A.~~~~~~~~~~~~~~~. 74/1~ V7 ita~yS-g/eS U /?f49V7 ,: I i. ~ ~"~, "'''" I 4 -3 N 4'. j B I' I OUTLINES PROXIMATE ORGANIC ANALYSIS. BY THE SA M3E A UTH10 R. l2mo, cloth, $1 50. CHEMICAL EXAMINATION os ALCOHOLIC LIQUORS. A MANUAL OF THE CONSTITUENTS ()OF TIIE ISTILLEI) SPIRITS FERMENTED LIQUORS OF CO0IMERCE, AND THEIR QUALITATIVE AND QUANTITATIVE DETERMINATIONS. () UTLTINES PROXIMATE ORGANIC ANALYSIS. FOR THE IDENTIFICATION, SEPARATION, AND QUANTITATIVE DETERMINATION OF THE MORE COMMIONLY OCCURRING ORGANIC COMPOUNDS. BY ALBERT B. PRESCOTT, PROFESSOR OF ORGANIC AND APPLIED CHEMISTRY IN THE UNIVERSITY OF MICHICAN, NEW YORK: 1). VAN NOSTRAND, PUBLISHIER, 23 MUIRRAY STREET, AND 027 WVARREN STREET.'Sm,.. Entered, according to Act of Congress, in the year 1874, by D. VAN NOSTRAND, In the Office of the Librarian of Congress, at Washington, D. C. PREFACE. THIS little work has been prepared more especially for the use of a class of chemical students who devote a semester to the analysis of vegetable products and other organic mixtures, taking previously at least two semesters in qualitative and quantitative analysis. After working with this class for several years, without other aid than a manuscript digest of directions and references, the author is convinced that a compilation in this subject is desirable-not alone for students in special applications of chemistry, but for the convenience of every general analyst. Proximate organic analysis is not altogether impracticable, and organic chemistry is not solely a science of synthetical operations even at present. It is true, as the chief analytical chemists have repeatedly pointed out, that in the rapid accumulation of organic compounds the means of their identification and separation have bbeen 5 PREF. A E'. left in comparative neglect. It is true, also, that the field is limitless; but this is not a reason for doing nothing in it. Fifty years ago, the workers in inorganic analysis were unprovided with a comprehensive system, but they went on exploring the mineral kingdom and using their scanty means to gain valuable results. That this compilation is a fragmentary and very brief exponent of this part of analytical science as it exists at present, the author is fully aware, but he hopes that, as a beginning, it may prove to be worth enough to afford an opportunity for its improvement hereafter. UNIVERSITY OF ICHIIGAN, Scptember, 1874. CONTENTS. PARAGtAPH. PAGE. PARIAGRAPH. PAGE. PRELIMINARY EXAMINATIONS. 23. Quinovic acid, - - - 38 24. Columbic acid, - - - 39 1. Carbon, uncombined, - 11 5 Genianic acid, - - 39 2. Carbon in combination, - 11 26. Carminic acid, - - - 40 3. Preliminary examination 2. Chrysophanic acid, - - 4 of Solids, - - 11 f28. Gambogic acid, - - - 41 4. Preliminary examination 29. Santalic acid of Liquids, - - - 12 5. References for Solids and Liquids; Fixed and Vola- SOLID VOLATILE ACIDS. tile; Acid, Fatty, Basic, 30. Benzoic acid, - - -42 31. Cinnamic acid, - - - 44 32. Succinic acid, - - - 45 SOLID NON-VOLATILE ACIDS. 33. Salicylic acid, - - - 47 34. Veratric acid, - - - 47 6. Tartaric acid, - - 14 35. Phenic acid, - - - 7. Racemic acid, - - - 18 36. Nitrophenic acid, - - 51 8. Citric acid, - - - - 18 37. Sulphophenic acid, - - 53 9. Aconitic acid, - - - 21 10. Malic acid, - - - - 22 11. Meconic acid, - - - 24 12. Digitalic acid, - - - 26 38. Lactic acid, - - - 5 13. Tannic acid, - - - 26 14. Gallic acid, - - - - 30 LIQUID VOLATILE ACIDS. 