absorb oxygen at different pres- sures, that a compound of hsemoglobin with oxygen (oxyhsDmoglobin,) is obtained when blood is agitated with air at ordinary pressure. Increase of pressurj in- creases the proportion of oxygen in this compound ; it also remains constant until the pressure is lowered to one-eighth of an atmosphere at 16°, but at the tem- perature of the bodies of mammalia it decomposes as the pressure is further removed. The blood on leaving the lungs does not contain as much oxygen aa it is capable of absorbing. Grehant has found that in agitating blood with oxygen the quantity which it is capable of absorbing is to the MhMMtMMMMMMMiMlwiMw ■MMMMiMiNMtoe ' ACTION OF OZONE ON THE BLOOD. 291 Laimal in 100 n di- imbined. • ses. i it takes jontrary, ydrogen, f venous ons upon ent pres- 1 oxygen agitated assuTJ in- )ound ; it wered to the tem- mposes as contain as Grehant .ygen the is to the quantity ordinarily found in it as ahout 26 to 16. But there is a great difference in this regard between indi- viduals, their state of health, eto. The opinion has been expressed that the blood oon- . tains ozone, but this cannot be admitted, as the blood, like all organic matter, destroys ozone. It is only necessary to agitate blood in a vessel with ozone to obtain proof that these two bodies are incompatible, for the odour of ozone disappears immediately. J. Dogiel (75-24-431) states, as the result of his recent researches regarding the action of ozone upon the blood, that the action of the ozone is chiefly upon the red blood-corpuscles; their colouring matter is expelled, and they become darker within fifteen minutes. After this change alcohol, ether, or chloroform pro- duces no separation of crystals of hsemoglobin. Upon passing ozone through defibrinated blood for a long time, flakes separate out, which, after washing with water, are not to be distingiiished from fibrin. By continued action of ozone blood becomes first of a dirty, yellowish-green colour, and, finally, colourless. Haema- tin is likewise rendered colourless by ozone. Blood poisoned with carbon oxide attains in a short time the properties of normal blood on exposure to the action of ozone, carbon dioxide being given off. Blood contain- ing carbon oxide is discoloured less quickly than normal blood, and does not so quickly lose its property of depositing crystals of hromoglobin. The change of the blood corpuscles produced by ozone should not be confounded with the change produced by carbon dioxide. 292 ANIMAT, CHEMISTRY. Carbon oxide displaces the oxygen of the blood, and is very deleterious when inhaled. Chlorine coagulates blood, removes the iron which enters into the composition of its colouring matter, and subsequently destroys the organic matter. The iron is changed into ferric chloride, capable of being detected with reagents. Arsenide of hydrogen completely changes the nature of blood, which assumes the colour of ochre. Deflbrinated blood becomes brown and then dark green under the action of hydrogen sulphide; the colouring matter is attacked and the globules de- stroyed. Certain neutral salts, the alkaline sulphates, phos- phates, and nitrates, redden the blood in the same manner as oxygen. Or^ (9-81-833, 990) asserts that acetic acid, sul- phuric acid, nitric acid, hydrochloric acid, phosphoric acid, or alcohol after being diluted with water, may be injected into the blood-vessels of a living animal with- out producing coagulation of the blood. DIFPERENCES BETWEEN ARTERIAL AND VENOUS BLOOD. We have incidentally noticed these differences in studying the various constituents of the blood. Longet sums them up as follows : L INDUSTRIAL USES OF BLOOD. 298 blood, wliioli •r, and iron is jteoted , nature in dark Le; the lies de- 3, pllCB* le same Bid, 8ul- ospliorio may be lal with- N0U8 fences va. 3rd. 4th. •5th. 6th. 7th. 8th. Venous Blood. Ist- Brown red. 2nd. Rich in albumen. ? 3rd. Haa less water. 4th. „ „ extractive matters. 5th. Contains about 22 parts of oxygen to 100 of carbon dioxide. 6th. Less coagulable. 7th. Globules more abun- dant in fatty matter. ? 8th. Has a different com- position in different parts of the venal system. We have indicated by ? such items in Longet's tabula- tion as are doubtful, or at least are not constant. Industrial Uses of Blood.— Coagulated blood serves as food in certain countries, as Germany, Sweden, and Italy. Freshly drawn blood is highly nutritious, and not unfrequently used by emaciated and greatly enfeebled invalids. The large quantity of albumen contained in the blood and the property which albumen possesses of coagulating on heating, causes blood to be employed in sugar refineries for the clarification of fiugars. Arterial Blood. 1st. Vermilion red. 2nd. Bich in fibrin. „ ., , jbules. ? ff ff SAxtS* Contains about 30 parts of oxygen to 100 of carbon dioxide. More coagulable. Less abundant in fatty matters. ? Has the same com- position in all parts of the arterial system. 294 ANIMAL CHEMISTRY. CHEMICAL PATHOLOGY OF THE BLOOD. Since the blood circulates throughout the entire body, it is evident that diseases which manifest them- selves at any point necessarily produce modificatioud in the blood, h' ace it may be asserted that an examina- tion of the blood famishes a valuable basis of dia- gnosis. Yet, from the fact that only blood taken from a superficial vein can be experimented with, and that the blood becomes contaminated in its passage through the body, the small quantity, therefore, of abnormal or noxious matter is often found to be too slight for the determination t' ite amount, or in some cases even for its detection. The chemical '^ts which we possess in regard to the variations of the biood in different diseases are few. It is only known that in such and such states there is a diminution or increase of this or that principle. We are not sufficiently informed as to the genesis of these substances to be able to decide, whether the morbid condition appertains to one organ rather than to an- other, or whether the disease is due to a given cause or to some other. The proximate principles of the blood may also seem to increase, without this increase being either real or as great as would appear ; this may be due to a diminution in the total mass of blood. "T" ANJEMIA. mn ■ ^ Plethora. — Plethora may be due either to an increase in the proportion of globules, or an augmenta- tion in the volume of the blood ; therefore we distin- guish between globular and sanguinary plethora. In the former the globules increase. ■ In sanguinary plethora— that is, in the augmentation of the mass of the blood— the reverse occurs, as the quantity of blood may increase in greater proportion than the globules. Anemia. — Here also there may be either diminution of the mass of the globules or a diminution in the total amount of the blood. In the first case, an increase of water and fibrin is noticed in the blood, and often the number of colourless globules increases. The clot is firm and often produces " buff"." The ansemic state occurs when the body does not repair the losses which it has undergone; it is pro- duced during growth, at the time of puberty, or after diseases which impede digestion. Iron and its prepa- rations have a very favourable influence on the develop- ment of globules. We have just stated that certain aneemio conditions correspond to an increase of colourless globules. The spleen then increases in size ; the blood which remains in the spleen is very rich in white globules, contain- ing 1 to 49 of the coloured globules. The blood of the splenic vein also contains large numbers of these globules. The eoagulum of the blood of this vein is :?r! Ifi; I 296 ANIMAI, CHEMISTRY. but slightly compact ; the serum which separates there- from coagulates after a short time. The following hypothesis based upon these factfi has been proposed: The spleen is an organ which destroys red globules, changing them into white globules which are carried along into the circulation and afterwards again transformed into red globules. These views are, however, not regarded as established. Leucocyth^mia — This name is given to a morbid state characterized by the abundance of white globules : the number of these may amount to one-fourth and more of the total number of globules. The blood is then milky, and often acid from the formation of acetic or lactic acid. Ciroi,EUA— Tyi'iioiu Fever— The globules assume irregular forms, and unite together during cholera and typhus. In this latter disease, and in tuberculosis in its advanced stages, the blood loses its property of becoming red in contact with oxygen, since this gas no longer unites with the globules. The blood of typhus patients contains ammonium carbonate, pro- duced by the transformation of urea, and it is probably this compound which leads to the alteration of the globules, as the same phenomenon is observed when ammonia is introduced into the blood. Ammonia and many toxic agents attack the enve- lopes of the globules ; hence, whenever these substances are present in the blood, the globules become ruptured, and death ensues in the absence of prompt antidotes. The blood is thick, and resembles gooseberry jelly in DISEASES IN WHICH THE FIBRIN Dl\i^NISHES. 297 tUere- Q factfi which white iulation lobules, dished, morbid lobules : rth and blood is of acetio \ assume ilera and ulosis in )perty of this gas blood of ate, pro- irobably n of the red when he enve- iubstauces ruptured, tidotes. Ty jelly in cholera ; globules, as well as albumen and extractive substances abound. The seruni is deficient, is dense, and generally poor in salts, yet the potassa compounds and phosphates increase. As the urinary secretion is diminished or suppressed, the urea increases in the blood, and there is produced ammonium carbonate. Scurvy. — The change in the blood is quile marked in this morbid state. It is disorganized on account of the dissolution of the globules, and the diminution of albumen and salts. Albuminuria. — The blood does not seem to change in the amount of fibrin. The proportion of globules and albumen is greatly diminished. Dropsy. — The globules and albumen diminish, and the serum is extravasated. Infi-ammatory Disevses. — The filrin increases in these affections, in pleurisy, pneumonia, and acute articular rheumatism. The proportioTi of this body, which, in normal blood, is 2 to 2.3, rises to 7.8 and even 9 parts in 1000. The fatty matters augment, and the albumen and globules diminish slightly. The blood is charged with carbon dioxide, which fact explains the retarding of the coagulation, as a large proportion of this gas prevents coagulation. Diseases in which the Fibrin Diminishes. — "When food is insufficient, also in cases of syphilis, in prolonged suppuration, in typhoid fever, and in scurvy, the fibrin generally diminishes, or loses its property of coagulating. The coagulation of the blood is very slow in diseases of the respiratory organs, when the hematosis is incom- Mi ^ 29S ANIMAL CHEMISTRY. plete, and after death hy syncope. It does not occur in the blood of persons asphyxiated, killed by lightning, or poisoned with oyanhydric acid, narcotics, hydrogen sulphide, or ammonia. Usually in a fatal* result there is a complete destruction of the globules. In this casn, oxygen ceased to unite with the blood, and the serum becomes coloured. The blood of persons who have died from the bite of a serpent coagulates very rapidly. It should be remarked that a decrease in the amount of fibrin in the blood does not always occur in the oases as cited above, and, indeed, it is claimed by Gorup-Besanez (21-364) that in no disease whatever 's there uniformly a diminution in the fibrin. Variation in the Albumen. — The blood becomes poor in albumen under a great many circumstances : after loss of blood, prolonged suppuration, in albuminuria and dropsy, in malarial fevers, in typhoid fever, and scurvy. The albumen seems to diminish in proportion as the fibrin increases. Variations in Alkalinity. — Normal blood is alkaline This alkalinity increases in typhoid and putrid fevers, which is probably due to the formation in the blood of ammonium carbonate from urea. The blood has been known to become acid after an abnormal production of lactic acid. The globules are then dissolved by this body, and death rapidly ensues. The alkalinity seems to diminish in inflammatory diseases. Variations in the Fatty Bodies. — The drinking of large quantities of fluids augments the proportion of the fatty bodies, and it seems certain that corpulent VARIATIONS IK SUGAR. 99» becomes 88 : after uria and . scurvy, irtion as jlood i& oid and aation in after an jules are ensues, mmatory drinking lortion of corpulent persons would grow thin on diminishing the quantity of liquid which they imbibe. The fatty matters generally augment during affec- tions of the liver, in phlegmasia, Bright's disease, and in tlie first stage of some acute diseases. Z. Pupier (9-80-1146) has lately found by extended researches that the use of sodium bicarbonate or alkaline mineral waters tends to increase the number of red blood-corpuscles both in man and animals. Other Variations. — The extractive matters become abuudaut in puerperal fever and scurvy. Claude Bernard recently (9-83-407) set forth the following, based upon his investigations regarding the quantity of sugar in the blood. The sugar of the blood is soon decomposed on the removal of the latter from the body. After death the sugar also rapidly decomposes, even when retained i" the blood-vessels. The presence of sugar is independent of the nature of the food ; in the arteries it is uniform in quantity, while in the veins, except in the hepatic, though variable, it is yet less than in the arterial system. The amount of sugar increases in diabetes. To extract the sugar of the blood, the latter is first defibrinated. To the serum is added its triple volume of alcohol ; the coagulum is separated and washed with water containing an equal volume of alcohol. It is now evaporated to dryness, and the residue treated with alcohol, which dissolves the sugar. V. Feltz (9-80-653, 1338) recently ascertained by his investigations upon the action of putrefying blood upon animals, that injection of the same into a vein of WJPWIWiWlffMTlTW^^ WM 80O ANIMAI- CHEMISTRY. an animal produced eepticsemia. The poisonous pro- perties of putrefied blood are not obauged by passing air through the same, but are lessened by the action of pure oxygen. II' the gases of the blood are removed with a pump and the blood allowed to remain in a vacuum for some time, it loses its poisonous properties. Feltz is of the opinion that the poisonous body is a gas. In all stages of putrefaction, even after being dried in the air, blood retains the property of produc- ing septicaemia. Uric aciWis sometimes observed to increase in the blood. The blood of icterical persons contains the colouring matter and other constituents of the bile. Urea accumulates in the blood when the kidneys perform their functions badly ; this condition is known by the name of urcemia. The urea winch accumulates in the blood is partially decomposed, producing ammonium carbonate. Von Gorup Besanoz (75-23-135) found in the blood of a man sullering with atroj'hy of the liver, besides the normal constituents, a body closely related to gluten, but very different in its -optical pr()i)erties, hypoxnnthin in not inappreciable quantity, formic acid, and volatile fatty acids, rich in carbon, also a non- volatile strong organic acid, soluble in water, alcohol, and ether, which, however, is not lactic acid. Urio acid, xanthin, leucin, and tyrosin could not be found. The proportion of salts diminishes in intermittent fevers, scurvy, Bright's disease, dysentery, and tyi)hoid states. It augments in intermittent fevers and cholera. ■Pi 10U8 pro- yr passing uotion of removed lain in a (roperties. . body is a 'ter being )f produo- theWood. I colouring le kidneys a is known ccumulates producing a the blood ver, besides related to properties, formic acid, also a non- ,ter, alcohol, acid. Uric , be found, intermittent and typhoid and cholera. T!f ABSPIKATIOM. 801 RESPIRATION. The atmosphere penetrates certain special organs, which are the liiug^ in man, hmnrhia in fishes, and trachea in insects. There is thus established a continual exchamje between the blood and the air, which is called res/iirafion. Tlie oxygen of the air coming in contact with the membranous walls of the respiratory organ, which are very thin and very permeable, traverses them and penetrates the blood. It is not dissolved in the serum of this liquid, but it fastens itself upon the globules, and forms with their substance a very unstable combi- nation. Inversely, the carbon dioxide and aqueous vapour on reaching the lungs in the venous blood escape through the same membranes, and are exhaled into tliP atmosphere to be again shortly decomposed by the green portions of plants. ■Map ^ 303 ANIMAL CHKMISTRT. THEORY OF RESPIRATION. DiFFKRKNT methods have been employed for studying the phenomena of respiration. Lavoisier was the first to solve the problem; his method, which has since- been perfected by Regnuult and lieiset, oouHists in plficing the subject to be experimented upon in a known volume of oxygon, absorbing the carbon dioxide ex- haled and renewing the oxygen, in a contiuuouB manner. A second method consists in placing the subject in a confined space and analyzing this air» determining the volume of gas exhaled at each expiration, counting the number of respirations ma.ie during ft c rtain time, and analyzing the air exhaled during this time. By this method absolute results cannot be obtained, oa nitrogen is also ex..aled during respiration, and thus we have two unknown data : the weight of the nitrogen exlialed, and that of the oxygen consumed to form water. Boufsingault made use of an indirect method, which consisted in feeding the animal in such a manner that its weight remained constant, also weighing and analyz- ing the food, as well as the excrements, and subtract- ing the weight of the latter from the former. It is clear that the difference between these two weights represents what had been lost by pulmonary ■and cutaneous respiration. THEORY OP RKSIMRATION. yoa studying ( tho first las bIuco - luaitits iu , a known oxide ex- outiuuous ibjeot in a lining the inting the time, and ) obtained, , and thus e nitrogen i to form tiod, whioh lanner that ,nd analyz- d Bubtraot- these two pulmonary Boussingault experimented ou horses, cows, and dovoB. Tho quantity of oxygen consumed is proportional to the en -jy with which the vital functions are executed. DuTT..