15. Pyrogallic acid, - - - 32 16. Quinotannic acid, - - 33 39. Formic acid, - - - 5 17. Catechutannic acid, - - 33 40. Acetic acid, - - - 58 18. Catechuic acid, - - - 34 41. Butyric acid, - - - 61 19. Morintannic acid, - - 35 42. Valeric acid, - - - 63 20. Caffetannic acid, - - 35 43. Separations, - - - 67 21. Boheic acid, - - -36 44. Volatile Fat Acids of the 22. Quinic acid, - - - 36 acetic series, - - - 67 8 COz~TEANTS. PA RAnnPRH. PAGE. PARAGRAP1. PAGE. FATTY ACIDS: LIQUID AND SOLID. 76. Caoutchouc, - - - 95 45. Non-Volatile Fatty Acids, 68. Colophony, - 95 46. Ricinoleic acid, 69 8. Copaiba resin, - 96 47. Oleic acid, - -69 Copal resin, - 248. ~inzoleic acid, -69 80. Dammara resin, - - - 96 48. Linoleic acid, - - - 49. Erucic acid, 70 81. Dragon's Blood resin, - 97 50. Lauric acid, - - 82. Gamboge resin, - - 97.51. Myristic acid, 70 83. Guaiacum resin, - - - 98 51. Palyrmistic acid, - - 70 84. Hemp resin, - 98 523. tearlic acid, - - - 70 85. Indigo-blue resin, - 99 54. Cerotic acid, - - 70 86. Jalap resin, - - - 99 >.'. 8-7. Jalapin resin, - - 99 55. Separations by Saponification, - - - - - 71 88. Convolvulin resin, - - 100 56. Separations by Fusion, - 89. La resin, - - - - 100 57. Separations by Solvents, 71 9 Mastic resin - - - 101 58. Quantitative Determina- 91. Myrrh resin, 101 tions, - -2 92. Olibanum resin,- - - 102 93. Peru balsam resin, - - 102 94. Podophyllum resin, - - 102 NEUTRAL SUBSTANCES: LIQUID oR 95. Sandarac resin, - - - 102 96. Scammony resin, - - 102 59.,Fixed Oils: (a) Liquid; (b) 97. Storax resin, - - - 102 Solid,. 72 98. Tolubalsam resin, - - 103 60. Methods of Examination 99. Separation of Resins, - 103 of Fixed Oils, - - 74 100. Volatile Oils: Classes of, - 104 61. Calvert's Methods, - 78 101. " Properties of, - 104 62. Tests with Argentic Ni- 102. " Solubilities of, - 105 trate, - 81 103. " How identified, - 105 63. Analysis of Butter, 81 104. " How separated, - 105 64. Analysis of Milk, 84 105. " List, with color 65. Separation of Fixed from and sp. gr., - 107 Volatile Oils, - 85 106. Examination by Alcohol, - 108 66. Glycerin, - - 85 107. Examination by Iodine 67. Methods of Analysis of and Bromine, - - 109 Soaps, - - 87 108. Examination by sulphuric 68. Resins: general- character- acid, etc., - - - - 111 istics, - - 92 109. Examination by Plumbic 69. Resins: how separated sulphide, 114 from other bodies, - 93 110. Examination by Sodium, - 114 70. Aloes resin; - 93 111. Resinified Volatile Oils, - 115 71. Amber resin, - 93 112. Turpentine oil, - - - 115 72. Ammoniac resin, 94 113. Valerian oil, - - - 115 73. Assafetida resin, - 94 114. Peppermint oil, - - - 115 74. Benzoin resin, - - 94 115. Canphoor, - 116 75. Canaiiba wax, - - - 9116. Creosote, - 116 COONTEXNTS.! PARAGRAPH. PAGE. PARAGnAPH. PA. GQ E, 117. Anthracene, - - - 117 137. Sulphuric and Chromic 118. Alizarin, - - - 117 acids, - - 146 119. Benzole; Petroleum, Naph- 138. Nitric acid, - -146 tha, - 118 139. Sulphuric acid and Nitrate, 147 120. Nitrobenzole, - - - 119 140. Chlorine, then Ammonia, -'148 141. Ferric Chloride, - - - 148 BASES: LIQUID AND SOLID.`142. Platinic Chloride (Quanti121. Anilin, - - - - 120 tative), - - - 148 122. Anilinof commerce, - - 120 143. Auric Chloride (Quantita123. Anilin Compounds, - - 121 tive), - - - - 150 124. Toluidin, - - - - 121 125. Methods of Determining GLUCOSIDES AND OTHER SOLID NETUAnilin, - 121 TRAL SUBSTANCES. 126. Alkaloids: classes of, - 123 127. Conia, - 123 144. Absinthin, - - - - 151 128. Lobelina, - - 123 123 Aloin, - - - 151 ~129. Nicotia, - 123~ 146. Amygdalin, - - -152 147. Asparagin, 152 130. Trimethylamia, - 123 148. Cantharidin, - - - 153 131. Comparative reactions of 149 Cathartin, - - - 15 Volattie bases, 124 150. Colombin, - - - 153 132. Non- Volatile Alkaloids: 151 Cubebin, 154 List, 1 125 152. Elaterin, - - - - 154 133. Table of Solubilities of, - 128 153. Frain, - - - - 54 134. Separation of, - - 130 154. Lactucin,....155 (1) Method of Stas-Otto, - 131 1 Phloridzin, 155 (2) Rodgers and Girdwood, - 132 (3) -Uslar and Erdmann, - 133 157 Quassin, - - 1 (4) Graham and Hofmann, - 134 18 Sarsaparillin, - 15 158. Sarsaparillin, - - - 156 159. Taraxacin, - 156 (6) Method of Dragendorff, - 134 160. Vanillin - 156 (7) Dragendorif (Alkaloids and 161. Separation of Glucosides, Glucosides), - - 136 etc6 etc.,...- 156 (8) by use of Alkalies, - 137 (9) Ether, Water, Chloroform, 138 NITROGENOUS NEUTRAL BODIES. 135. Identification as Alkaloids, 139 a. by Potassio Mercuric Io- 162. Albumenoids, - - - 157 dide, - - - 139 163. Ovalbumen, - - - 158 b. Phosphomolybdic acid, - 140 164. Seralbumen, - - - 158 c. Metatungstic acid, - - 141 165. Casein, - - - - 159 d. Potassio Cadmic Iodide, - 141 166. Milk Albumen, - - - 159 e. Picric acid, - - 142 167. Deterrm. Casein and Albuf. Tannic acid, - 143 men in Milk, - - - 159 g. Iodine in Iodide, - - 144 168. Quantitative Anal. of Milk, 160 136. Alkaloids with Sulphuric 169. Commercial Examination acid andlFri hde'sreagent, 1144 of Milk, - 160 10 (O'X N'NT'S. PAAGRaH. PAGE. E PARAGRAPH. PAGE. 170. Gelatin, - 160 187. Glucose, 168 171. Leather, 161 188. Lactose, - - - - 171 189. Sucrose, - -- 172 CARBOHYDRATES. 190. Mannite, - - - - 174 172. Gums,.161 173. Gum Arabic, - - - 162 ALCOHOLS AND THEIR PRODUCTS. 174. Gum Tragacanth, - - 162 191. -Methylic Alcohol, - - 175 175. Dextrin, - - - - 163 192. Ethylic Alcohol, - - 176 176. Starch, - - - - 163 193. Aldehyde, - - - - 177 177. Pectous Substances, - - 166 194. Sulphethylates, - - - 177 178. Pectose, - - - 166 195. Ether,- - - - - 179 179. Pectin, - - - - 166 196. Nitrous Ether, - - - 180 180. Pectic acid, - - - - 166 197. Chloroform, - - 180 181. Parapectin, - - - - 166 198. Chloral Hydrate, - - 182 182. Parapectic acid, - - - 166 199. Iodoform, - - - - 184 183. Metapectin, - - - 167 200. Croton Chloral Hydrate, - 184 184. Metapectic acid, - - 167 201. Amylic Alcohol, - - 184 185. Cellulose, - - - - 167 202. Fusel-Oil, - - - - 185 186, Nitrocellulose, - - - 168 203. Nitrite of Amyl, - - 186 O UTLINES OF PROXIMATE ORGANIC ANALYSIS. PRELIMINARY EXAMINATIONS. 1. CARBON (uncombined) is recognized by its sensible properties (as charcoal, graphite, or diamond), by not vaporizing when heated, and by resisting ordinary solvents —neutral, alkaline or acid-except that graphite is oxidized by digestion with chlorates and sulphuric or hydrochloric acid, or with bichromates and sulphuric acid, or with mnixed nitric and sulphuric acids.-Also, on ignition in the air, or in a close tube with oxide of copper, carbonic anhydride is obtained from carbon alone, as well as from its compounds. 2. THE COMPOUNDS OF CARBON-except the alkaline carbonates-yield carbonic anhydride when ignited in the air or in a tube with supply of oxygen (as with dry oxide of copper). The non-volatile " Organic" Compounds of Carbon leave a residue of carbon after partial combustion i.e., they carbonize by ignition. 3. Preliminary examination OF SOLIDS to determine whether inorganic or organic, or both. a. Heat gradually, to prolonged ignition, in a glass tube open at both ends, or on platinum foil. (1) The substance is permanent: Inorganic. (2) Carbonizes and burns away, leaving no residue: Organic. See 5, a. 11 12 PREbLIIVA4 I Y EXAMIIXA ION.S. (3) Carbonizes and leaves a fixed residue: Organic and Inor-. ganic. See c. (4) There is doubt as to carbonization: test according to b. (5) The substance vaporizes-wholly or partly: test according to b. Also consider ammronium salts, the volatile elements, and the inorganic volatile acids, oxides, sulphides, etc. Examine according