«. experimenting ou himself, found that the absorption of oxygon was at the maximum 2.'} litres or ii'i grammes per hour, or about 800 grammes for 24 hours ; l.'i litres of carbon dioxide are produced ; the air expired contains 4 per cent, of this gas. Substantially, tho amount of oxygen consumed varies between 20 and 20 litres per hour, or 29 to 36 grammes for an adult man in a state of repose. Wo are indebted to Soharling, Andral, and Gavarret, also to Pettenkotfer, Regnault, and Eeiset for important researches on respiration. The apparatus of Soharling consists of a chamber of one cubic metre capacity, made absolutely tight by a covering of sized paper. The subject is placed in this for half an hour to one hour. The air enters the chamber through an orifice in the lower portion, and is drawn in by d water aspirator. The products of respi- ration pass into a series of flasks, the first of which contains sulphuric acid, which retains the moisture, the remainder containing alkaline substances to absorb the carbon dioxide formed. Two important objections to this method may be stated. The air is not sufficiently renewed, and the chamber is too small. It results, therefore, that 'the air of the box becomes charged with carbon dioxide and aqueous vapour, and becomes elevated iu temperature PnUMunH'MMI MO'li .''< "^ 804 ANIMAL CHEMISTRY. in an unnatural manner. These ciroumstances exert a deleterious influence upon respiration, and must ueces- sai'ily bring about abnormal conditions. Scharling found that in the respiration of a man 34 grammes or 17 to 18 litres of carbon dioxide are pro- per hour. Andral and Gavarret took special care not to effect any modification of the normal conditions of respiration. A mask of thin copper, the edges of which were fu^-nished with a cushion of caoutchouc in order to pitiveut any escape of gas, is fixed firmly to the face of the subject, which it covers without binding. This mask is large enough to receive the product of an entire respiration, and opposite the eyes it is pierced with two orifices closed with glass. ^ The air penetrates the mask by two tubes, which enter the mask at the height of the corners of the lips. The air expired does not pass out through these tiibes, as they contain two little balls of elder-pith, which serve as valves. The air escapes through an opening situated opposite the mouth, and enters into three flasks, from which the air htis been exhausted, "ti<^ whose capacity is 140 litres. The chief difficulty consisted in regulating the open- ing of the cock which separates the flasks from the opening in the mask, in such a manner that respiration could take place easily, both for inspiration and expira- tion. The operation lasted from eight to thirteen minutes, and the gas collected was about 130 litres. THEORY OF RESPIRATION. 306 exert a i neces- man 34 lie pro- to effect piration. .oh were order to le face of roduct of is pierced es, which f the lips, ese tuhes, hich serve situated asks, from capacity the open- Irom the respiration ,nd expira- n minutes, The cock was closed, the air was permitted to ooiol iu the flasks, and the pressure and temperature determined. Then these flasks were placed in connection with three others exhausted, but separated from the first by tubes aiTB 'inmal heat. The temperature of the body of an infant or an old man is less than that of an adult, and we have observed that the respiratory phenomena diminish in energy at the two extreme points of life. If an important reduction in temperature is pro- duced after eating, it must be attributed to the fact that the blood rushes to the muscles of the digestive apparatus, which act with increased energy at this time. o mmmmmmmtSMmmammam wm 318 ANIMAL CHEMISTRY. Like the fuel of an ordinary engine, a part heats the animal machine, the other is converted into mus- cular activity, which produces either external work (walking, movements of the arras, head, etc.), or in- ternal work (digestion, assimilation, etc.). Thus the observed heat is equal to the difference between the heat produced and the heat which is transformed into work. Now, since we know the meclianical equivalent of heat, that is, the quantity of work which a certain amount of heat will accomplish, the heat produced can be measured. If the n^osole contracts without producing mechanical effect, the heat developed will be greater, since there is only heat developed, and that not utilized in the form of work. But even if the muscular power does produce an external mechanical effect, there is still in addition a production of heat in the interior of the body. Ex- periment has shown that when a muscle contl-acts the quantity of oxygen consumed is greater than when it is in repose: thus 100 volumes of blood, leaving a muscle which is in action, instead of furnishing 6 volumes of oxygen, furnish only 5 volumes. All chemico-phy Biologists are in accord in adnitting that heat and motion are due to the oxidation of the food. The amount of carbon dioxide exhaled does not indicate the amount of oxidation which has taken place in the body. Every movemenc, every chemical action, every passage of the food from a solid to a liquid state in the blood, all friction of the liquids in the body, are actions which go to produce an ■Inm ANIMAL HEAT — MUilCUI.AR POWER. 319 part heats into mus- srnal work tc), or in- Thus the )etween the formed into 1 equivalent h a certain- roduoed can ; mechanical nee there is . in the form ioes produce in addition body. Ex- ionttaots the han when it I, leaving a urnishing 6 les. in adrutting ation of the ed does not has taken Bry chemical solid to a the liquids prodiice an elevation or decrease of temperature. Consequently there are incessant gains and losses of heat, and we perceive, on the whole, only the resultant of these different actions of which the complexity is extreme. The carhon dioxide is not the only product of oxida- tion ; water and other matters (urea, uric acid, etc ) are formed, which escape in the different excretions. And the whole of the oxygen which oxidizes is not derived from the air ; a considerable part is obtained from the oxygen of the food itself. There is a difference of opinion as to the manner in which the action is produced. According to some, it results from the oxidation of the aliments as they are found in the blood. Others do not admit that the process takes place in the blood, but that it is a direct oxidation of the muscles by ^he oxygen which produces heat and motion. The second view is that most generally admitted ; nevertheless, the recent researches of Meyer and Frank- land on this subject appear to prove the contrary. An average man has about 7.5 kilos of muscles, oonsidered in a dry state. According to Meyer, they would be completely oxidized in eighty days if they served to produce median icnl work. It is rational to regard the muscles as instruments for the transformation of potential energy into motion. We can only give a few conclusions deduced from the work of Frankland. 1st. The muscle is a machine destined to convert potential energy into uiechanical force. mm a mam 320 ANIMAL CHEMISTRY. 2nd. The mechanical force of the muscles is derived principally, if not wholly, from the oxidation of the substances contained in the blood, and not from the oxidation of the muscles themselves. 3rd. In man the principal substances employed in the production of muscular power are non-nitrogenous ; but nitrogenous substances may also be employed for the same object, hence the great increase in the evolu- tion of nitrogen under a diet of animal food, even with no increase in the amount of muscular work performed. 4th. Like all other parts of the body, the muscles are constantly being renewed ; but this renewal is not apparently more rapid during great muscular activity than during comparative repose. 6th. After a sufficient quantity of albuminous sub- stances has been digested for the renewal of the tissues, the best food for the production of work, both internal and external, are the non-nitrogenous substances, such as oil, fat, sugar, starch, g^m, etc. 6th. The non-nitrogenous portions of the food which enter into the blood transform all their potential energy into effective force ; the nitrogenous substances, on the contrary, leave the body, taking with them a part (one- seventh) of their potential force. 7th. The transformation of dynamical force into muscular power is necessarily accompanied by a pro- duction of heat within the body, even when the muscular force is exerted exteriorly. This is, without doubt, the principal though not the only source of animal heat. »?»" lerived of the im the yed in renouB ; yed for evolu- en with fonned. jcles are . is not activity 3UB Bub- 9 tissues, internal ces, such jd which 1 energy , on the lart (one- )rce into y a pro- len the without source of TRANSFORMATION OF ALBUMINOID SUBSTANCES. 321 Fick and Wislicenus, in an asceuaion of the FauUiorn in 18C5, determined the amount of work i)eribrnied by their muscles, and the quantity of muscular matter oxidized to produce this work. This latter calculation was made by determining the amount of nitrogenous matters in the urine emitted, and collecting them in the form of urea, and based upon the fact established by Frankland, that 1 gr. of dried muscle transformed into urea produces 4,368 heat units. They arrived at the result that the work accomplished was about twice as great as that which would be produced by the com- bustion of the substance of the muscles transformed into urea. TRANSFORMATION OF FOOn JN THE BOPy. We recognize three principal classes of food, albumi- noid, farinaceous, and fatty. Tramformntion of Albuminoid Substances. — It was formerly believed that albuminoid matters were not modified in the body, but simply fixed in the tissues, and taking no part in the respiratory phenomena. The name of plaslic food given to these bodies illustrates perfectly this manner of regarding them. On tlie other hand, the fatty and fariuaceou bodies were thought to take part in the production of the respiratory pheno- mena alone. Hence the name respiratory aliments, which has been given them. This view, however, is too limited ; carbon dioxide and water are the principal but not the only products exhaled. Others are formed, as urea, uric acid, and these substances are nitrogenous. There msmmmmm rtmmmm temm 322 ANIMAL CHEMISTRY. escapes also in the gas exhaled by the luugs a certain quantity of free nitrogen. It is well known that the framework of animal tissues is nitrogenous ; but n is none the less certain that different tissues are filled with non-nitrogenous matters, such as the fat of adipose tissue and rjlyoogenous substances. The albuminoid matters undergo in the blood, and afterwards in the organs to which the blood carries them, numerous transformations, most frequently pro- duced by oxidation. To prove this it will only be sufficient to enumerate the different nitrogenous principles found in the body. These are mainly : — Urea Uric acid Urine \ Hippuric acid . j C^stin I Aanthin . Perspiration — Sudoric acid . ^ Taurocholic acid Liver . . .( Glycooholio acid (. Cholesterin f Leucin . Pancreas J Tyrosin . I Lactic acid . f Creatin . . Crentinin . Inosite . Inosio acid . Sarcosin . Sarcin (Hypozanthin) Osseous tissue — Ossein. Muscles CH.NjO C,H,N03 CaH^NSO- CsH^N^O^ CioH«0,,N? - C3eH,,N0,S C,eH«NOo CffH,3N0, C,,H„N03 ^sHfiOs C4H9N3O8 CJiyNjO CeH,oO„+2H20 C^HsNA? C3H7NOJ 0^H,N40 ■Be m^i GLUCOSE IN THE MVEtt. Transformation of Amylaceous or Farinaceous Food. — Starchy matters are only found in small quantities in the tissues of the body — a fact which is quite natural as regards carnivorous animals, but very surprising in the case of herbivorous animals; and which seems to prove that starch is the chief respiratory idiment, and that it is very easily oxidized or burned. The greater part of the starch is transformed into carbon dioxide and water. Another portion is con- verted into fat, and the rest (a minute fraction) is fixed in certain tissues. Glx'cose in the Liver. — The existence of amyla- ceous matter in animal tissue is connected with a remarkable discovery made in 1849 by the illustrious physiologist, Claude Bernard — a discovery which we shall now describe, as well as the researches which led to it. If a carnivorous animal be subjected to prolonged fasting, sugar will be found in the hepatic tissue. The proportion of sugar foimd in the liver of carnivorous animals, or of animals fed exclusively with meat, is substantially the same as that in the liver of herbivorous animals, or of animals fed with amylaceous or saccha- rine food. Hence the production of sugar does not depend upon the existence of amylaceous and saccha- rine substances in the food. Objections might be raised to such experiments, on the grounds that the blood, in passing through the liver, might leave sugar behind it in this organ, and that sugar is merely retained and accumulated by the liver. Wiilliiiiitiimi^ ■■H r»'n':" 824 ANIMAL CHEMISTRY. Bernard responds to these suppositions by an experi- ment as interesting as it is conclusive. If a dog is killed and fhe liver removed, and, after washing this organ in such a manner as that all the sugar shall be dissolved, it is allowed to remain exposed to the air for a day, it is foimd to again contain a very large proportion of sugar. If, also, the blood of the vena porta be analyzed before it reaches the liver, as well as after leaving this organ in the superior hepatic veins, a considerable increase in the amount of sugar is observed. In order to extract the sugar of the liver, the latter is cut into very small pieces and treated witk boiling or even with cold water till nothing more is dissolved. The liquid is decoloured with animal charcoal, and evaporated over a water bath almost to dryness, and the residue treated with alcohol. The alcoholic solution furnishes glucose on evaporation. « Bernard found 23.27 gr. of sugar in the liver, weigh- ing 1,300 grammes, of a hanged criminal of forty-three years, and 25.70 grammes in that of another, aged twenty -two, and whose liver weighed 1,200 grammes. Qlycogene. — Sugar is produced in the hepatic tissues by means of a third substance — a sort of animal starch, designated glycogme — which has also been found on the internal surface of the amniotic membrane of ruminants, between the maternal and footal placenta of rodents, in the muscles, and in the lungs of the foetus, and later in the liver ; also in different parts of the Crustacea and articulates. GI,UCOSE IN THK LIVKK. 326 To prepare glycogene, the liver of a dog recently killed is out into very small pieces and thrown into boiling water to precipitate and destroy the ferment which would otherwise change the starch into sugar. Tlie fiagmentk are now withdrawn, triturated with animal charcoal, and the pulp obtained boiled for about twelve minutes, with five times its weight of water, filtered, and the residue treated with additional water. A liquid is obtained, from which the glycogene may be precipitated by alcohol. Glycogene is a white powder, soluble in water, which it renders milky, and insoluble in alcohol. The solution turns tlie plane of polarization strongly to the right. It has the composition of starch, x {G^li^Jd^, is coloured violet-red by iodine, is converted into pyroxam by fuming nitric acid, and furnishes dextrine and glucose under the same circumstances as vegetable starch. The transformation of glycogene into sugar is effected by means of a ferment «.nalogous to diastase, which is found in fresh liver and even in the blood. According to Pavy, the proportion of glycogene in the liver varies with the nutrition ; it is large if the food is vegetable, and is, on the contrary, small if the food is animal. Amount of Glycogene in the Liver. Dog fed with amylaceous food. 17.23 per cent. „ „ „ meat. . 6 97 „ „ „ „ „ mixed with sugar .... 14^.50 „ WifiiWiy''"""''™^"'"'**^'^"'"^^ ilfT 326 ANIMAI, CHEMISTRY. Bouget arrived at analogoiis results. On the other hand, Sanson has announced that on giving animals very farinaceous food, dextrin is found in th.