to 4, b. b. Mix the (dry) substance. (free from carbonates yielding C002 on ignition) with dry oxide of copper; introduce into a short combustion-tube or a hard-glass test-tube; connect, by a cork and bent narrow tube, with a solution of lime or baryta, or basic acetate of lead, and ignite. If a precipitate is formed, test it as a carbonate. c. Ignite a portion in a porcelain capsule, until free from carbon-cooling and adding a drop or two of concentrated nitric acid from time to time, if necessary to facilitate the combustion. Submit the residue to inorganic analysis. Examine another portion for organic bodies-applying the solvents, as in 134 (9) or (7). For an index of some of the most common organic solids, see 5, a. 4. Preliminary examination of LIQUIDS, to determine whether partly or wholly organic or not, and to separate dissolved solids. a. Evaporate a portion, on a slip of glass, at a very gentle heat. If, after cooling, a solid residue is obtained, test it according to 3. If there is an insufficient residue, obtain for this examination a larger quantity by distillation, as directed in b. b. Distil from a small retort or connected flask, admitting a thermometer, using a very gradually-increasing heat, and changing the receiver as often as the boiling point is *seen to rise. Cool the residue and distillates. Test the solid portions according to 3; the liquid portions, also, according to 3, a or b-then referring as indicated in the next paragraph. For index of Organic Liquids, see 5, b. PRELIMJI-XA P. Y L-U ~ A1 1,0 A[. 13 5. c. SOLIDS. NON-VOLATILE. Fixed Oils-59, b; 60 to 63. Acids: ~Aconitic-9. Soaps-67. Boheic-21.'Resins-99, and 68 to 98. -Caffetannic-20. Alkaloids (fixed)-132 to 143. Catechuic-18. Carbohydrates: Catechutannic-17. Cellulose-185.,Carminic —26. Dextrin-175. "(Chrysophanic)-27. Gum-172. -Citric-8. Gun-cotton-186. Columbic-24. Pectin, etc.-177 to 184A Digitalic-12. Starch-176.,(Gallic)-14. Sugars-187 to 190. Gambogic-28. Albumenoids-162 to 167. Gentianic-25. Gelatin-170, 171.,Malic-10. Meconic-11. VOLATILE. Morintannic-19. Acids t'Benzoic-30. ~(Pyrogallic)-15. (Chrysophanic)-27. Quinic-22. i Cinnamic-31. Quinotannic —16. (Gallic)-14. Quinovic-23. Nitrophenic-36.,Racemic-7. (Pyrogallic)-15..Tannic-13. i Salicylic-33. &Tartaric —6. Succinic-32. Santalic-29. Sulphophenic —37. Fatty Acids: Veratric-34. Cerotic-54. -Camnphors-115, 101, and 111. Erucic (melts at 340 C.)-49. Anthracene —117. Lauric-50. Alizarin-118. Myristic-51. Anilin compounds-123. Palmitic-52. Chloral hydrate —198. Stearic-53. 1 Iodoform-199. Fixed salts of volatile acids. Salts of Volatile Alkaloids. b. LIQUIDS. NON-VOLATILE. VOLATILE. Acid:- Lactic-38. Acids:.Acetic-40. Fatty Acids: ~ utyric-41. -Linoleic (melts, 18~ C.)-48. Formic-39. Oleic-47. i Valeric-42. Ricinoleic-46. - Volatile Oils-105, 104, and 100 to 114. Fixed Oils-59. -Creosote-116. (Soft Soaps)-67. Volatile Alkaloids-131 and 126 to Glycerin-66. 130. 1 4 S0 L,.) O. - t'O LA I.ro;r A7 (Ar,7)S. Anilin — 11. Solvents-Continued. Solvents: Ether —95. -Alcohol-192. Co. Ethers-40b, 41b, 42a, Aldehyd-193. 44, etc. Amyl. Alcohol-201. Meth. Alcohol-191. Benzole-119. Nitrobenzole-120. Chloroform-197. Petroleum-119X. SOLID NON-VOLATILE ACIDS. 