> blood and even in the muscles; consequently muscles sup- plied as food would furnish amylaceous matters directly. There also exists in the muscles a saccharine substance called inositc, CaHijOa, and lactic acid ; consequently a diet of meat forms in the body amylaceous products. Amylaceous matter is also found in the muscles of new-bom mammalia, and in the muscles of an organ \vhen in absolute repose for a certain time. This all leads to the belief that there is an amylaceous matter which takes part in the formation of muscular tissues, but which disappears under ordinary circumstances, and is transformed into inosite and lactic acid. From these facts, and the existence of glycogene in other parts of the body than the liver, it follows that the liver is not absolutely the only organ having the property of transforming starch into sugar, but that It possesses it in a much greater degree than do the others. The sugar thus formed in the liver then passes into the blood, and there disappears, under normal condi- tions, being burned by the oxygen ; but certain natural or artificial conditions may diminish or increase the formation of this sugar. If the spinal cord be dissevered below the phrenic nerves, the circulation becomes weaker in the abdominal region, the temperature is lowered, and sugar is no longer found in the hepatic veins. ■f^^—'"'*^'"'™" OLUCOBE IN THE URINE. 327 ARTIFICIAL AND NATURAL DIABETES. the It is observed that the amount of sugar increases in the blood of the buperior hepatic veins when tbe pneurao-gastrio nerves are irritated, when a special point in the wall of the fourth ventricle is pricked, when essence of turpentine, ether, or chloroform is in- jected into the vena porta, or simply when large proportions of these agents are inhaled, or, finally, when poisoning is produced by ourariuu, Btrychnia, or brucia. Let us follow step by step the research of Bouchardat, in order to study the theory of natural diabetes. And first we will recall the fact, that the digestion of amylaceous substances takes place in the intestines under the action of the pancreatic and intestinal juices, that the greater part of the starch is only changed into dextrine in the intestine, and that the further transformation of this dextrine takes place chiefly in the blood, under the action of the intestinal diastase absorbed simultaneously with the dextrine. Whenever there is an excess of glucose in the blood, this sugar passes into the urine. This fact may be demonstrated by injecting glucose into the veins : if there is but little, none is found in the urine ; if there is a large amount present, reagents will indicate its presence in the urinary secretion. The causes which produce an excess of glucose in the blood may be of two opposite characters : either the sugar is due to too great a secretion, or it may result 328 ANIMAL CllKMISTRY. from an insuffioieut destruotiou ; but more often veri- table glycosuria characterized by a constant excess of sugar, is due to both of these causes combined. It has been demonstrated that the sugar passes into the urine whenever there is more than 3 to 6 grammes in the blood at one time. There may be an incompleteness in the destruction of the glucose in the blood, either because the oxygen is not present in sufficient quantity or because it meets with substances which are more easily oxidized. Diabetes will result when, the nutrition being very starchy, there is an excessive transformation of amyla- ceous substance into glucose in the digestive canal. In fact the glucose is observed to increase with the propor- tion of amylaceous food. In persons afli'cted with glycosuria the transformation takes place in the stomach, and this fact consequently explains why all albuminoid' substances are susceptible of acting upon starch ; they differ only in the rapidity of their action. It has also been shown that if the pancreas of a pigeon be removed it will still be able to digest amylaceous substances. Bouchardat has also observed that the stomach of persons having glycosuria is generally very much en- larged, and that persons who have a tendency to diabetes prefer farinaceous food, that they eat a great deal, and also that they eat rapidly, which circum- stances occasion a longer sojourn of the food in the stomacL When an organ is much used it acquires greater strength, and it is not unreasonable to admit that under these circumstances the gastric juice may TUANSrORMATION OP FATTY 8UB8TANCK8. ;i29 not be sensibly changed, and become incapable finally of dissolving amylaceous matter. Diabetes is accompanied by continual thirst ; hence it will be understood that since the food requires 8 to lO times its weight of water for digestion, the gastric juice must be iusufRoiont if the digestion of the farinaceous food takes place in the stomach at the name time as the albuminoid. The sugar in the urine of diabetic persons ordinarily disappears on submitting them to a diet formed ex- clusively of meat, if the disease is not too advanced. In general, any cause on the other hand which pro- duces a diminution of the respiratory plienomena tends to retard the destruction of glucose in the blood and produce diabetes if the tissues are saturated with glycogenic matters. in TBANSFORMATION OK FATTY SUBSTANCES. It has been established by a large number of experi- menters, who have operated upon different animals, that all of tlieiu not only assimilate fatty matters, but that they produce fat as well. Fat alone given as food pro- duces inanition. If animals be submitted to varied nutrition, there is much more assimilated fat found than there was in the food originally supplied them. Fatty bodies mixed with the other food facilitate growth. Amylaceous and saccharine substances are readily changed by digestion into fatty matters. It has not been demonstrated that nitrogenous foods are transfoi-moc) into fats. 1^- 330 ANIMAL CHEMISTRY. Till' Jidle of Mineral Compounds in Nutrition is but little understood. Iron exiets iu different parts of the body, and princi|ially in the l)]of)d globules. Sodium chloride is found in inot-t auimal fluids. It is thought, as we have already stated, that this substance ip ihe origin of the hydrochloric acid of the gastrio juice, and of the soda, which in found in the inteHtinal juices. It is known that this salt forms a compouud with glucose (p. 186), also the existence of a compound of sodium chloride and urea has been shown ; and this is the reason for the belief that salt assists in the transformation and elimination of sugar and of urea. It aids in the solution of albumen and casein in certain humours. It prevents the dissolution of the blood globules, of the chyle and lymph, and we have reason to believe that it, like other salts elsewhere, is an important factor in the absorption of liquids by different membranes. Weiske and Wildt (7-1874-123) have made inves- tigations as to the action of food poor in lime and phosphoric acid, upon animals of rapid growth. They experimented upon three lambs about two and a-half months old, and in a healthy condition, feeding one with food poor in lime compounds, one with food poor in phosphoric acid, and the third with the usual kind of food; while the latter prospered and gained 13.5 pounds in fifty-five days, the first two lost thirteen and fourteen pounds in weight, and were by this time nearly dead. The animals having been killed, the com- position of their bones, as regards their inorganic con- stituents, were alike, but the amount of fat in the bones TRANaVORMATION OK KA'ITY 8UB8TANCK8. 381 t is but } of the Lb. Iti» ibstance rio juice, A juices. I glucose ' sodium 16 reason ition and ) solution preveuts jhyle and like other bsorptiou de inves- lim« and h. They nd a-half iding one food poor al kind of ned 13.5 irteeu and this time , the com- S^anic con- the bones of the animal fed with normal food was greater than in both the others. A diet poor in calcium and phospho- rous compounds does not affect the constitution of the bones as regards their mineral constituents. Sodium Phosphate is capable of facilitating the absorp- tion of carbon dioxide by the blood, and consequently it is regarded as playing an important part in re- spiration. Calcium Phosphate is found in the majority of animal substances. Tliis salt forms the greater part of the mineral matter of the bones, it exists in the ash of albuminoid compounds. It enters the body diasolved in water by means of carbonic acid. This substance, as well a& the celcium carbonate, magnesium phosphate, and silica assist in giving solidity to the animal structure, and Chossat has asserted that the bones of pigeons completely deprived of calcium phosphate become so thin as to break. Magnesium phosphate cannot replace calcium phosphate. Weiske (36-'77) has investigated the influence of common salt upon the live- weight and the disassooiation of nitrogen in various animals, and ascertained : that if the amount of salt in the food increases, and the animal be allowed all the water it desires, the amount of water consumed increases ; that with the increase of salt in the food and the consumption of water, as far as an increase in the production of urino accompanies the same, the disassooiation of nitrogen increases ; that when the salt is removed, the consumption of water, as well as the production of urine, and disassociation of -vr wm ANIMAL CHEMISTRY. nitrogen, decreases; nevertheless the latter remains higher for a longer time than if a large ingestion of salt had not taken place. The increase in weight following a diet composed largely of salt is not due to increase in the amount of flesh, but to the accumulation of water in the body. Salt given in the food increases the desire for eating, but a notable increas or decrease in the digestibility of the food has not been proven. •■t^»p-- r remains ion of salt following norease in n of water the desire ase in the URINE. 3sa URINE. Human urine in its normal state is a liquid of an amber colour, the concentration of whicb, ««.nd conse- quently the density, varies with the age, sex, and state of digestion. This secretion is much more abundant, relatively, in infants than in grown persons, but the urine of infants is also richer in water, paler and less dense than that of adults. Parrot and A. Bobin have lately (9-82-104) studied the urine of newly-born infants, and find that the secretion amounts to four times as much, referred to the weight of the body, as in adults. The quantity of urine in woman is to that in man nearly in the proportion of 13 to 12. The urine of man is pale, and charged with water aftrsr abundant ingestions of this liquid. Normal urine is that obtained soon after rising, its density is about 1.018, it varies between 1.012 and 1.022 ; its density may fall as low as 1.003, and rise to 1.030 after a hearty repast ; it is then yellow. Water is evacuated from five to six hours after having been taken into the system. The proportion of urine is extremely variable ; ^ ,200 to 1,300 grammes H "t^' 334 ANIMAL CHEMISTRY. is about the mean in men in twenty-four hours ; 1,300 to 1,400 grammes in women. But this quantity may sometimes increase to 2,000 grammes, and descend to 900 grammes. The three principal causes which influence the amount of this secretion are : — Ist. The nature of the blood ; a very aqueous blood increases it. 2nd. The rapidity of circulation in the kidneys. 3rd. The activity of the pulmonary and cutaneous respiration. The urinary secretion varies in inverse proportion to the respiratory phenomena; thus the quantity of urine emitted is grea' jwin winter than in summer, in cold countries than in warm countries. After a cold bath the uxinaiy secretion attains its maximum. Certain salts — nitre, for example — increases the quantity of urine ; they are denominated diuretics. Other substances retard and diminish this secretion, as cantharides, etc. The proportion of solids extracted from the body by the urine may vary from 40 to 80 grammes in twenty- four hours. Composition of Normal Urine of Man. "Water. . . 936.76 931.42 SoUd constituents. 63.24 68.58 932.41 67.59 1000 00 100(1.(0 10(0.00 INFLUENCE OF FOOD ON THE URINE. 336 rs; 1,300 itity may Lescend to lenoe the 30U8 blood ineys. cutaneous in inverse ; thus the ter than in 1 countries. attains its creases the diuretics, is secretion, the body by m twenty- Vfan. 932.41 H7.59 10( 0.00 The solids axe composed of- Urea Uric acid . Lactic acid . Aqueous extract . Alcoholic extract . Lactate of ammo- nium Chloride of sodium and of ammo- nium Alkaline sulphates Sodium phosphate Calcium and mag- nesium phos- phates . . Mucus. . . 31.46 1.02 1.49 1.62 10.06 1.89 3.64 7.31 3.76 1.13 0.11 63.48 32.91 1.07 1.66 0.59 9.81 1.96 3.60 7.29 3.66 1.18 0.10 32.90 1.07 1.61 0.63 10.87 1.73 3.71 7.32 3.98 1.10 0.11 63.72 64.90 (Lehman.) INFLUENCE OF THE FOOD ON THE COMPOSITION OF THE URINE. Nature of the Food. .5?''*' J? lOOu parts. Honey 67.82 Animal 87.44 Vegetable . . . .69.24 NoB-nitrogenouB . . 41.68 Urea. ;Urio Acid. Add and Extractive liit?S,^ Matter,. 32.498 63.198 22.481 14.408 1.183 1.478 1.021 0.735 2.725 2.167 2.669 6.276 10.489 16.196 6.499 11.864 (Lehman.) "7* r,» 'f i I^M '".■ K^-" •■ J^i-J^-? . ■f£-^t*"' -■■*« .■v»->i«* ■: 336 ANIMAI- CHEMISTR-y. Normal human urine is aoid. This acidity is due to the action of the uric acid and other acids of the urine upon the alkaline phosphates. These acids deprive them of a portion of their alkali, and acid phosphates result. Uric or hippurio acid may also be found in excess in urine. The quantity of free acid evacuated in twenty-four hours represents 2. to 2.6 grammes of oxalic aoid. The reaction of the urine depends upon the character of the food. In fact, this secretion is alkaline in herbi- vorous animals, since their food, which is very rich in carbon, forms bicarbonates with the bases which are in this secretion ; but the urine of an herbivorous animal may be rendered acid on submitting it to a diet of flesh food. The urine of herbivorous animals is turbid, and contains urea, hippurio aoid, and a small quantity of phosphates ; it does not contain uric acid. Inversely the urine of carnivorous animals is aoid and clear. It is rendered alkaline by forcing the animals to an exclusive vegetable diet. The urine of oarnivora contains more urea and uric aoid than that of man or herbivorQjis animals, while hippurio acid is wanting in it. Regarding the occur- rence of phenol, E. Bauraan has recently observed that albimien and pancreas in putrefying form a. certain quantity of phenol, and he believes in this reaction can be found an explanation of the existence of phenylsul- phates in the urine of dogs fed exclusively with meat (60-77-685). Violent exercise, fatigue, and excesses render human is due of the a acids ad acid ay also nty-four id. haracter n herbi- rich in h are in 9 animal t of flesti rbid, and antity of is i» acid cing the and uric ala, while he occur- jrved that certain action can lenylsul- with meat lev human AWMONIACAL URINE. 337 mine alkaline. This fact is due to the combustion which, under these circumstances, transforms the urio acid into urea, and tliis body does not possess, like urio acid, the property of removing from the phosphates a portion of the alkali which they contain. Gosseliu and A. Robin (9-78-72j liave made experi- ments upon animals, injecting ammouiacal uriue sub- cutaneously, and found that animals subjected to this treatment became feveribh, and when larger quantities were injected they died. Thus in diseases of the bladder, the ammouiacal ui-ine, if reabsorbed, must be deleterious, hence it would be advantageous to the patient that the amount of ammonium carbonate in the urine be reduced ; this, according to investigations of GosseUn and Robin, is effected by the administration of benzoic acid. Pasteur (9-78-46) claims that the ammoniacal nature of urine is due to tlie action of a ferment which obtains entrance through the urinary passages, or sometimes is introduced mechanically by means of chirurgical instruments. He recommends, therefore, that the instruments before being used be plunged into boiling water, or heated, then quickly cooled, and at once employed. A. Lailler (9-78-361) is of he opinion that the ammoniacal fermentation of iirine depends in a great measure on the amount of mucus it contains. Gubler (9-78-1054) asserts that the decomposition of urea into ammonium carbonate, as is the ease in the bladder in certain diseases of this organ, is due to small pus-corpuscles {niocytes). -jif 338 ANIMAL CHEMISTKY. W. Zuelzer (60-1875-1670) has lately fouud that after a diet composed wholly of meat, the urine of a dog contained for every 100 parts by weight of nitrogen, 12 to 14 of phosphoric acid ; ^ 'len fed with potatoes and bread, it contained 20 to 30 of phosphoric acid to 100 of nitrogen. In a healthy man, 20 to 25 years of age, the food being mixed and sufficient, the urine contains 17 to 19 of phosphoric acid to 100 of nitrogen ; with a diet of meat the proportion of phosphoric acid decreases, with a vegetable diet it increases. The time of day and the state of health have great influence upon the relative proportion of these two substanceu. Under normal conditions a man eliminates 12 to 14 of sul- phuric acid, 0.3 to 0.7 of lime, and 0.6 to 1.0 of magnesia to 100 of nitrogen. The urine, on leaving the body, deposits mucus after a certain time ; it often also deposits urates, especially during fevers. But its acidity soon increases, in consequence of the formation of more uric acid ; this acid is often seen to deposit in the form of rhomboidal prisms. Other acids are also formed, chiefly acetic and lactic acids. At the end of a few days the urine loses its acidity and becomes decidedly alkaline fr i the formation of a considerable quantity of ammonium carbonate. This salt is formed from the urea thus : — CO") CO"\q, n, N-|-2Hp=2(NHj ) "^ Hj ) This transformation of urea is favoured by the -W NORMAL CONSTITUENTS OF THE UIMNE. ab9 luud that 3 of a dog TOgen, 12 atoeB and id to 100 18 of age, e contains in ; with a L decreases, ime of day ) upon the Hi. Under 14 of sul- to 1.0 of nucus after 1, especially icreasfes, in acid; this rhomboidal acetic and urine loses le fr ^ the ammonium •ea thus : — ured by the presence of the mucous sediment which mine deposits when exposed to the air, also by the action of beer, yeast, and albuminoid substances. It is a true fermentation, accompanied by the development of an organized vegetable substance {Toriilacece), which reproduces itself by germination. Often its action is impeded by the formation of infusoria, which maintain the acidity of the urine for a long period. Cohn finds the organisms to be Micrococus ureac. NORMAL CONSTITUENTS OF THE URINE. Of the solid constituents, urea is the most abundant. The urinary secretion in man furnishes about 30 grammes of urea in 24 hours, but this quantity may vary greatly. The average in women is 20 grammes ; it falls to 9 grammes in old men. A very nitrogenous diet increases it, while food which is poor in nitrogen diminishes it. Urea does not even dieappear in an animal rigorously kept without food ; it is then formed at the expense of the tissues. When the urinary secretion ' increases, even though from the drinking of large quantities of water, the amount of urea produced also increases. It augments likewise, according to some authorities, during severe physical labour. We may admit, in general, that urea diminishes when the circulation of blood is sluggish, and that it increases when the circulation becomes active. There is only a very small quantity of urea in the -W •team m 340 ANIMAL CHEMISTRY. blood; it becomes gi-eater when tho kidneys perform their functions badly. Urea is not formed in the kidneys. Dumas and Prevost showed in 1823 that the blood of animals, from which these organs have been removed, contains considerable amounts of urea. This fact has been confirmed by Bernard and Barreswil, who also showed that, after the removal of the kidneys, the gaitrio and intestinal secretions increase. The gastric juice remains acid but contains ammonia. When the mimal becomes entirely ex- hausted, urea is found in the blood in a very notable quantity. Pioart and Meissnep have obtained the same results, which have, however, been doubted by Oppler, Perls, and Zal^sky. The question has been taken up by Ghrehant, who conceived the idea of determining the amount of urea with the greatest care, and he has perfectly demonstrated that urea accumulates in the blood in consequence of nephrotomy. 