6. TARTARIC ACID. H12C4H1406. CLaracterized by the form of its crystals and its rotation of polarized light (a); by its odor Nwhen heated, and its color when treated with sulphuric acid (b); by the properties of its salts of calcium, potassium, lead, and silver (c); by the extent of its reducing power (d).Separa'ted (as free acid) from salts or other substances insoluble in alcohol by its solubility in that menstruum, and from aqueous solutions by its solubility in amylie alcohol (e); from alcoholic solutions by the iusolubility of tartrates in alcohol (c); fiom citric acid by the precipitation of calcium tartrate in cold water andcl of potassium tartrate in aqueous alcohol (c); from substances not precipitable by oxide of lead by the method given under Acetic acid at g (40). —b)etermined by acidimetry (f); gravimetrically as lead, calcium, or potassium tartrate (g); by sp. gr. of wjrater solutions (see Storer's'"Dictionary of Solubilities "). a. Ordinary tartaric acid, or "dlextrotartaric acid," crystallizes in colorless, transparent, hard, nlonoclinice (oblique rhombic) prisms, permanlent in the air, soluble in 1.5 parts cold water, 0.5 part hot water, 3 parts alcohol, not soluble in ether. The solution rotates the plane of polarized light to the right. b. When heated to 170~ to 1800 C., the crystals melt with formation of metatartaric acid, etc.; by higher heat in the air, arious clistillation products are generated, and the mass burns with the odor of burnt sugar and the separationl of earbon.:~'; CTA -1 RI O1l'IP A CID. 1C 5 Pure tartaric acid dissolves in cold concentrated sulphuric acid, colorless, the solution turning black when warmed. c. The normal tartrates of potassium, sodium, and ammonium, and the acid tartrate of sodium, are freely soluble in water; the acid tartrates of potassium and ammonium are sparingly soluble in'water; the normal tartrates of non-alkaline metals are insoluble or only slightly soluble in water, but mostly dissolve in solution of tartaric acid. Tartrates are insoluble in. absolute alcohol. Aqueous alkalies dissolve most of the tartrates (those of mercury, silver, and bismuth being excepted), generally by formation of soluble double tartrates. For this reason, tartaric acid prevents the precipitation of salts of iron and many other heavy oxides by alkalies. Hydrochloric, nitric, and sulphuric acids decompose tartrates. A solution of tartaric acid added to cold solution of lime, leaving the reaction alkaline, causes a slight white precipitate of calcie tartrate (distinction from Citric acid, which precipitates only when heated). The sanme precipitate is produced with a tartrate and calcic chloride solution; but not readily, if at all, with free tartaric acid and calcic sulphate solution (distinction from Racemic acid). The precipitate of calcic tartrate is soluble in cold solution of potassa, is precipitated gelatinous on boiling, and again dissolves on cooling (distinctions from Citrate), and is dissolved by acetic acid (distinction from Oxalate). Solution of potassa, or potassic acetate, precipitates concentrated solutions of tartaric acid, as the acid tartrate of potassium in microscopic crystals of the trimetric system, soluble in alkalies and in mineral acids, not soluble by acetic acid. The precipitate is soluble in 230 parts of water at 150, or in 15 to 20 parts of boiling water, but insoluble in alcohol, the addition of which promotes its formation in water solutions (distinction and separation from Citric, Oxalic, and Malic acids).-Tartaric acid is distinguished from citric acid, in crystal, anld:'thb former is detected in a crystalline mixture of the two acids, as follow:: * * Hager's "Untersuchungen," B. 2, S. 103. 14( SOLID NfONY-VOLATILE A CIDS. A solution of 4 grammes of dried potassa in 60 cubic centi' meters of water and 30 cubic centimeters of 90 per cent. alcohol is poured upon a glass plate or beaker-bottom to the depth of about 0.6 centimeter (one-fourth inch). Crystals of the acid under examination are placed, in regular order three to five centimeters (one to two inches) apart, in this liquid, and left without agitation for two or three hours. The citric acid crystal. dissolves slowly but completely and without losing its transparency. The tartaric acid crystal (or the crystal containing tartaric acid) becomes, in xCfewiminutes, opaque white (in a greater or less degree), and continues for hours and days slowly to disintegrate without dissolving and with gradual projection of spicate crystals, fibrous and opaque, also trimetric prisms. (See, also, Citric acid, e.) Solution of lead acetate precipitates free tartaric acid or tartrates as white normal tartrate of lead, very slightly soluble in water,'insoluble in alcohol, but slightly soluble in acetic acid, readily soluble in tartaric acid and in tartrate of ammonium solution, and freely soluble in amnmoniacal solution of tartrate of ammonium (distinction firom Malate), somewhat soluble in chloride of ammonium. Solution of silver nitrate precipitates solutions of normal tartrates (not free tartaric acid) as white argentic tartrate, soluble in ammonia and in nitric acid. On boiling, the precipitate turns black, by reduction of silver, some portion of which usually deposits as a mirror-coating on the glass. The mirror is formed more perfectly if the washed precipitate of argentic tartrate is treated with ammonia just enough to dissolve nearly all of it, and the solution left on the water bath. (The reduction is a distinction from Citrate). Free tartaric acid does not reduce silver from its nitrate. ci. The copper sulphate with potassa is not reduced by tartaric acid. Potassium permanganate solution is reduced very slowly by firee tartaric acid; but quickly by alkaline solution of tartrates, with separation of brown binoxide of nmngnnesnp(dis TARTARIC ACID. 17 tinction from Citrates which separate the brown binoxide of manganese slowly or not at all, leaving green solution of manganate). e. Tartaric acid may be extracted from tartrates by decomposing with sulphuric acid and dissolving with alcohol, sulphates being generally insoluble in alcohol. Free tartaric acid may be extracted firom water solutions by agitation with amrylic alcohol, which rises to the surface. Quantitative. —f. Free tartaric acid, unmixed with other acids, may be determined volutmetrictcly by adding a normal solution of soda, to the neutral tint of litmus. Weighing 7.500 grammes, the required number of cubic centimeters of normal solution equals the number per cent. of acid. y. In absence of acids forming insoluble lead salts, tartaric acid may be precipitated by acetate of lead solution, washed with dilute alcohol, dried on the water bath and weighed as normal lead tartrate. PbC4:406 ~ 12C414H:: 1: 0.422535. In absence of acids forming insoluble calcium salts; tartaric acid may be precipitated from solution of neutral sodium tartrate by chloride of calcium. If ammonium salts are present, the ammonia should first be mostly expelled by adding sodiumn carbonate and heating-the excess of carbonate being neutralized with acetic acid. The precipitate of calcium tartrate should be heated and left aside for completion, washed with a little water and then with dilute alcohol, and dried (in a tared filter) at 40~ to 50~ C. Ca C4H40,+411,0: HIC1241O1:: 1: 0.577. In presence of citric acid, oxalic acid, sulphuric acid, phosphoric acid, etc., the tartaric acid may be determined as potassium bitartrate. The solution of acid is made nearly neutral by addition of soda, or the solution of salt (tartrate) is made sfightlyacid ly addition of acetic acid; this water solution is obtained in concentrated form and treated with a little alcohol but not to cause a precipitate, and then precipitated with concentrated solution of acetate of potassium. The precipitate is washed with alcohol, and dried on the water bath, KHE C41II40'; 12C4H40,: -1: 0.797. Rtesults approximate. 