100 grammes of arterial blood contained : Before nephrotomy Three hours and forty minutes later Twenty-one hoxtxB later . . Twenty-seven hours later • . Urea. 0.088 grammes. 0.093 „ 0.252 ■„ 0.276 „ The urea increases, therefore, after the operation, and the increase takes place in a continuous manner proportional to the time. -» URIC ACID. 341 jerform in the hat the re been rd and loval of )cretif)n8 contains rely ex- ■ notable 3 results, r, Perls, I up by ning the he has is in the prammes. n » ti )peration, manner The ligature of the ureters renders the kidneys totally inactive, for the blood which leaves this organ is found to contain the same quantity of urea as on entering. Hence, after the ligature of the ureters, following nephrotomy, urea accumulates in the blood. The amount of urea excreted by man represents very nearly the whole amount of nitrogenous food which has failed to be assimilated, for the surplus is obviously found in the excrements, and they contain very little. The urine, therefore, is the liquid through which the nitrogen is eliminated, and the urea is almost the sole agent for effecting this. ' For this reason the determination of the urea is highly important as furnishing us with data relative to the elimination of the nitrogen from the body Urea is not produced in the muscles ; though creatin is easily transformed into urea when out of the body, yet, in spite of the considerable quantity of creatin which exists in the muscles, no urea is found in muscular tissue. On the contrary, it is sufficient to take in the food, creatin, gelatin, or analogous matters, to observe that the uroa is thereby formed in greater quantity in the urine. It is therefore rational to admit that these substances are oxidized in the blood, and that their nitrogen is eliminated in the form of urea. Uric Acid. — The urinary secretion furnishes each day 1.183 grammes of uric acid on an average (Wundt). It increases during digestion, and diminishes when the body is fatigued. In general it is produced .enever oxidation is impeded, and an increase in uric acid is .,-1. wm 342 ANIMAL CHEMISTRY. associated with a oorreBponding diminution of urea. This acid is found in the urine of persons affected with %rlid. urate of ammonia, and urate of sodium are often deposited in u.... a few hours after emission. Himmic Aci» is found in small quantity in human ^^e It increases with vegetable nouxishmeut, in Tabetes and in certain other diseases. It ib lormed, tolecui: for molecule, when a benzoic compound is Sken nto the stomach. Lactic acid is only produced !n the urine when digestion and respiration are im- paired it is formed if fevers, and whenever digestion and circulation are impeded. .!,,„,:„« Creatinin, and possibly creattn, exists m the urine In adult throws off, in the urinary secretion, about 1 16 gr. of creatinin in twenty-four hours. J. Mudc (60-76-1799) finds over '008 per cent, sulphocyan- hvdric acid in normal urine. .,, j-fl^^j sLdler considers phenio acid and two ill-defiAed Jll-damlic and darmluric acids.-to which the odotr of the urine is supposed to be due as constan o^ituents of the urine. Sclerer -gar^ ^^^^^^^^ fixistinff normally in the unno, though only in traces. It tL amorphous substance, soluble in acids and 't^cUntto Schunck, urine contains always «a«^ This name is given to a body not as yet obtained xn a orvstaUre condition, soluble m water, alcohol, and Sr and - essentially characterized by ite property of iLomposing in presence of strong hydrochloric acid, INDIOOOEN. 343 f urea. 3d with Bodium mission. I human aeut, in i'orraed, )ound is produced are im- digestion unne. on, about J. Munk Iphooyan- ill-d'efiAed vhich the constant xanthin as r in traces, acids and lys indican. tained in a Icohol, and B property iloric acid, furnishing, by combining with water, indigo and a Baoohuriuo matter, indiglucin. CAiNO,,+2H20=C8H£0+3C£^ Indican Indigo Indigludn The formation of this body accounts for the violet and reddish tints which are sometimes observi-'d in urine undergoing decomposition. These pnenomena take place only in the presence of atmospheric or other oxygen, as the indigo blue is very easily reduced. 2C8H.no +H2=C,eH,2NOa ' TJrozanthin and still more appropriately indigogen are modem synonyms for indican. The substance which imparts to urine its yellow colour has been called urochrome by Thudioum. According to Heller, ether extracts from urine, which has been evaporated almost to dryness, a matter which he was not able to isolate, and which he calls uroxanthin. It is remarkable from the fact that, under the action ot acids and in certain pathological states, it is transformed by oxidation into two other substances — one blue iiroijlaucin, the other red vrrhodin. Since these substances have not been isolated with certainty, we shall not further dwell on them. Gi-ucosE. — Glucose is always present in normal urine, according to some chemists, though doubted by Seegen and Gorup-Besanez. The quantity of sugar present in normal urine amounts in twenty-four hours to 1 to 1.5 grammes r' 844 AMMAI. CHEMISTRY. aooording to Briioko, also accurdiiig to Benoe Jones. It is therefore lebs than one-thoueaudth. FAITY BODIES, SALTS, AND OASES IN TTRINE. Fatty bodies are found in the urine, but their proportion is very minute. The quantity of saline matter in the urine is con- siderable. It amounts to about 15 grammes in twenty- four hours. This quantity may increase to 25 grammes, and decrease to 8 grammes. It is less in women, and still less in children. Among these solid matters r,.re prominently phosphates, sodium phosphnte, calcium phosphate, ond magnesium phosphate. The quantity of phosphoric acid eliminated in the urine varies from 3 grammes to 5 grammes in twenty-four hours. This acid increases during digestion. It diminishes in preg- nant women, and iu the eighth month there is STi little that both its reactions and those of calcium are hardly perceptible. Urine always contains alkaline chlorides, and chielly sodium chloride. The quantity increases as the amount ingested increases, but- the whole of this substance is not eliminated through the urine. The proportion of chloride increases after eating, and is at its minimum during the night. Exercise increases the amount. The weight of chlorine evacuated in twenty- four hours is about 10 grammes. When all salt is removed from the food the amount diminishes • v the urine, and remains fixed at 2 to 3 grammes per day, ■rt FATTY HOniES, 8AI,T8, AND OA8E8 IN URINR. 346 !e Jones. .INK. but their ne is oon- II tweiity- graniraes, jmen, and latters rre , oalci am 5 quantity raries from ars. This es in preg- is sn little are hardly ) chlorides, |r increases lole of this rine. The J, and is at loreases the in twenty- all salt is hes • > the s per day, which amount is derived troni tlio tiasuos, and a rapid enfouhlement results. 8ulpliatos are found in the urinarj' secretion. The quantity increases during digestion ; it averages 2 grammes in twenty-four liours. Normal acid urine contains no ammonium salts, but contains them on becoming alkaline, some time after its voidanco. The same is the case with the urine of herbivora, which is always alkaline. Many substR'ices taken into the body which do not serve as aliments are found again in the urine, in c"se they are not capable of uniting with certain principles of the body to form insoluble compounds. Those metallic suits are among these latter, which form precipitates with albuminoid substances. Substances not precipitable in the organism and diflBcultly oxidized — such as. chlorides, iodides, sul- phates, nitrates, urea, quinine, and most fragrant and colouring matters — reappear unchanged in the urine. Oxidizable substances, on tlie contrary, undergo the same transformations which they sustain when acted upon by oxidizing agents. Alkaline sulphidjs are converted into sulphates, alkaline organic salts into carbonates, benzoic and cinnamio acids into hippuric acid, uric acid into urea, salicine into 8.:ligenin and salicylic acid. The oxidation of certain other matters is more complete; they furnish carbon dioxide and water, which are the ultimate products of the oxidation of organic bodies. This is probably also what occurs to many substances which never reappear in the urinary secretion, even after abundant ingestion of the same ; ■■ii ^ 346 ANIMAL CHEMISTRY. Buoh are mannite, ether, resins, the colouring matter of leaves, litmus, cochineal, amygdaline, anilin, camphor, etc. The rapidity with which these bodies pass into the urine depends upon their solubility. Potassium iodide is found in the urine in a few minutes after being administered. A longer time is necessary for the urine to assume the odour which is developed after eating asparagus and the inhaling of the vapours of turpentine. Ihc gases of the urine are oxygen, nitrogen, and carbon dioxide. A mean of fifteen experiments made by Moring gave for a litre of fresh urine- Oxygen Nitrogen . Carbon dioxide 0.6$ 0.0. 7.77 „ 15.96 „ These figures are probably too small, as the method by which the gases woi-e determined was that of MagnuK. "*■ . Walking increases the amount of carbon dioxide. Carboa dioxide. Nitrogen. Oxygen. Urine during repose . 11.877 7.494 0,493 „ when walking . 22.880 8.204 0.466 The renal secretion of ophidians is solid, and com- posed chiefly of uric acid ; that of batrachians is liquid, and contains urea. The urine and excrements of birds contain chiefly acid urates, earthy phosphates, and a small amount of urea. -w nm ANALYSES OF DIABETIC UKINE. 347 Pathological States. — The urinary secretion in- creases in certain diseases (diabetes, polydipsia). In the first case its density may increase, as sugar is often present in large proportions ; it sometimes is as high as 1.040. In polydipsia the density falls to 1.001. It diminishes in cholera, in diseases of tho liver, and i: fevers. Diabetes. — The quantity of sugar excreted in the urine may amount to 1200 to 1500 grammes in 24 hours. Bouchardat, to whom we are indebted for important investigations relative to this disease, has shown that the formation of sugar may be lessened or even arrested by submitting the patient to a nourishment devoid of farinaceous and saccharine matter, by furnishing him for example, instead of ordinary bread, bread made of gluten or flour freed from starch by washing. The uric acid diminishes in quantity, or disappears in the urine of diabetic persons, ANALYSES OF DIABETIC URINE BY SIMON AND BOUCHAKDAT. Simon. Bouchardat. Density . . Water Solid constituents Urea . • I 1.018 957.00 43.00 traces. II. 1.016 960.00 40.00 7.99 I. 837.58 162.42 8.27 1 Mi 348 ANIMAL CHEMISTRY. Simon. /- Urio acid . . Sugar Alcoholic extract \ Aqueous extract | Salts . . ) Phosphates and mucus . . Albumen . Oxide of iron I. traces. 39.80 2.10 II. traces. 25.00 6.60 Bouchardat. I. traces. 134 42 6.27 0.52 0.80 0.24 traces. traces, traces, traces. traces. 0.14 Murkowuikoff (72-182-362) finds acetone and ethyl alcohol, and believes they are formed from the glucose by fermentation. Ciaude Bernard has shown that diabetes can be produced artificially by puncturing the "fourth ventricle." A slow poisoning of frogs with curari, the slow action of strychnia, the destruction of the spinal column of frogs, etc., produce dip^ s. Artificial diabetes is dependent upon the liver^as this state can never be obtained in a frog from which the livor has been removed. Saikoweky has shown that if 'he for- mation of gly oogenous matter in the liver of.r. rabbit be arrested, a result which is easily produced by the action of arsenates, this animal canuot become diabotio neither by oirari nor by puncturing the fourth ventricle. F. W. Pavy (n2-?3-?9; ^4^1) obtains diabetes OTHER ABNORMAL STATES OF THE URINE, 349 lohardat. I. raoes. 34.42 5.27 0.24 iraces. 0.14 and ethyl be glucose tea can be le " fourth t the slow the spinal Artificial state can livor has if 'hefor- of.f. rabbit ced by the me diabetic the fourth Qs diabetes artificially in dogs by passing defibrirated arterial blood through the liver ; saliva used instead of blood produced no glycosuria. Upon inhalation of oxygen Puvy noticed a like appearance of sugar in the urine. Aluuminuria. — Albumen does not exist Uvumally in the urine. When it is found, it is due either to the secretion of an albuminous urine by the kidneys, or to an admixture of blood, pus, or lymph. Albuminous urine is pale, acid, opaline, often of a density less than normal. As much as 20, 30 and even 35 grammes have been found to have been secreted in twenty-four hours. The albumen increases after taking food ; it is at its minimum during the night. It increases with nitro- genous food. According to Lehman this albumen exists in two states, one part is the modification of albumen called metaglobuline and paraglobuhne, and is precipitable by carbon dioxide. The ether remains in the liquid after the passage of the gas, and is precipitated by ordinary acids. An;emia. — The urine is pale and scarcely acid in anepraic persons ; it sometimes even becomes alkaline. It is rich in salts and poor in most organic con- stituents. Other Abnormal States of the Urtne. — The urinary secretion decreases considerably in fevers, and is of a deeper colour and more dense than normal urine. Its acidity increases on account of the uric acid which forms abundantly, and of the lactic acid which is also 360 ANIMAL CHEMISTRY. developed. The urea disappears in about the inverse proportion. The extractive matters increase ; the salts, and especially the sodium chloride, decrease. The proportion of urea increases in intermittent fevers, also at the commencement of ty{)hoid fever. The quantity of urea, and especially that of uric acid, increases in inflammatory diseases. At the com- mencement of acute attacks the urea L-o been observed to amount to 60 grammes. The urine of persons affected with phthisis is richer in uric acid than normal urine, and fatty substances are also observed in it. The urea diminishes in nervous affections. In scarlatina and small-pox the urine contains am- monia, although it retains its acid reaction. A. Fohl found oholesterin (40-7t)-737) in the urine of an epileptic patient who had taken large doses of potassium bromide. Epithelial cells are found in large quantities m the urine in erysipelas, in scarlatina, in the commencement of Bright's disease, and in different urinary affec- tions. Fibrin and blood-globules appfearln the urine during inflammation of the genital and urinary organs. In catarrh and in paralysis of the bladder the urinary secretion contains urate of ammonium. The urine is decomposed in the body of persons affected with catarrh of the bladder ; and in the urine are observed monads, vibrionB, and mycoderms. Mucus is present in small quantity in normal urine. In various diseases of the genito-urinal organs, the OTHER ABNORMAL STATES OP THE URINE. 