1S SOLID XOiVN VOLATILE ACIDS. 7. RACEMIC ACID. Isomer of tartaric acid, from -which it is distinguishecd as follows: By forming triclinic crystals, I-2C4H406O. H2O; soluble in 5 parts cold water or 48 parts of' alcohol of sp. gr..809; slightly efflorescent on the surface; losing, th cwater of crystallization at 1000. By its solution (uncombilled) being able to form after a short time a slight precipitate in solution of calcic sulphate and a precipitate in solution of calcic chloride; the precipitate of calcic racemate being, after solution ill hydrochloric acid, precipitated again by ammonia, that is, not soluble in chloride of ammonium solution. By being inactive toward polarized light. S. CITRIC ACID. Ic6H50,,. Ccharacterrzed by the form, solubilities, and fusibility of its crystals (a); by the properties of its salts of calcium, barium, lead, silver, potassium (b); by the limits of its reducing power (c).-Sepacrated (as free acid) from sulphates and other substances insoluble in alcohol by its solubility in this menstruum (d); from tartaric acid, approximately, by the slight solubility of the potassic tartrate in dilute alcohol (e); from acids which form soluble lead salts by method given under Acetic acid at g.-Determimzed by acidimetry (f); by precipitation as barin citrate to be weighed as barium sulphate, or as bariurm citrate. a. The citric acid of commerce is crystallized (from rather concentrated solutions) as HCo 507.,O, in large, transparent, colorless, and odorless prisms of the trimetric system. These crystals slowly effloresce in the air between 28~ and 500 C., and lose all their water of crystallization at 1 000 C. A different form of crystals, containing one molecule of water to two molecules of acid, is obtained from boiling, concentrated solutions.-Citric acid melts when heated, and at 175~ gives off pungent, characteristic vapors, containing acetone (see Acetic acid, 40, c), while Aconitic acid (9) is formed in the residue. (The odor is distinctly unlike that of heated Tartaric acid.) —Citric acid is soluble in less tlan its A-e.ight of wiater, in 1.5 parts of 90 per CITIRIC A CID. 19 cent. alcohol, insoluble in absolute ether, but soluble to a slight extent in ether containing alcohol or water; also slightly soluble in chloroform containing alcohol. b. The alkaline citrates are freely soluble in Mwater; iron, zinc, and copper citrates, moderately soluble; other metallic citrates mostly insoluble, calcium citrate being somewhat soluble in cold water, but nearly insoluble in hot water..' Ammonio-ferric citrate is readily soluble in water. Citric acid prevents the precipitation of iron and many other heavy metals by the alkalies, soluble double citrates being formed. The alkaline citrates are sparingly soluble in hot, less soluble in cold. alcohol.-Solution of lime, added to solution of citric acid or citrates, causes no precipitate in the cold (distinction from Tartaric, Racenic, Oxalic acids)'; but on boiling- a slight precipitate is formed (distinction from Malic acid). Solution of chloride of calcium does not precipitate solution of free citric acid even on boiling, nor citrates in the cold, but precipitates citrates (neutralized citric acid) when the mixture is boiled. The precipitate, Ca,(C61H,07)2. 210, - is insoluble in cold solution of potassa (which should be not very dilute and nearly free from carbonate), but soluble in solution of cupric chloride (two means of distinction from Tartaric acid); also soluble in cold solution of chloride of ammonium and readily soluble in acetic acid.