351 e inverse the salts, ;ennitteiit d fever, it of urio the com- a observed ns affected mal urine, ntains am- 1 the urine ge doses of ities m the imeneement nary affeo- irine during ^ans. In the urinary he urine is with catarrh veA monads, ormal urine, organs, the mucus increases to such an extent as to render the urine turbid or milky. Pus is found in the urine when suppuration is esta- blished in the geuito-urinal tract. The urine in jaundice contains the acids and colour- ing matters of the bile. These acids also pass into the urine in pneumonia. The bile itself is often found in the urine, and in this case boiling ether agitated with the urine takes on a green colour. The urinary secretion diminishes or ceases entirely in cholera. The proportion of phosphates increases in nervous' affections. The quantity of chlorine decreases chiefly in pnewmonia, in obstinatp diatrhoea, and during cholera. Chyle and casein are found in certain urines. The urine is brown in acute rheumatism ; it is red in many diseases in which the colouring matter of the blood passes into the urine ; it is almost colourless in megrim and in nervous affections. Von Meriing and Musculus (00-1875-662) have examined the urine of a person who for a long time took 5 to 6 grammes of chloral hydrate every evening. The urine had an acid reaction, reduced alkaline coj)j)er solutions, contained neither chloroform, formic acid, nor sugar, but it contained chloral hydrate in small quantity, and turned the plane of polarization to the left ; this latter property was due to an acid which they called nrochloral acid, obtained by evaporating the urine acidified with sulphuric acid, and extracting the acid with a mixture of alcohol and ether. This new acid >."■ 'Hfe^i***^* W4 •^^tMMOi ini^n- 362 ANIMAL CHEMISTRY. ! Ill orystallizes in colourless silkea needles, dissolves in water, alcohol, and a mixture of alcohol aud ether, but ia insoluble in pure ether ; with potassium, sodium, barium, and copper it gives well cryslullized salts ; its composition is expressed by the formula CyHiaCL.Og. F. Baumstark (60-1874-1170) louud in the urine of a person suffering with leprosy two peculiar colouring principles which he calls urorubrohrmatin aud uro- JUclmoltemntin. Urorubrohematin is a light bluish-black mass, insoluble in water, alcohol, ether, chloroform, or a solution of salt, soluble in alkalies, ammonium hydrate, alkaline phosphates and carbonates, alcohol containing acids, difficultly soluble in dilute sulphuric acid, and solutions of salt acidified with hydrochforio acid. The acid solution shows a characteristic absorp- tion spectrum. The formula obtained by analysis is CggHg^NgFeaO^o (?). Urofuchsohematin is black, i>itchy, insoluble in water, alcohol, ether, chloroform, aciHs,- or acidified or non-aoidified salt solutions ; it is soluble in alkalies, ammonium hydrate, alkaline phosphates and carbonates, and acidified alcohol. Analysis shows its formula to be CggHiooNgOjj (?). J. Miiller (60-1874-1526) found in the urine of a child pyromtevhin. Urinary Sediments. — Human urine abandoned to itself often deposits solid crystalline bodies. During fever, urate of sodium is observed to form a short time after emission. These crystals are microscopic, aud the appearance of the deposit is corpuscular and colourless. •mmm -mm DRINARY CALCULI. 363 )lve8 in her, but Bi>dium, alts; its urine of lol.'iiring Liid uro' ish-black oform, or imonium 1, alcoliol Bulpburio irochrorio absorp- aalysis is k, pitchy, aci3^8,- or soluble in lates and sbowB its inne of a nd'oned to During sliort time c, and the colouiless. They are recognized by their disappearance when the urine is heated. The urine sometimes deposits, three or four hours after emission, prismatic crystals of uric acid having a rhombicf base. When ammoniaoal fermentation takes place in urine, a deposit of urate of ammonium is observed mingled with calcium phosphate or eaibonate and amnionio- magnesiura phosphate. This sediment forms whitish opaque grains, insoluble in water, soluble in acetic acid, and insula bio in ammonia. At otlier times, crystals of calcium oxalate and ammonio-magnesium phos|:)hate separate out. C. Stein (1-187-99) finds in certain rare oases in whicli the urine is alkaline that magnesium phosphate occurs in the sediment. There also separates out from the urine, under unusual ami not well understood circumstances, an organic matter called q/ntiti, containing sulphur. riiis substance is colourless, insoluble in hot water, and soluble in ammonia. Besides these crystalline substances, tbe urine de- posits organized matters ; mucus is alway present in it, sometimes pus, spermatozoids, blood globules, and coagulated albumen. XiuiNARY Calcilt. — THs name is given to concre- tions of solid substances which form in the bladder. At times they escape with the urine in small grains or powder ; they are then known as gravel. WM 854 ANIMAL CHEMISTRY. These deposits are formed of various substances : urio acid, urate of sodium or ammouium, oaloium car- bonate, oxalate or phosphate, ammonio-maguesium phosphate, cystin or xauthio oxide. The cystin may be obtained by treating the calculi with sodium carbonate and adding acetic acid to the liquid, when it deposits oystiu in handsome hexagonal plates. This substance may also be obtained from the kidneys. A cystin calculus is soluble in caustic alkalies, and even in solutions of alkaline carbonates, wihh the ex- ception of ammonium carbonate. It is dissolved by the mineral acids, and precipitated by acetic acid- Heated in the air, it furnishes sulphurous oxide. Heated with an alkali it furnishes a sulphide. The nature of the calculi formed of cystin will be described further on. ** ■» ANALYSIS OF URINARY CALCULUS. Urate of sodium • • 9.77 Calcium phosphate . • • 34.74 Ammonio-mftgnesium phosphate 38.35 Calcium carbonate , , . 3.14 Magnesium carbonate • • '2.55 Albumen . • • 6.87 Water and loss . . • 4.58 • 100.00 (Lindbergson.) et ANALYSIS OF A CYSTIN CALCULUS. 355 jstances : oiuin car- aguesium he calculi 3id to the hexagonal from the jolies, and Lhh the ox- Bsolved by icetio acid. •0U8 oxidfl. aide, stin "will 1)6 100.00 idbergson.) ANALYSIS OP A FERRUGINOUS URINARTJ CALCULUS. Ferric oxide Alumina Silica Calcium Water Loss. 38.81 23.00 17.25 8.02 10.89 2.03 100.00 (BoussiugaiJt.) ANALYSIS OF A CYSTIN CALCULUS. Cystin 97.6 Calcium phosphate and oxalate . . 2.5 100.0 (Lassaigne.) ir*woMr)pr«wsr.«j-iTti#wW«i ■I 366 ANIMAL CHEMISTRY. ANALYSIS OF URINE. The whole of the urine voided during 24 hours is col- lected and its volume measured ; of this 250 grammes are taken and allowed to stand for 24 hours ; or the urine first voided in the morning after sleep is taken for analysis. We commence by determining by means of litmus paper the reaction of this urine, and then determine its density ; as the presence of water or albumen dimuushes ' its density, while the presence of sugar and salts au-niouts it. There are used for this test ^special areometers or hydrometers, called urinometers ^It is ,vell to verify once for all the graduation of these instruments by menus of urines whose specific gravity has been determined by the ponderal method. GLUCOSE. • We have already stated that abnormal urine may contain very large proportions of sugar; b-^™ !« usually sweet and denser than ordinary urine, it is Tee Lie of fermentation, turns the plane of polaxi^a- tion to the right, and is but sUghtly coloured. "^jg^- " ' * QUANTITATIVE ANALYSIS OF URINl 367 urs is ool- immes are urine first analysis, of litmus termine its diniinislies and salts lest special tersT -It is a of these lific gravity d. urine may uoh urine is trine. It is of polariza- led. If it is desired to extract lue sugar, basic lead acetate is added iu excess, the solution filtered, the excess of lead prer "pitated by hydrogen sulphide, again filtered, and evai-orated until it crystallizes. The Qualitative Tests. — Its presence merely may be detected by the tests given on page 187. It should, however, be remarked that these reactions are not reliable unless a precipitate appears within one or two minutes boiling, as secondary reactions are produced with the other substances contained in the unne. QUANTITATIVB DETERMINATION OP THE SUGAR BY THB KEDUCl'ION OF COPPER SALTS. Preparation op the Liquid.— Weigh out 200 gr. of pure Rochelle salt, which place in a flask graduated to 1 litre ; add 500 c.c. of a solution of sodium hydrate of 24- Baura^ (D = 1.199). or 600 c.c. of a solution 22°Baume (D =zl 180). The solution is facilitated by agitating and slightly heating in a water bath. In another vessel dissolve 36.46 gr. of commercial copper sidphate, which has been purified by two or three recrystallizations, in 140 c.c. of distilled water shghtly heating. This solution is slowly poured into the first, stirring at the bame time, that the precipitate may be dissolved. Rinse out the vessel which con- turned the copper sulphate two or three times, and after Mi 368 ANIMAL CHKMI8TRT. placing the litre-flask in a vessel of cold, common water, add enough distilled water to bring the liquid in the flask up to 1 litre. This solution is very reliable, and may be preserved for months exposed to the light with- out alteration. For an improved reagent, see p. 187. Each 10 CO corresponds to 0.050 gr. of pure cane sugar, or 0.0526 gr. of pure glucose. The determination is made by placing 20 o.o of the oupro-alkaline solution in a porcelain dish, bringing the same to boiling, and adding gradually- at the same time agitating with a glass rod— the saccharine urino from a burette graduated to tenths of a cubic centimetre. There is first formed a yellowish, then a red precipitate. When the colour appears constant remove it from the flame; the supernatant liquid soon becomes clear; if it should appear greenish, again heat and add more of the urine drop by drop. The liquid must be neither greenish nor yellow. As long as there is any copper in the solution a drop of urine will produce an orange- coloured ring when it falls into the reagent. The amount of urine necessary to effect this will, of course, be an amount containing 2x0.0526 or 0.1052 gr. of glucose. Deiermination of Gltjcos:r iv the Urine, by means of lead acetate.— In clinical experiments it is often sufficient to add to the urine a few drops of a con- centrated solution of lead acetate, separate the precipi- tate formed by filtering, and after bringing the filtrate to a known volume employ it in the same manner as the urine in the preceding operation. >-..-.-•■.. .vS^P*" ANALYSIS OF URINK — ALHUMEN. 369 (ommon iquid in ible, and ;lit with- ure cane ).o of the bringing the same rine luine jntiraetre. recipitate. t from the J clear; if d more of he neither my-copper an orange- ent. The ^ of course, 1052 gr. of CThtne, hy mentB it is ps of a con- he precipi- the filtrate anner as the The lead salt has the offect of precipitating the foreign matter. Tiie glucose is not iirecipitated by the ituetate unless ammonium hydrate is added. When diabetic urine is highly charged with sugar it must be diluted with 5, 10, or 20 times its volume of water. Glucose can also be determined by adding yeast to the urine, and from the loss of carbonic acid in the resulting fermentation calculating the glucose present. It can also be estimated by means of a polarizing appa- ratus, suoh as is used for determining the strength of saccharine solutions for sugar refineries. As it is not within the scope of this work to supply elaborate instructions with regard to urine analysis, those desiring full details regarding the examination of urine for this or other constituents should consult some author on chemical analysis, or specifically on the chemical examination of the urine. A liberal amount of laboratory work is requisite, however, for such as would acquire a practical acquaintance with the chemistry of abnormal urine. ALBUMEN. Albumen is coagulated by heat and nitric acid. It is necessary to have recourse to these two reactions to detect with certainty the presence of albumen in urine. In fact, by simply heating the urine it often becomes turbid, owing to the precipitation of the earthy phos- iifiiiirmi 360 ANIMAL CHEMISTRY. phateB or carbonates; these salts may be recognized, however, by adding a drop or two of nitric acid, which will redissolve the precipitate formed. On the other hand, nitr;c acid will produce a whii.e precipitate in the urine of a patient who has been taking various resinous remedies. When it has been found that four to five cubic cen- timetres of urine coagulates on heating, and that it continues to coagulate after adding eight to ten drops of nitiic acid, we may conclude that this urire contains albumen. In order to estimate the amount of albumen we com- mence by ascertaining whether the urine is alkaline or not ; in case it is, it should be slightly acidulated with acetic acid. 100 c.c. of the urine are taken and heated 80 as to cause coagulation — that is, until the urine just commences to boil. The liquid is then thrown upon a double filter, i.e., two filters of equal size and weight placed one within the other. The albumen remdlns upon the inner filter; it is washed with wator, then with alcohol, and when it has well drainfd the two filters are dried at 110°. The difference between the weight of the filters with the precipitate and the filters empty is the weight of the albumen. Another determination to check Ihd first may be made, precipitating the albumen with dilute nitric acid. , . mmm ifa DETERMINATION OF UREA — BILE. 361 gnized, •whicli 3 other s in the esiuoua bio oen- that it n drops Bontaina we com- ialiue or ted with d heated Lrine just 1 upon a d weight remains tor, then the two ween the the filters may he ite nitric UREA. We have already mentioned the importance of noting the variations in the amount of urea, since these varia- tions give us light upon certain points in the process of nutrition. In order to ascertain whether a given urine is very rich iu urea, a few drops are placed on a watch- glass with an equal volume of nitric acid and the glass floated on cold water ; after a few minutes crystals of nitrate of urea are to he seen. In order to determine the amount of xirea, Leconte's method may he employed, which is hased upon the oxidation of the urea by hypochlorites : — CH4N2O + SNaClO = 3NaCl + CO2 + 2H2O + Nj. Carbon dioxide and nitrogen are disengaged: the former is absorbed by a solution of sodium hydrate, and the latter collected and measured ; from the volume obtained the amount of urea can be determined. BILE. I. Gives with sub-acetate of lead a greenish-yellow precipitate. II. Gives with a drop of nitric acid, green, blue, yellow, violet, and red coloration. III. Gives with a solution of white of egg, on adding nitric acid, a precipitate which is bluish-green ; ■whereas in the absbuce of bile it is white. 4 t62 ANIMAL OIEMI&rRY. IV. Yields with tincture of iodine a green colora- tion. According to W. G. Smith (7-[3]8-299) this reac- tion distinguishes bile &om the so-called indican. URIC ACID Is recognized qualitatively by the test given on page^ 125. I\; is usually determined quantitatively by adding to a given amount of urine — not less than 160 to 200 c.cm. — suflBcient hydrochloric acid to fully precipitate the uric acid, and allowing tho liquid to stand for twenty-four to thirty-six hours. Traces of uric acid still remain in solution which, however, according to Neubauer, are compensated for by the amount of the urine pigfment which also falls with the uric acid. The precipitate is filtered ofiP, washed, dried^ and weighed. URATES. The urates of sodium and ammonium are among the constituents of normal urine ; they are often deposited after voidance when the urine has become cold ; a deposit is then observed which disappears on slightly heating. These \irates may be recognized oy charac- teristics which will be given under Urinary Deposits. 7T mmm^ INORGANIC SALTS IN UEINE. 863 OOloMk- is reao- '.an. HIPPTJRIC ACID. If hippurio acid is founc' to exist in notable quan- tities in urine, it may be determined by the method already given under the general discussion of this acid. on page rely by 3S8 than to fully liquid to Craces of however, r by the with the ed, dried» mong the deposited cold; a slightly oharaO" )epo8itB. 'y CREATININ. Creatinin may be detected and even quantitatively determined by the following method: Milk of lime, then calcium chloride, is added to 300 to 600 o.c. of urine until a precipitate no longer occurs ; after being allowed to stand for a few hours the solution is filtered and the filtrate evaporated in a; water-bath to the con- sistency of a syrup ; 40 c.o. of 90 per cent, alcohol is then added, and the whole allowed to digest for twenty- four hours. The clear liquid is decanted off, and a solu- tion of zinc chloride, as nearly neutral as possible, is added- A compound of zinc chloride and creatinin is formed, which is collected on a filter, washed with quite oold water, and dried. INORGANIC SALTS. The amoi^nt of salts in urine may be determined by evaporating 6 to 10 grammes in a porcelain dish. The residue is ignited at a slightly elevated temperature and weighed. The chlorides, sulphates, ])hosphate8, lime, etc., may be determined by the methods usually employed in inorganic quantitative analysis. -n 864 AlflMAL CHEMISTEY. r TJEINAEY DEPOSITS. . If the urine has produced a deposit, its natme may he determined by plunging one end of a glass tube, whioh has been drawn out to a point, down into the deposit, the other end being closed by the finger ; the finger is then removed, a quantity of the deposit allowed to run iuto the tube, the finger replaced, and the tube withdrawn. A certain quantity of the deposit is thus obtained, whioh may be tested -with different reagents and examined under the microscope. Urine whioh contains an excess of uric acid is acid and limpid ; the deposit is then crystalline and slightly coloured, and is soluble in potassium or sodium hydrate, insoluble in ammonium hydi-ate or acetic acid. Nitric acid imparts a darker colour to urine rich in uric «cid ; a brown deposit may also be formed, which is soluble in alkalies. Urine containing urafrs becomes turbid shortly after voidance ; this deposit is white, or coloured and muddy. On heating it dissolves, as well as by adding potassium or sodium hydrate. Sometimes this deposit is coloured. Urine cdhtaining earthy phosphates may become turbid, but this deposit cannot be confounded with the preceding, as it does not dissolve on heating, is soluble in acetic acid, while not soluble in potassium or sodium hydrate. Urinary deposits formed of calcium oxalate are white; URINARY DEPOSITS. 8^6 they are insoluble in ammonium hydrate and acetic acid; they also do not dissolve on heating, but are soluble in mineral acids. If the deposit were formed of calcium carbonate^ it would dissolve in acetic acid with the dirjengageraent of carbon dioxide. Deposits of ammonio-magnmum phosphate are white ; soluble in acetic acid insoluble in ammonium hydrate. Urine containing cyatin has an acrid and even repulsive odour. It furnishes a deposit which does not dissolve on heating, and is soluble in ammonium hydrate. Certain urines become turbid on account of the mucus they contain, or because decomposition has set in. The presence of bhod renders the urine red, the presence of bile greenish. Urines are sometimes met with which are whitish or opalescent; agitation with ether renders them clear. Blue and blackish urines also occur. If a drop or two of a urinary deposit is viewed throiKjh a microscope magnifying 250 diameters, and the preceding reactions employed, they will appear much more distinct. We would, however, add the following : Uric acid occurs in crystalline plates of a diamond shape ; their angles are often rounded off. These plates are often isolated, sometimes united in the form of rosettes and stars, and rarely in the form of needles. The urates are sometimes amorphous, sometimes crystalline. Deposits of urates may be distinguished from those of uric acid by their solubility in hot 866 ANIMAL CHEMISTRY. water. They axe generally found when the urine is alkaline. Crystals of xirates, heated with a small quantity of nitrio acid, give a residue of uric acid. More nitric acid forms alloxan, as do deposits of uric acid, and this yields a characteristic red colour with ammonium hydrate. Caloiura phosphate is amorphous. Ammonio-magnesium phosphate occurs in prismatic crystals. Calcium oxalate crystallizes in regular octahedrons. Cystiu, CgHyNSOj, occurs in beautiful hexagonal plates. It is obtained by treating the deposit with ammonium hydrate, and allowing the liq^oid to stand ; the oystin separates out, and by the aid of the micro- scope the form of the crystals may be distinctly seen. Under these conditions the uric acid would not dis- solve, a fact which permits of distinguishing bat ween deposits of oystin and those of uric acid. Cystin is neutral, insoluble in water, alcohol, ether, or acetic acid. It is soluble in the mineral acids, also in oxalic acid. Ignited on platinum foil, it gives off an allia- ceous odour. It is coloured, like uric acid, upon treatment with nitric acid and ammonium hydrate. It dissolves in alkaline solutions. Heated with potas- sium or sodium hydrate in presence of lead oxide, it blackens on account of the formation of lead sulphide. Cystin is of rare occurrence, and its physiological and chemical relations have not been fully studied. Loebisoh (1-182-231) has shown that no diminution UKINARY CALCULI. 367 urine la mtity of '6 nitrio cid, and .monium prismatio ihedrons. lexagonal osit with to stand ; he micro- lotly seen. I not dis- r bstween Cystin ifl or acetic ) in oxalic an allia- icid, upon 1 hydrate, jvith potas- oxide, it Id sulphide, lysiological y studied, diminution of urea or uric acid occurs in cases oi cistinuria, though earlier investigators, and recently also Nieman (1-187-101), have come to the conclusion that urio acid at least decreases. Nieman estahlished in the same research that there is no change in amount of Biilphur in urine by reason of the presence of oystin. Pw« may be recognized by the spherical globules, in which two or three nuclei are observed, on the addition of acetic acid. This matter is converted into a jelly- idke mass in contact with potassium or sodium hydrate. Mucus may be distinguished by its ropy consistency and its coagulation with aoetio acid ; various kinds of cells are observed floating in the liquid. In these deposits epithelium cells are almost always found ; they are oval or irregular. Wo also find in urinary deposits : Blood Globules. — If the urine remains acid, they appear as quite characteristic discs ; if the urine becomes alkaline, they are destroyed. Tube Casts. — These may be: epithelial, fibrinous, mu- eous hyalin, (or colloid) and amyloid. The first have special diagnostic importance in diseases of the kidneys. These casts are generally nearly straight, though sometimes curvilinear, and not unfrequeutly are difiicult to find. The epithelial cells which cover them are nearly normal in appearance. Epithelial Cells. — These may originate from the kidney, the bladder, the ureters, or the canal of the urethra. Vibrions. — Linear in form, and exhibiting character- istic movements. 868 ANIMAL CHEMISTRY. r UEINARY CALCULI. Physical Aspect. — 1. TJrk Acid. — Form, round; colour, brown or reddish ; fracture, earthy or partially crystalline. When sawn through, a powder is obtained ' resembling the sawdust of wood. 2. Urate of Ammonium.— T\\q%q calculi are small, and of a clay or ash colour, with an earthy fracture. They are formed in concentric layers. 3. Cydin, — These calculi are voluminous, pale yellow, rounded in form, glossy, crystalline, and sometimes 'striated. 4. Cahium Oxalate. — Calculi of this substance are called mulberry calculi, from their resemblance to the fruit of the mulberry-tree, their surface being covered with rounded tubercles. They are usually grey, though sometimes dark brown, which colour is due to the organic matter which covers them. Their fmcture usually is granular, sometimes crystalline. 6. Ammonio-magnesium, Phosphate. — These calculi are white, crystalline, semi-transparent, covered with small brilliant crystals ; they are very easily pulverized. 6. Calcium Phosphate. — These calculi are white, amorphous, and formed in concentric layers. The following table indicates in brief the method to be followed in examining different calculi. We should mention, however, that calculi are not always composed of a single siibstauce ; they are quite frequently formed of several compounds. This table of reactions applies as well to urinary deposits. '*^^fc ^"iv-ii-:^/i">'''— '"■^''-'-Jij^i'-^' "•■■■ i'%. ^/. IMAGE EVALUATION TEST TARGET (MT-3) V ^ {/ Jy^^'i^^ % Ua fA 1.0 I.I ;ff i- 112.2 U! 1^ 2.0 1.8 125 1.4 1.6 41 6" ► r,' U-.. Photographic Sciences Corporation 23 WEST MAIN STREET WEBSTER, N.Y. 14580 (716) 872-4503 .MsMMMMiMSMMiV L<9 % CIHM/ICMH Microfiche Series. CIHM/ICMH Collection de microfiches. Canadian Institute for Historical Microreproductlons / Institut Canadian de microreproductions historiques •JSIH*«iKr; ■wil l ■ i i w."" !! .wji!8 ''tr gyffy, ''! !P ''yK' '^ K ^'M'i "''^''iJSESigS^'J^ "S5;.»-?*?T^-^ J'l ;i' MUCUS. 373 Jt_^^mostreadil, extracted from pulmonar, e.peo- acid added The turbid liquid is washed ou a filter with dibte acetic acid as long as the filtrate gives a preoTpiT e wth potassium ferrocyanide. The solutionf are' hea Irom the solution by acetic acid. This body appears to be argely soluble in water; it is prec^ifable by alcohol and dilute acids, and soluble in alkalies ^ It IS distinguished from albumen in not coagulating Vhoat. It also furnishes tyrosin under the fct on of dilute sulphuric acid. G. Gaelchli (18-78-77) found that mucin on putre- fyn^g^generated indol, phenol, and a .gallike Normal mucus does not contain albumen An analysis of uasol mucus by Nasse yielded : Water Mucin Lactates and extract soluble in alcohol Extract soluble in water and phosphates Alkaline chlorides Sodium hydrate ... 1000.0 J f "■: M \ ■'. V {if fa I 'f 'r- '^. If- 1^ MM 374 ANIMAL CHEMISTRY. Urine left standing for a short time often deposits mucus which is whitish, soluble in the alkaUes, and partially in acids. It facilitates the transformation of the urea present into ammonium oarbouate. Serosity effects the lubrication of various surfaces of the body, preventing friction ; its composition varies slightly in different organs. Albumen, mucus, and soda are ordinarily found in it. Synocia is thv3 serosity which lubricates the joints. It is dense and slightly alkaline. It differs from mucus in containiug albumen. According to Berzelius, it contains : — Water ....•• Albumen ..... Extractive matters and soluble salts Calcium phospliate Its composition, however, varies according to amount of exercise taken. 926 64 6 1.0 ANALYSIS OF THE HYDROCEPHALUS FLUID. 0.112 0.124 0.664 trace*} Mucus with a trace of albumen Sodium carbonate . Sodium chloride Potassium chloride and sulphate Calcium phosphate Magnesium phosphate . Iron phosphate . . • "Water 0.020 99.080 100.000 (Marcet.) . deposits ilies, and [nation of lurfaces of on varies icus, and he joints, om mucus 926 64 6 1.0 to amount UID. 0.112 0.12-t 0.664 traces 0.020 9.080 0.000 tfarcet.) COLLOIDIN. ANALYSIS OF 'SUE IIYDROPSICAI, FLUID. 375 Albumen . . . . . 2.38 Urea 0.42 Sodium chloride . . . . 0.81 Sodium carbonate .... 0.21 Sodium phosphate, with traces of sodium sulphate . . . 0.06 Mucous substance . . . . 0,89 Water 95.2:i 100.00 (Marchand.) VESICULAR SEROSITY. Coagulable albumen 5.25 Albumen more soluble in water 0.50 Salts 0.26 Water !);3.99 100.00 (Brandes and Ileinuiim.) CoLLOiniN. — Gautier, Cazeneuve, and Daremberg (97-[2] 21-482) have examined the jelly-like couteuts of a large ovarian cyst : they diluted the same with water, heated to 110 degrees in closed vessels, filtered after allowing to cool, dialyzed the filtrate in order to remove the salts, and precipitated with alcohol, whereby they obtained a white floceulent mass, soluble in water, 376 ANIMAI- CHEMTSTRV and not precipitated either by metallic salts or mineral acids, but procipitablo by tannic acid and alcohol. Thoy have called this substance colloidin, and give as its formula C,,TI,-NO,.,. According to Goi-up -Besanez this body is closely allied to mucin. MILK Milk is a white, opaque liijuid, inodorous while cold, and of a slightly sweetish taste. Its density, varies but little : — Human tni] Cows' » Goats' j> Asses' » Sheep's >> . 1.0320 . 1.0300 . 1.0341 . 1.0355 . 1.0409 Human milk is alkaline. The milk of horbivora has generally the same reaction. That of carnivora is believed to be acid ; at least it acidifies so quickly when onoe drawn that it is difficult to state its reaction positively. Milk is formed of an almost colourless and trans- parent liquid, in which float an immense number oi oleaginous globules. These globules are visible only under the microscope; their size varies from 0.0027 m.m. to 0.0041 m.m. They are opaque, and it is to these globules that the opacity of the milk is due. The fatty bodies of which they are formed are probably MILK. 377 or mineral ,d alcohol, md }?ive as ip -Besanez while cold, 1.0320 L.o;jOo 1.0341 L.0355 1.0400 horbivora larnivora is lickly when ts reaction and trans- niunber oi ire visible aries from jue, and it nilk is due. re probably contained in an albuminoid membrane. If to milk we add a little potassium hydrate and ether, the alkali disRolves the membrane, the ether absorbs the fatty bodies, and the milk is changed into a limpid, transparent liquid. On placing some milk under a microscope, and moistening it with a drop of acetic acid, the membrane will be seen ta be attacked, and the fatty bodies will immediately run together, while if it be simply agitated with ether, the globules remain unchanged. liobiii, however, supposes that the milk globules have no special envelope, but are surrounded by a thin layer of a saponaceous matter formed of fatty bodies, salts, and allmminoid compounds. Milk left to itself separates into two layers; that formed above, by the union of the globules, constitutes the cream, that bslow forms a white liquid, having a slightly blue tinge. On subjecting milk to a violent and prolonged beating, the globules unite and separate from the liquid, and butter is obtained. The fatty bodies of milk are formed of several principles : — Butyrin, caproin, caprin ; about . . 2. Olein 30. Margarin 68. And a small amount of stearin. But these proportions are necessarily very variable. R Tisserand (46- [3] 9-440) has summarized the following data : — 1^ 378 ANIMAL CHKMISTRY. I. The separation of cream occurs the more promptly accordiug as the temperature approaches 0°. II. The lower the temperature the larger the volume of cream and the yield of butter ; at the same time the butter milk, butter, and cheese, are all of a better quality. In human milk the mean percentage of butter is 2.42. It ranges between 2.80 and 3.00 in cows* milk. According to different experimenters the margarin is very impure ; it contains stearin, myristin, and even other compounds. The lower layer contains various substances, of which the principal ones are : — Casein, an albuminoid matter previously described : the milk contains more of this substance after a nourishment of nitrogenous food tliau after one of vegetable matters. Sugar of milk. Different salts, principally phosphates and chiefly calcium phosphate ; sulphates are not present. Milk allowed to stand in the air rapidly loses its alkaline retietion and becomes acid. It then coagulates. This effect is due to the lactic acid which forms spon- taneously in milk. It is formed by a fermentation called lactic fermentation. The sugar of milk is the substance which is trans- formed into lactic acid with the co-operation' of nitro- genous ferments. The coagulum is formed of casein and fatty sub- lore promptly 1°. iT the volume same time the of a better of butter is .50 hi cows* the margarin ;tin, and even ubstances, of ly described : mce after a after one of i and chiefly sent. )idly loses its en coagulates. I forms spon- fermentation hich is trans- tlon' of nitro- ad fatty sub- MILK. 379 stances the liquid which remains is known as butter milk. A. Vogel (75-23-505) confirms the observations of Schwalbe (36-1872-833) that oil of mustard pre- vents the coagulation of milk ; according to his investi- gations the formation of lactic acid is in a great measure hindered by the presence of the oil of mustard. Oil of bitter almonds and oil of cinnamon prevent the formation of this acid to a less degree, while oil of turpentine, oil of cloves, benzol, carbolic acid, carbon' bisulphide, and hydrogen sulphide are almost without action. It is an alkali, soda, which holds the casein in solution in fresh milk, and milk may be kept fresh for a very long time by simply adding to it a few thousandths of an alkaline bicarbonate. On the other hand, milk will at once coagulate on the addition of an acid. Besides the acids, a large number of substances possess the j)roperty of causing milk to coagulate ; such are alcohol, tannin, different salts, many plants which are not acid, the flowers of the artichoke, of the thistle, and of the butter wort (P/w^/. iciiJa riOle, for it is observed to give rise to fibrin and other mtro- genovis substances under certain circmustances, and especially in the incubation of the egg; -^^^^-^^ ologlsts have also thought that m digestion all n o- geifous substances are conve-ted into albumen, and that fn nutritioTi the albume'. is changed into fibrin a substance which, from the facility with which it coagu- lates, is the principal agent in the creation and renewal of the tissues, that is, of the solid portions of our bodies. Ml'SCUI.AR TISSUK. 888 0.025 0.2150 02.875 lOO.OUO ntly I'ouiid in )m milk sugar, I regard to the plea (albumen, ed into assimi- inner in which substances the principal rdle, ,iid other uitro- imstances, and certain physi- 3stion all nitro- umon, and that into fibrin, a which it coagu- on and renewal )ortions of our These ideas are probably exaggerated, or at the least their correctness has not been demonstrated. Muscular Tissue.— The muscles are constituted of a reddish contractile tissue, formed of fusiform olon- gated colls and of striaiod filaments, constituting an external envelopo, called the sarcolemma, and ol' inter- nal substances, from which a variety of fibon, syntonin, may be 'ixtracted. This latter is probably the substance into which albuminoid matters are changed durinj^ digestion in the stomach (parapeptone). Solutions of syntonin in adds are not coagulated by boiling ; tliey aro precipitated by chlorides and alkaline sulphates, Syntonin dissolves in caustic alkaline liquids and in dilute solutions of carbonates, and is repreiipi- tatod when these solutions are neutralized, oven in the presence of alkaline phosphates. Tliis last character distinguishes it from the albuminates. The fibres of the muscles are surrounded by a fluid ■which -nay be considered ^s the plasma of the nuiscles. It may be prepared accMiding to Kiiiine by removing the muscles of un animal recently killed, and freezing thei'i at ' temperature of about -7°, whereby they become very brittle. Tliey are pulverized in a well- cooled mortar, and thereupon subjectetl to a heavy prchhiu'o in an appropriate press. A liquid is thus obtained, which is placed upon a filter surrounded by a refrigerating mixture. The liquid, which filters very slowly, is opaline-\cllowish, viscid, and alkaline. It coagulates at ordinary temperatures, furnishing tmtm 884 ANIMAL CHEMISTRY. uiyoHin, which raoy be readily obtained by causing the filtrate to fall into water at the ordinary temperature. If acid solutioTiS of myosin are saturated, it is then no longer this body which precipitates but syntonin. Syn- tonin differs from myosin by not dissolving in solutions containing less than 10 to 12 per cent, of common salt. Myosin may also be. obtained more simply by pounding flesh with water containing 8 to 9 per cent, of common salt. After allowing this to stand twenty-four hours it is filtered by being pressed through cloth, and the myosin precipitates on pouring the liquid into water. The liquid which remains after the coagulation of myosin contains, according to Kiihne, two albuminoid substances, one coagulable at 76°, the other at 45°, and alkaline albuminates; also salts, wliich are chiefly phosphates, lactic acid, and lactates ; sugar and various organic substances, as creatin, creatinin, inosic acid, inosite, sarcosin, sarkin, and ^anthin. This liquid is coagulable by heat, and of a red colour ; its acidity is due to lactic acid and acid phosphate of potassium, which may be extracted from the muscles by dilute alcohol. It is claimed by Fremy and others that there exists in the muscles a special acid, called oleophosphoric acid, and that this acid is combined with sodium. According to Dubois Eeymond, the muscles do not possess an acid reaction imtil after death, and while contractile their reaction is slightly alkaline. In certain pathological states, urea, urio acid, and various other products are present. r causing the temperature. it is then no itoniii. Syn- l in solutions common salt, by pounding .. of common ;y-four hours loth, and the into water. )agulation of ) albuminoid r at 45°, and are chiefly r and various inosic acid, 'his liquid is its acidity is af potassium, es by dilute ; there exists osphoric acid, n. iscles do not h, and while lie. xio acid, and COMPOSITION OF FI.KSH. 385 H. Struve (60-'7G- G2-3) find? in fatty muscular tissue a new body which gives the absorption spectra of blood, but is cliiinged, unlike the latter, by the action of alkaline sulphides and acids. COMPOSITION OF FLESH. Pectoral Muscles. Water . . . . Muscular fibres, vessels, and nerves . Fats . Extractive matters Cellular tissue . Soluble albumen Man. 7^.46 16.83 4.24 2.80 1.92 175 Woman. 74.45 15.54 2.30 3.71 2.07 1.93 100.00 100.00 (Von Bibra.) Flesh leaves from 2 to 8 per cent, of ash, formed chiefly of alkaline and earthy phosphates; sodium chloride and sodium sulphate are also present. The brcth produced by digesting muscular tissue in water contains, according to Chevreul : — Water 988.57 Organic substances dried in a vacuum 12.70 Salts (phosphates, sulphates and chlo- rides of potassium, sodium, calcium, magnesium, and iron) . . . 3.23 1004.50 M wi t«i mi 386 ANIMAL CHKMISTRY. Cheat, N, C,noN.,0_, + H,0. Creatinin, C4H7N,0. SaRCOSIN, O3H7NO2. These three bodies have the highest importance in conuection with the study of muscular tissue. Liebig found in : Muscular flosh of the ox . 0.69 creatin. „ „ „ horse . 0.72 „ Creatin is prepared by treating meat cut into very small pieces with cold water as long as anything is dissolved, and the solution evaporated ; the concentrated liquid, filtered, furnishes creatin. This body occiu-s in rectangular prisms, without taste or odour, soluble in 74 parts of cold water, but more soluble in boiling water. On being boiled with strong acids it furnishes creatinin. HCl + C.HgNjO^r^HjO + C.H^N.OJICl Chlorhydrate of creatinin . This chlorhydrate decomposed furnishes creatinin as a crystalline allvaline substance, more soluble than creatin in both Avater and alcohol, Creatinin may be reconverted into creatin by boiling with lead oxide. It forms with zino chloride a combination which is but slightly soluble in cold water. According to Neubauer, creatin does not exist in flesh, but creatinin only, and the creatin which is found is formed by the transformation of the creatinin. Creatinin also exists in urine, and in the muscles of the crustaoea. K*^ Bs creatinin as soluble than reatinin may ith lead oxide. ,tion which is According to but creatinin brmed by the in also exists acea. XANTHIN. 387 On submitting creatinin to a prolonged ebullition with baryta water another substance is formed, called mrcosin. H,0 + C.HBNsO^rrCIT.NjO +a,H7N02 Urea. Sarcnsin. This body crystallizes in rhombic crystals, wliieh are colom-less, very soluble in wa.ter, somewliat soluble in alcohol and insoluble in ether. Sarcosin melts at a temperature above 100', and is volatile. It possesses the characters of glycocol and its homologous sub- stances. Inosu: Acin.— The mother liquor of creatin is acid, and has an odour of meat broth. Extract of meat treated with baryta furnislies on evaporation inosate of barium, and the liquid contains inosite. The formula of inosio acid is usually given as C5HhN',0,3, though some >mth()r.< regard it as CioHnN.O,, {'2l--m). Xanthin.— CjH.N^Oo. To prepare this substance muscular tissue is well beaten, and alcohol and water successively added as long as anything is dissolved. These two liquids are now united and heated, in order to coagulate the albumen and drive off the alcohol. The liquid is filtered, and lead subacetate added. The precipitate is collected, washed, and decomposed with hydrogen 8uli)]iide while suspended in water. The filtered liquid is boiled and evaporated. The xanthin deposits in a uon -crystalline mass. It can also be prei)ared from the liver. Xanthin is soluble in cold 388 ANIMAI, CHEMISTRY. water, alcohol, and ethor. It forms with acids salts which aro generally crvstallizablo ; it is precipitated even from very dilute solutions by mercuric chloride or nitrate. It dissolves in alkaline liquids. If calcium hypo- chlorite be added to one of these solutions, a greenish precipitate is formed which becomes brown aad then disappears. This reaction is quite delicate, and a useful test. OTHER TISSUES. Cells.— The cells are the simplest structures of the body. Their mass is very minute, and their form variable. They are not always enclosed by an envelope, and they vary in their chemical nature. They contain one or more nuclei, and when new a gelatinous liquid ('protoplaxm), capable of contractile movements under the influence of chemical agents, of electrical or meclianical forces. If old, they contain different matters, derived either from modifications of the proto- plasm or the introduction of foreign substances. The protoplasm cf)iigalate3 after death. It appears to contain myosin, also other albuminoid, fatty, and saline constitvieiits. Areolar Tissue is chemically characterized by the action which hot water has upon it. At first it swells, assumes a jelly-like appearance, and finally dissolves, producing gelatin, which, on cooling, is of a tremulous consistency. J h acids salts precipitated c cliloride or ,lciura hypo- s, a greenish wn aud tlieu cate, and a ictures of tlie [ their form an envelope, rhey contain tinous liquid ments under electrical or lin different of the proto- mces. It appears i, fatty, and erized hy the ) appearance, I, which, on TISSUES. 389 Dilute inorganic acids and dilutn alkalies also elFeot this transformation. There is believed to exist in tliia tissue a substance (coUagene, glutine, golino) analogous with ossein, which, in contact with hot water, funiislies gelatin; also a substance (elastin) not furuisliing gelatin. , Tiinnin and mercury dichlpride form with these matters imputrescible compounds. Cellular tissue is converted into a transparent and colourlfss jelly by the action of strong acetic acid ; but the fibre is not attacked, for if the acid be saturated with ammonia water it reappears in its ordinary condition. Tlie c/mfic iimtcfi do not dissolve even after an ebulli- tion of sixty hours, and do not furnish gelatin. Hydrochloric acid dissolves them, turiiing brown at the same time. With sulphuric acid they furnish leucin and not gelatin. This may be obtained quite piire by boiling cellular tissue with water, then with acetic acid, and macerating the residue with a dilute alkaline solution. To the product thus obtained the name of e/astin has been given. The mucous areolar tkbiie differs chemically from ordinary conjunctive tissue, in that it does not furnish gelatin on being boiled with water. The reticular iisfiiie of the cutis contains the pig- ment called melanin, the colouring matter of the skin. This tissue is not reproduced completely where destroyed, but is replaced by cellular tissue, and the cicatrix is due to the fact that this latter tissue is colourless. 390 ANIMAI, CIIKMISTRY. The epi'fermis inrnhhes gelatin on boiliag with water. It appears to contain iron, and H. P. Floyd (84-34 17!') has found it to contain in the negro twice as maciv of this element as in whites. Sulphuric acid softens and dissolves it, nitnc acid colours it yellow, alkalies dis^lve it, the sulphides render it of a brown colour, and silver salts blacken it. The epidermis, hair, bristles, feathers, nails, horns, and epithelium have an almost identical composition. Carbon llydrogcu . Nitrogen Oxygeu and sulphur . Epi- dennis. 50.31 G.81 17.22 25.63 100.00 Epi- Hiiir and thelium. Uristle.s. 61.53 7.03 16.GI 24.80 100.00 50.00 O.tO 17.00 2G.G0 100.00 Nailf. 51.00 fi.S2 17.00 25.18 lOO.OO Feathers. 52.42 7.21 17. 8i) 22. 4 S 100.00 Horn. 50.94 G.G5 10.28 2G.13 100.00 The horny tissues are formed of cells containing nuclei which have united and dried. Indeed, when these different tissues are treated with alkaline solu- tions, ovoid cells are seen, eaf-h containing a nucleus. Sulphuric acid likewise renders this structure api.arcnt. This tissue leaves about 1 to 1.5 per cent, of ash on '^ Horn treated with fused potassium hydrate and with dilute sulphuric aei.l, furnishes tyrosin and leucin. Hydrochloric acid renders it blue, nitric acid yellow ; aqua regia attacks it with energy. Feathers possess the same general properties. Iho colour of the feathers is due to different pigments, rarely soluble in water, sometimes in ammonia, and ag with water. H. P. Floyd in the negro lites. it, nitric acid tlie sulphides ilts hlacken it. I, nails, horns, il composition. Feathers. Ilorn. fylA'l •)0.94 7.21 (1.05 17.8i) 10.28 22, 4S 26.13 100.00 100.00 ;lls containing Indeed, when alkaline solu- ling a nucleus. cturo apitarent. cent, of ash on ^drate and with md leucin. ric acid yellow ; )roperties. The jrent pigments, ammonia, and CARTIL.VGINOrS TISSirK. 391 ordinarily in alcohol. They generally contain less oxygen and more silica than horn and analogous tissues. Hair has the same composition and chemical char- acters as homy tissue. Its colour is due to oils of various tints. With age this oily secretion ceases to be produced and the hair whitens ; the white colour seeming to bo due to tlie fmt that the tubes contain no secretion, but are fillod with air. The fatty bodies of the hair are formed from llie volatile acids of perspiration, and also of margarin, ol«in, and stearic acid. Hoilgkinson and Sorby ob- tained (2H--J22-592) from black hair and feathers a black pigment, to which they ascriba the formula Hair contains 0.5 to 2.0 per cent, of inorganic sub- stances, containing a considerable proporfiou of iron and small qunatities o? silica. Mulder found in epi- dermis an organic sulphur compound he called /.v ratin. Oahtii.aginous Tissue. — The cartilages are ordi- narily formed of a flexible tissue, whose composition is not greatly diiferent as to its organic constituents from that of the preceding substances, thougli varying in organic composition with age and in the diiferent parts of the body : — Carbon 50.1)1 Oxygen {j.9() Nitrogen 14.90 Oxygen 27.23 100.00 i ^ 392 ANIMAI, (HKMISTIIV. Iloiipo-Soylor found in a proximate analysis of cartilago from the knee of a man aged twenty-two years : — 11,0 . . . Organic matter . Inorganic matter 70.09 24.87 IM 100.00 This tissue is not homogeneous ; under the micro- 8coi)(! it appears composed of a colourless fihro and cells containing granulated proto[)lasm The matter of the ceils is dilforent from the gelatinous substance forming their envelopes. It dues not dissolve in boiling water even under pressure. Tiie cartilaginous substance proper, cfirfi/df/riii, fur- nishes, with boiling water, a substance Avhich resembles gelatin in its composition, but from whi(!h it differs in several characteristics, and especially by its giving a precipitate witii acids, lead acetate, and alum, while gelatin gives no reaction with these substances. It is called by the name of choudrin. Chondrin turns the plane of polarization to the left. Treated with liydro- chloric acid it furnishes a variety of glucose {clioni/ro- (llncone) and various nitrogenous substances of which little is known. A distinction has lately been made between the cartilages just s]ioken of and the fibro-cartilages. These last contain a fibrous matter without nuclei, differing NEKVii TISSUK. 393 ) analysis of 1 twenty- two 24.87 1.54 100.00 5r the micro- liltro 1111(1 cells n Hitter of the iinoe forming boiling water r/ihirjriii, fur- ich resembles I it differs in its giving a alum, wliile auces. It is ■in turns the , with liydro- 'ose {clioii)lro- 3es of which between the lages. These ilei, differing from the ordinary oavtilaginous substanne l»y produoing with boiling water a suljstanre whioh is lm( slightly precii)i)atod by tannin. The lil)ro-(Mrtiliige of tlie knee must also be disfinguished from the jncccding, i'rom the fact that it prodtiees gelatin with boiling water. Cartilaginous tissue contains •">■") to 75 per cent, of water, 2 to 5 per cent, of fatty bodies, and 1.5 to 6 per cent, of minoral substances. Nkhvk Tissi'K — Of it are composed the nerves, ganglia, brain, and tlie spinal cord. It is observed to coutain cells and cylindrical tubes ; these are formed of an envelope of areolar and fibrous tissue and of a Bcmi-liquid medullary substance (myelin of Yirohow), which riifracts light strongly, and is sometimes observed to How out when a nerve is cut. These tubes are united in bundles which are enveloped in a colour- less, lustrous, and fibrous membrane sometimes called li(!Un7r/HHl(l. This membrane may be rendered apparent by treat- ing nervous tissue with a cold dilute solution of caustic potassa, which dissolves tlie nervous substance with the exception of the neurilemma. This membrane is dis- solved, on the contrary, by hydrochloric acid and strong sulphuric acid ; it is not coloui-ed yellow by nitric acids. The ganglions of the nervous centres are formed of cells of variable size, composed of a very thhi envelope and a nucleus containing a dense liquid, in which are granules in suspension. Concentrated alkaline solutions attack and dissolve ■■ i' % 394 ANIMAL CUKMISTRY. ^il ii the xiervG cells and tubes. Htrong inorganic acids Bhorton and thicken the fibres. An aqueous solution of iodine colours them bright yellow. A mixture of niercui'ous and mercuric nitrates renders tliem rigid and tenacious. The reaction of the nerves appears to be neutral during life, it booomcs acid after death, and finally, at the moment when putrefaction sots in, it lins an alkaline reaction. Diilercnt investigations made recently on the mutter of the nerves uiid liiain have shown that wo are far from completely undni;.standing its compositions ; Liebrich's proKu/on is now roganled as a mixture of W. Miiller's cerebrin and lecithin, aTid the same may bo said of Kohler's myoloidin and myeloidinio acid. TiiF CoNSTiTUKNis oi- THE Bkain, moro or less constant and normal, thus far determined with apparent certainty are : — W(t/ri; — albuminoid bodies resembling ni>/o.v'ii, — rM»fin {f)—nn(rokrmtiii,~HHch'in, — collafi('H, —soluble (ilbitmon, coagulating at 7rj\~cc)rhrin and lecithin,— yhjcct'inphoxplioric acid,— fats {?),—eholpnt<'rin, i)mit,—hypoxan th in , xaiit/i in, krcafin,— lactates,— vola- tile fattij acids and uric acid. Inorganic substances : calcium, potassium and maf/ncsium phosphates, iron oxide, silica, alkaline sulphates, sodium, chloride, and fluorine. (Korsford.) Although very extended and repeated investigations of the chemical nature of the brain have been made, )rgauic acids eous solution A. mixtiiro of s them rigid be ueutral id finally, ut I, it lias an )n tho Tiiattor that we are lonipositioiiB ; a mixturo nd the Hamo niyoloiJinio novo or less r'itii apparent 8 resembling 'n, — coUdijcH, ccirhrin and — c/iokulcrin, cfafcs, — vola- ' siibfttmices : sphafcfi, iron h/orklf, and ivestigations been made, ('ONHTlTtKNTS OK THK HRAIN. 396 it yet remains, chemically, one of the most iucomplotoly- known animal organs. It waH \V. Miiller who first obtained the nitrogenous neutral body from the bruin called crrvbrin. It is extracted on coogulating by heat an aqueous extract of the cerebral substancv, , this coagulum is separated and washed with water, and trcntod while boiling with a mixturo of alcohol and other, and filtei'cd hot. White flakes separate out of the solution, wliicii contains cholestorin, lecithin, and cerobrin. This matter is the cerebrio iicid of Frcray. Cerebrin has the formula C,,II,N(X, It is dissolved by sulphuric acid, the solution being of a purple colour. It is rendered resinous by hydro- chloric acid, and is transformed by boiling nitric acid into an oil which solidifies on o()C)ling. Gobley claims to have also found cerebrin in the yolk of eggs. E. Bourgoin (5>''j«.»(«nr->' ; -r-,-. ,-' £ 408 AMMAI, t'UKMIsri' Piis contains J.O to Ki por cont. orwiliiLlo matter, the must iiiiiKU'tuut of whifli is ulbuuion. Tlio (>xihtenoe of a siil)Htiiiu'e cttUod pyin has bwu tlolectod in it, hut aocording to Leliiniui this body is an ubnornuil j.roduot. It ^^cnorjillycontiiiiiH a hirgor proportion 1' sohiblo suits thiiii tliH 8unim of the Idood. Boodocker found in u pus slightly alkaline :— "Water . 88.76 Albumen ..... . 4.;}8 3'yiii 4.G5 I'litty bodies and cholesterin 1.09 ►Sodium cldoride 0.59 Other alkaline salts . . . . 0.(32 Earthy phosphates . . . . 0.21 100.00 Certain vo,rietie8 of pus have the property of impart- ing a blue tinge to linen. Fordos has discovered the principle which produces this o-iloration : it is a Ci-ystalline substance which he has named pi/ocynnhi. Pus swells, and assumes the appearance of gehiHn ou being niixrd with aramouium hydrate. This reaction distinguishes it from mucus. Pure pus, placed in a vessel and allowed to remain for several hours, separates into two layers. The lower, curdy layer contains the globules and the solids; the upper, opalescent layer constitutes the serum. l)lo matter, the 10 oxiKtenoe of tod in it, hut )nufil jirocliiot. ■f solublo salts ine : — 8H.7G 4.38 4.G5 1.09 0.59 '\-62 0.21 lOD.OO ty of irapart- iscovered the m: it is a d pyocyanhi. of gelaHn on rhis reaction sd to remain , The lower, e solids; the m. \ PVtB. 400 C. Tlohin gives the following analysis of the sonim in 1,000 parts: — 937.80 to 970.55 3.11 traces 0.50 1.87 .10 traces 4. (JO •J.2'2 2.20 3.11 .96 1.00 Water . Sodiu'u pliopphato . Phosjihato of soda Earthy and ammonio- niagncsium pliosphatcs Sulphates and ourbouates of sodium and potassium Suits of iron and silica Salts with organic acids, formiates, butyrates, vulorialDS, etc. Leucin, tyrosin, and ex- tractive substances Seroliu .... Cholesteriu Fatty bodies . Lecitliiu .... Mota-albumen and serin . Among the extractive substances there have been found: Parr globulin, tyrosin, leucin, xanthin, in-ea, glucose (in diabetes), bilirubin, uric and ohlorrho- dinic acids (in necrosis), and a special pus product, hydropsin. 15.00 20.00 1.00 8.30 3.50 10.00 10.00 19.00 G.OO 10.00 11.00 48.00 ^/^ -r!r-r^.»«- r" 410 LIST OF ORIGINAL AUTHORITIES. 6. 7. 8. 9. 10. 11. 12. i;j. 14. 15, 16. 17. AimiiK II (Icr fhcniio und I'liuiiiiai.'ic; V. Liel)iR u. W.ihl.T. Anniilcii ili'i- Phj'xik uiul Clu'inie voii rof,'^fn(lort'. Arcliiv (Icr rimnuiicic. Iliilli'liii (Ic III sdcii'tc d'cn- coiini^'. Kiilli'tiii do la .sofit'te dc Miillioiisi'. TIic Kiifi;iiic('r. <'li(iiiis<'lii's ( 'eutralblatt. Clii'iniciil Xf'Ws. ComptLs ri'iuliis. Duutsehe liidustriczeit. Zcitscliril't iiir l!iolof,'ic. ;or. Milchzc'itung (Dantzic). Practical Mpobanics'Joiimal. QuartcrlyJourn.of the Cbonu Soo. )RITIE8. t'iir prnkfisclii' lustriu u. Oowei'l)t'- ournnl of Arts, (Icr i)liysit)liiK'. L'. (i(iru])-lk'sari('Z. 1 K(l. 1H7H. ii^i'ii (Ics Guwer- ins iiir Iliinnover. s l'"iii'l)i'i'/('itiiiij<. 'lit. fVntnillmllu v. Arcliiv. V. Liesc- 1. (Vntriill)lutt. s' .Mii;f;izini'. Poljti'chn. Journal. 1. Noti/blatt V. r. ung (Diintzic). McohanicsMoiirnal. f'Journ.of tho Chem. MHT (»K OIlHilNAL AI'TIIOKITIKS. 411 33. Ackcrinnnn'Hflpworlio/i'itunn > 36. 34. Ilcpcrtdiy of putciit iavcn- UoiiH. 07. 3A. TcchnologiRto. HH. 3(i. .lahrt'dhcrioht dor rhcmio 37. ZcilHtlirift I'iir auuljtiHche 50. ('lu-mie. .'al Magazine (London). 105. Phann. Journal and Trans- actions. 106. Pharm. Zeitung (Bimzlau). 107. Zeitschriftfiir Chcm. Gross- gcwerbe. 108. Die Chera. Industrie auf der Austellung in Philadel- phia. 109. Zcits.liiitt fur Physiolog. Chemio. Ilopne-Styler. 110. Moniteur de la teinture. ES. E the Franklin In- 1 Chemist. (1 Gewerbe (Nurem- luchvoerterbuch der il3. 's C'hera.-tech. toi'ium. Iiical Magazine on). Journal and Tran3- .s. i^eitung (Riinzlau). ftl'iir C'iicm. Gross- be. u. Industrie auf der lung in Philadel- It fur Physiolog. o. Ilopne-Seyler. • de la teinture. INDEX. FAGB. Acenapthene, Q2Hio= 154-. 38 Acetatnide, C2 Hs NO=59. . 136 Acetanilide, C8lIi)NO=i3S. 130 Acetic oxide C.| He O3 =102 103 Acetochlorhydric glycol 63 Acetone, C3 Hg 0=58 99, 108 Acetyl acetate, C4 Ng O3 ... 103 Acetyl chloride, C2CIH3O. 103 Accyl hydride or aldehyd, C2H,iO=44 86 Acetylamine, C2 H5 N=43.. 129 Acetylene, C2 H2 =26 18 Acetylide, cuprous 19 Acid.acetic, C2 H4 O5 =60. . 99 Acid, aconitic, Cf, Hg Ob =95 174 Acid, acr) ..c, C3 Hi 02 =72. 91 Acid, adipic, Co H10O4 =148 91 Acid, alloxanic,C4 H4 N2 O5 125 Acid,alpha-cymic, CnMuOa 91 Acid, amalic, Q, H7 N2 O4 . . 169 Acid,anchoic, Cg H16O4 =iSS 93 Acid, angelic, C,-, Ilg 02 =108 91 Acid, anisic, Cs Hs O3 =152. 92 Acid, arabic, Ce H10O5 -342 217 Acid, arichidic, C20H40O2 . . 90 Acid, atropic.Cg Hs O2 =148 164 Acid, benzoic,C7 He O2 = 1 26 . . 91, 109, 126 Acid, benzoglycolic 126 Acid, butyric,C4 Ha ©2 . ..90, 108 Acid, cafTetannic 196 PAGE. Acid, camphic, CioHif,020=9i >68 Acid,campholic, CigHi804 .. 91 Acid, camphoric,CioHi804 41, 93 Acid, caprylic, Cs Hi602 ... 90 Acid, caproiCiCe H12O2 = 1 16 90 Acid, capric, CioH2o02 = 172 90 Acid, carballylic, Ce Hs Ofi . 95 Acid, carbainic, CH3 NO2 ... 1 1 Acid, carbazotic,( Picric) CH3N3 07=229 33 Acid, carbolicCe He 0=94. 32 Acid, carbonic,C2 n3 0=62. 92 Acid, catechic 196 Acid, cerotic, C27H54O. ..90, 180 Acid, chelidonic, C7 H4 Oo .. 95 Acid, chlorbenzoic,C7 Hg CIO = 130.5 160 Acid, cholalic, C24H40O5 =408 95 Acid,choIesteric, Cs HioOg .. 95 Acid,choloidic,CiiH3s04 = 39o 94 Acid, cinnamic, Cg Hs O2 = 14S 91. I" Acid,citraconic, C5 Hg O4 93, 121 Acid, citric, Ce Hs 07.H2 0= 192+18 120, 95 Acid, coccinic, Ci3H2602 ... 90 Acid, comenic, Ce H4 O5 .. . 95 Acid, coumaric, Cg Hg O3 . . 93 Acid, croconic, Cg Ih O5 . . 95 Acid, crotonic,C4 He O2 -.91, 17S Acid, cumic, CioHiaOj = 164 91 lwi^r .w. 'W i ? " j y** ' ^ ' w«^ ''j siMi j-^aa^r^r ieimr^r'^^jrvrr^'r. Miild 414 I N D i; X . Acid, cyanacetic, C2H:)(CN)0.. =85 103 Acid, cy anhvdric,! ICN = J 7 . 161 Acid.dextroracemic 117 Acid.dialuric, Ci Ha n'/Oi 125 Acid, dinitrobcii/oic, C7H.|(N02)aOj=2i3... 110 Acid,doeglic,Ci9H:i60a =296 91 Acid, c'laidic 1 77 Acid, erucic, C-jHioOi =338. 91 Acid, ethalic, CitiHwOj =256 179 Acid, etlivlsulphuric, QHsHSOt =126 71 Acid, formic, Cllj O. =50.98, ip Acid, fumaric,C4 II4 O4 = 1 16 93 Acid, gallic, C7 He O5 . -95. "97 Acid, glucic, C12 lis O9 =306 iS''^ Acid, glyceric, C3 He O.i . . . 93 Acid, glycolic, Q Hi 0:i .Co, 92 Acid, guaiacic, Cn lis On . . . 92 Acid, gumtnic, C12 II>i On- 217 Acid, hippuric, Oj II9 NO3 •• 125 Acid, insolinic, C9 Hs O4 . . . 94 Acid, itaconic, C5 Hg O4 .. 121 Acid, lactic, C3 Ho Oa ..92, i2j Acid, lauric, CiiH-iiOo = 200 90 Acid, leucic, Ce II12O3 = 132. 9- Acid,lichenstearic, Cg H14O3 92 Acid, lithic, C5 H4 N4 O3 . . 123 Acid, lithofellic, CjoHscOi . . 93 Acid, malic, C4 He O5 = 134 i'5 Acid, malonic, C3 H4 Oi • • • 93 Acid, mannitic 183 Acid, margaric, CnHsiOo . . . 177 Acid, meconic, C7 Hi O 143 Acid, melissic, CaoHooOj . . 90 PAOB. Acid, mellitic, Ci Hj O4 94 Acid, mesoxalic, Cs H2 O5 .. 94 Acid, inclaguiTiinic 217 Acid, monochloracetic, C2CIH3O2 =945 201 Acid, moringic, Ci5H2802 ■ . 91 Acid, moriiitannic 196 Acid, mucic, Co H5 Os =205 95 Acid, inyristic, Ci4n28O20- • • 90 Acid, ccnanthalic, C7 Hu02 90 Acid, ocnantliic, C14H28O3 . . 92 Acid, oleic, C18H31O2 =283. 91 Acid, opianic. . . 127 Acid, oxalic, C2 H2 O4 . ..93i >" Acid, oxarnic, C2 H3 NO3 . . 11 Acid, oxybenzoic, C; He O3 19.S Acid, oxybutyric, C4 Hg O3 92 Acid,oxycuminic, C10H12O3 92 Acid.oxynapthalic, CioHe O4 94 Acid, oxy valeric, C5 H10O3 .. 92 Acid, palmitic, Ci6H;s02 .90. i77 Acid, parabanic,C3 H2 N2 O3 125 Acid, paraflnic, C2|H|802 . . 23 Acid, paralactic 127 Acid, paramalic, C4 H4 O4 ■ • 1 16 Acid, paratartaric J 1 7 Acid, pectic, C16H22O5 =294. 218 Acid, pectosic 218 Acid, pelargonic, C9 H18O2 ... 90 Acid, phenic, C« He O =94 . . 32 Acid, pheny Isulphuric, Ce He 048= 174 32 Acid, phloretic, Cg H10O3 ■ . 9^ Acid. phtalic,C8 He O4 = 150 94 Acid, physetoric, CieHsoOa •• 9^ Acid, picric, Ce H3 (NO2 )3 O 33 4 PAGE. c, Ci Hi Ot . . . . 94 alic, Ca H2O5 .. 94 LiiTiinic 217 ;hloracetic, >2 =945 201 gic, CisHfflOa . . 91 tannic 196 , CgH5 0s=^o,s 95 tic, CuIIjsOjo- •• 0° halic, C7 HuOj 90 liic, CuHfflOa . . 9- C18H31O2 =283. 91 c... 1^7 , QII2 0.I ...93, 112 ic, Cj H3 NO3 . . 1 1 nzoic, C; Hb O3 1 95 ityric, Ci Hg O3 92 minic, C10H12O3 92 pthalic, CioHe O4 94 leric.CsHioOs.. 92 tic, CiiiH;a02 .90. 177 inic,C3H2N2 03 125 Inic, C2iH|802 . . 23 ictic 12^' lalic, C4 H4 O4 . . 1 16 irtaric 117 :,Cl6H2205=294- 2 18 dc 218 jonic, C9 H18O2.. . 90 c,CbH6 0=94.. 32 ■Isulpliuric, S=i74 32 etic, Cg H10O3 . . 92 ic,C8H6 04 =150 94 ;toric,CioHso02.. (,1 ;,C6H3(N02)3 33 INDEX. 415 PAOR. Acid, pimelic.Ci III jOi 93 Acid, pinaric,Cai)H;ip02 =302 41 Acid, pinic, C^jHaciO) = 302 . . 91 Acid, pipcric,Ci2Hio04 =218 94 Acid, propionic, C3 Hg O2 7^1 90 Acid, prussic, IICN = 27. . . 161 Acid, pyrogallic, Cti Hf, O3 . . 198 Acid, pyroligneous icx> Acid, p_yromeconic,Cr, H4 O3 92 Acid, pyrotartaric, Cr> Hg O4 = 132 9.S. '17 Acid, pyroterebic, Ce Hin02 . . 91 Acid, pyruvic, C;j H4 O3 =88 g'i Acid, qiiinic, C7 HiiOe =144. 93 Acid, quinotannic 196 Acid,raceniic,C4 Hb Or, =150 117 Acid, ricinoleic, Ci8H,;iO:i,y2, 180 Acid, roccellic, CiTH;fi04 . . 93 Acid, salicylic, C7 H5 O3 195,32,92 Acid, sarcolactic 122 Acid, scammonic, C15HK1O3 92 Acid, sebic, C10H18O4 =202.. 93 Acid, sorbic, Co Hg 0< =112. 91 Acid, stearic, Ci8H3f,02 . .90, 177 Acid, suberic.Cg H14O4 = 1 74 93 Acid, succinic, C| He O4 93, 115 Acid, sulphocarbolic, C6H6S04=i74 33 Acid, sulphoglucic 185 Acid, sylvic,C2oH:io02 =302. 41 Acid, tannic, C27n220i7=6i8 J96 Acid, tartaric, ^^4 Hf, Oe . ..i 16, 95 Acid, tartrelic, C4H4O5... 117 Acid, tartronic, €3 H4 O3 . . 94 Acid, terebic,C7 H10O4 = 1 58 93 Acid, terechrysic, Ce Ho O4 94 PAGE. Acid, thionuric, C4H5NO3 803=195.... 125 Acid{ tliymotic, CuHuOa .• 92 Acid, toluic, Cg Hg O2 =136 91 Acid, trichloracetic, HC2 CI3 O2 = 163.5 102 Acid, tropic, C9 HioOs = 166. 164 Acid, uric, Cr. Hi N4 0:\ =168 123 Acid, valeric or valerianic, Cb H10O2 =102 109, 90 Acid, veratric, CoHioOg... 94 Acid, xylic, C9 HioOi =150. 91 Acids 95 Acids, aromatic 91 Acids, fatty 90 Acids, general methods of preparation, 96 Acids, organic 90 Acids, defined 95 Acids, polyatomic 112 Acids, pyro 97 Aconitina, C30H47NO7 -533- 165 Albumen 228 Alcohol, amylic, C5 H12O . 56, 45 Alcohol, benzyl, C7 Hg 0= 108 46 Alcohol, butyl, C4 HioO=64 45 Alcohol, ceryl,C27H5fiO= 396 45 Alcohol, cholesteryl 46 Alcohol, cinnyl, C9 HioO. . 46 Alcohol, cuneol 46 Alcohol, cymol, C10H14O.. 46 Alcohol, melissic, CaoHezO . . 180 Alcohol, methyl, CH4 O. .45, 46 .\lcohol, myricyl, C30H62O.. 45 Alcohol, octy 1 , Cg H igO = 1 30 45 ■fe 416 INDEX. PAGE. Alcohol, ordinary, or ethyl, Q He 0=46 49 Alcohol, propyl, Ca Hg O... 45 Alcohol, sexdecyl, CieHsiO.. 4s Alcohol, sextyl, C'g I luO 45 Alcohol, vinyl, Q Me 0=46 45 Alcohol, xylyl.Cg IIioO= 122 46 Alcohols, diatomic 58 Alcohols, monatomic 44 Alcohols, polyatomic 59 Alcohols, sulphur 82 Alcohols, selenium 82 Alcohols, tellurium 82 Alcohols, tetratomic 59 Alcohols, triatomic 64 Aldehyds 86 Alizarin, QoHe O3 = 174. . . 39 Alkalaniides 136 Alkaloids 127 Allantoin, C4 He N4 O3 = 158 124 Alloxan, C4 H4 N-j O5 =160. 125 Alloxantin, Cg II10N4 Oio. . 123 Allyl iodide, C3 II5 1= 168. . 57 Allyl sulphide, Ce IIicS=ii4 57 Allyl sulpho-cyanide, C4ll5NS=99 57 Allylamine, C3 11? N=57. . . 127 Allylene, C3 H4 =40 20 Amane, C5 Hi2=72 23 Amber 26, 42 Amides 136 Amidoxypropyl, C3H4(NH2)0=72 75 Amines 133 Ammelide 172 PAGE. Ammonia aldehydate, C2n4 0NIl3=6i 87 Ammonia citrate of iron... 121 Vmmoniacum 43 Ammonias, compounds 131 Ammonium, cyanate,CH4 N2 172 Ammoniums 137 Ammoniums, quarternary. . 136 Amygdalin, CjoII^rNOu... . 193 Amyl, acetate, C7 H14O3 . . 56 Atnyl, chloride, C5H11CI.. 56 Amyl, hydride, Cj Hi2=72. 23 Amylamine, Ca Hi3N=87.. 121 Amylene, C5Hio=7o 23 Anhydride, tartaric, C4 H4 O5 =132 117 Aniline 30,127, 131 Anthracene, Ci4lIio=i78. .29, 39 Arabin Ci2H220ii = 342 217 Arbutin C13H16O7 =284 193 AricinaC23ll26N2 O4 =397. . 129 Arnicin 42 Aromatic compounds 89 Arsines 128 Asphalt 26 Assafoetida 43 AtropiaCnllasNOs ==289. 164,129 Balsams 41 Bases organic, 125 Bases quarternary, 136 Bassorin 218 Belladona 164 Benzene Ce He = 78 27 Benzine 24 Benzoic aldehyd, C7 He O.. 86 Benzol, Ce He ==78 27 PAOK. ehydate, '3 =61 87 ate of iron. . . 121 ' 43 )mpounds 131 :yanate,CH4 N2 172 137 quarternary . . 136 -2oII«NOii.... 193 ;, C7H14O3.. 56 le, C5 HuCl.. .s6 e, Cj Hi2=72. 23 i;8Hi3N=87.. 121 Hio=7o 23 irtaric, 132 117 30, 127. 13' :i4Hio=i78..29, 39 iOii = 342 217 16O7 =284 193 ;N3 04 =397-' ^29 42 pounds 89 128 26 43 NOs ==289.164,129 41 125 lary, 136 218 164 6=78 27 24 lyd, C7 He O.. 86 = 78 27 INDEX. 417 Benzone "9 Benzonitrile "'o Benzvl cliloride '-6 Benzylcne -" Bezoar -^7 Bidecane 28 Bidccvl hydride 23 Bilifulvin 257 Bilirubin 257 Biliverdin 257 Bile 250 Bile, action on food 258 Bitumen 20 Biuret >72 Blood 272 Blood, action of different gases on the 291 Blood, chemical pathology of the 294 Blood, coagulation of 276 Blood, gases of the 288 Blood globules 281 Blood, iron of the 287 Blood, uses of 293 Bones 399 Borneol .S8 Brain constituents 394 Brandy 5^ Brucia 161, 129 Butane 23 Butter 179 Butyl hydride 23 Butylamine 128 Butylene 20, 22 Cacodyl 79. 'OS Caffeia (caffein) 130, 168 PACE. Campholic alcohol > « 7 Camphor, artificial 37 Camphor 4° Camphor, monochlor 41 Camphor, oxy- 4' Camphor of Borneo 58 Cantharidin '('S Candles if> Cannabin 42 Caoutchouc 3^. 43 Caprylamine 127 . Caramel 190 Caramelane 190 Caramelene '9° Caramelin 19° Carbo-hydrates, defined 7 Carbon dioxide 3^3 Caries 40> Carbonic eiher 74 Cartilagein 392 Casein, animal 226, 233 Casein, vegetable 219, 234 Castor oil "So Castorin 42 Cellulose (cellulin) 203 Ccrasin 217 Ccrebrin 395 Cetene 33 Chitin 184 Chloral §7 Chloral hydrate 88 Chloroform 47 Chloropropyl : ' S Cholera ^'/' Cholcsterilene 255 Cholesterin 255 « m I 418 INDEX. Cholesterophan Cholin Chondrin 227, 314, Cliondroj,'lucose Chyle Chyme Chymosinc Cinchoniii (cinchonine). 129, Cinchoniciji (cinchoiiicinc). . Cinchonidiu (cinchonidhie) 158, Cinnamene Coaguluin Codeia 14.6, Colchinia Colloidin Collodion Colophony Compound ammonias Conia (conine) 141, Conicin Coniferin Convolvulin Conylia 141, Cotarnin Cream of Tartar. Crcatin 188, Creatinin Creosote Cresofol 29, Crotonj'lene Cumene Cumidin Cuprous acetylide Ciu'ari Curarina 'AOE. 169 2.SI 39-2 39-' 2()l) 2(,H -47 'S6 '58 129 38 281 129 163 375 208 4> 131 129 129 •93 193 129 '47 116 3S6 386 34 34 20 28 127 20 163 162 PAOB. Cyanopropyl i ^ Cyciamin loj Cymene -^^ Cy tiiogene 24 Cyniol ^, Cy>tin ,e, 1 )aphnin j„^ Daturia, (atropia) 164, 129 Decane ■,, -4 Dextrin 212, 214 Dental tissue 403 r^'"''i^''^^s 327, 347 Diastase 212 Diethylamine 128 Diethylpropyl 15 Diethylenic diamine 170 Digestion 237 Digitalin 166 I^'gitin 166 Dimethylphosphine 128 Draconyl 38 T'ropsy 297 Dulcite, (dulcose) 183, 181 Duodecylene 23 Dysentery 266 Dy stisin 253 Elaidin jy^ Elaine lye Elayl 21 Elemi a\ Emetia 167 Emetics 1J9 Emydin 226 Ergotin . , 42 ?'ry thrite 49 Esculin I9J IN DEX. 410 PAOK. '5 193 3S -24 4« 353 '93 164, 129 -M 212, 214 403 327. 347 212 128 IS line 170 237 166 166 line 128 38 297 ■) 183, 181 23 266 253 '75 '75 21 43 167 "9 226 42 49 •• '93 PAGE. Essence of mirbane 29 Essence of thyme 34 Essential oil of cloves 37 Essl. oil of berf^aniot 37 Essl. oil of copaiba 37 Essl. oil of cubcbs 37 Essl. oil of clcnii 37 Essl. oil of juniper 37 Essl. oil of lemon 37 Essl. oil of orange 37 Essl.#oil of pepper 37 Ethal '79 Ethane '3. '5. -3 Ethene '3> '5 Ether, acetic 1?, Ether, butyric S' Ether, chlorhydric 75 Ether, common 7° Etlier, cyanhydric 77 Ether, ethyl 7o Ether, formic 81 Ether, hydriodic 7^ Ether, hydrosulphuric 83 Ether, oenanthylic 81 Ether, oxalic 74 Ether, oxamic "7 Ether, sulphuric 7° Ether, valerianic 81 Ether, vinic 7° Ethers 69 Ethers, simple 69 Ethers, compound 73 Ethers, miscellaneous 81 Ethers, mixed 38 Ethine '3 Ethyl 'S PACE. Ethyl chloride ». 75 Ethyl cyanide 77 lithyl foruiiate 9 Eth'yl,i,'lycol 61 Ethyl-hexyl ether 84 Ethyl hydiide 23 Ethyl iodide 7f> Ethyl mercaptan 83 Ethylinethylaniline 3" Ethyl oxide (> li X . PAOK. Nonyl hydride jj Nony Icnc jj Niitrilion iif, Nutrition, role of mineral compounds in 330 Octane JJ Octylglycol yj Octyl liydride j^ Octylene a Oils, fatty ,7^ Oils, essential tf, Olein lyr " Oleomargarine" i^y Oleo-resins ^2 Opium 1^2 Orcin ,53 Organizable substances 20s Organometallic compounds. 78 Ossein 226, 2;j4 Osseous tissues -jyy Oxainide 7^ Oxanthracene 35 Oxycamphor ^i Oxygen 3,, Pancreatic juice 261 Pancreatin 262 Para-arabin igi Paralbumen 226 Plants, respiration of 201 Plants, nutrition of 204 Polyamines i-q Polymerides g Polymerism 9 Populin 103 Potassium, binoxalafe uj Potassium, ferrocyanide. ... 170 l>AOK Paraffin 22^ 24 I'apavcrin 129, 148 Paraniorphia 148 Paraniylcne 22 Pariipeptone 249 Pittiii 3,8 Pectose , 2j8 Pentadecanc 34 Pentadecyl hydride 24 l'»^'P>*>" 227, 247 Peptones 225, 249 Petroleum 24 Phenol 33 Phenol, pota^sic 32 Phenol, trinitric 30 Plienyl 30 Phenyl hydrate 32 Phonylamine 127 Phlorizin 193 Phlorylol 34 Phosphines J28 Phtalidamine 127 Picroloxin 160 Pinite x8i Pipcridine 141 Piperine 141 Pitch, Hurgundy 43 Plethora 295 Potassium, formiate 88 Propane ,3, ,5, 23 Propenyl 15 Propine 13 Propone 13 Propyl ,5 Propyl hydride 23 Propylamine 127 INDEX. 423 PAO«, 23, 34 >29. "48 148 32 249 3l8 , 318 24 ride J4 227. 247 22s, 249 24 32 = 32 ■ 30 30 32 127 «93 34 J28 127 160 181 14' '41 42 29s iate 88 '3. 15. 23 15 J3 '3 15 23 '27 PAOI. Propyleni' 2J Proplene iodide 64 Protein 225 Ptvalin 213, 127, 238 Pi'iK 407 P^in 227, 407 P^in-yanin 40S Pyrethrin 4- Pvrocatechlii 35- Pvrolignite iof> Pyroxylin 207 Qucreite '81 QiicrcUrin '93 Quinia, (quinine) 151, 129 Quiiiicia 154, «J9 Quinidia 129 Quinidia, oxalate of 155 Quinoidin 15^ Quinolein, (quinolin) 130,153,157 Quinovin 193 Rachitis 402 Radicles, defined «4 Radicles, organometnllic ... 78 Radicles, organoinetalloid. . 81 Reagent, Fehling's 187 Reagent, Haines' 187 R( agent, Troiiuner's 1S6 Resins 25, 41 Respiration 272, 301 Retinasplialt 25 Retiiiite 25 Rliigolcne 24 Rice 216 Rochelle salt 118 Rosanilin 3' Riitvlene 20 rAOE. Rye 2, 2(/t mi, 3^'S 352, 364 ••• 3.13 • • • 3.S6 ••• .343 ••• 343 • • • 35i ■■■ .113 ••• 343 ... 179 ... 52 ... 32 ••• 49 ... 28 . .. 127 ...46 ... 79 • 79. '-26 m^ 4 r<