-Solution of acetate of lead precipitates from solutions of neutral citrates, and from even very dilute alcoholic solution of citric acid, the white citrate of lead, Pb,(C11,07)2. —1,20, somewhat soluble in free citric acid, soluble in nitric acid, in solutions of all the alkaline citrates and of chloride and nitrate of ammonium, soluble in ammonia (formation of basic citrate of lead then soluble with the citrate of ammonium produced). (Malate of lead is not soluble in malate of ammonium.) c. Nitrate of silver precipitates from neutral solutions of citrates, white normal citrate of silver, not blackened by boiling (distinction friom Tartrate).-Solution of permanganlate of potassium is scarccly at all affected by free citric acid in the. cold. 20 SOLID NONX- VOLATILE ACIDS. With free alkali, the solution turns green slowly illn the cold, readily when boiled, without precipitation of brown binoxide of manganese till after a long time (distinction from Tartrate). d. Citric acid is separated from "extractive matters" and from acids which form soluble barium salts by precipitation, as baritmvb citrate, which is then carefully decomposed with sulphuric acid.-From citrates soluble in water, the acid may be obtained by decomposing with sul2phitric acid (not added in excess), then removing the water by evaporation at a temperature below 100~, and extracting the citric acid from the residue by alcohol. e. One part of citric acid dissolved in two parts of water, and treated with a solution of one part of acetate of potassium in two parts of water, will remain clear after addition of an equal volume of strong alcohol (absence of Tartaric, Racemic, and Oxalic acids). For a method by treatment of the crystals with alcoholic solution of potassa, see Tartaric acid (1), c. Quantitative. —f. Uncombined citric acid, not mixed with other acids, may be determined volumetrically by adding a standard solution of soda or potassa to the neutral tint of litmus. Weighing 7.000 gramm6A ( v of I of C0IO807 1 HO) the number of cubic centimeters of normal solution of alkali required equals the number per cent. of crystallized acid.* g. The precipitation of alkaline citrates by barium acetate is made complete in solution of alcohol of sp. gr. 0.908-as follows:1 The citric acid is obtained as alkaline citrate; if free, by neutralization with soda; if combined with a non-alkaline base, by warm digestion with an excess of soda or potassa, filtering and washing-the filtrate being neutralized by acetic acid. In either case, the carefully neutralized and not very dilute solution is treated with a slight excess of exactly neutral solution of acetate of barium, and a volume of 95 per cent. alcohol, equal to twice' Results a little too high. —J. CREUsE. d J. CarusE, Amnericctn CGhciist, I., 4TM4 (1871). a CIO NITIC AI CID. 21 that of the whole mixture, is added. The precipitate is washed on the filter with 63 per cent. alcohol, and dried at a moderate heat. The citrate of barium contains a variable quantity of water, and is transformed into sulphate of barium by transferring to a porcelain capsule, burning the filter, and heating with sulphuric acid several times, till the weight is constant. 3BaSO4: 2HCI6H5O,07. 120':: 0.601. Hager directs that barium or calcium citrate (washed with alcohol) be dried at 1200 to 1500 and weighed. Ba3(CH10,,),: 211H01C,0. 1H20': 1: 0.53232. 9. ACONITIC ACID. 1 1C6H201. A colorless solid, crystallizing with difficulty in warty masses, at 160~ C. (320~ F.) resolved into: liquid itaconic acid. Soluble in water, alcohol, and ether; its solutions having a decided acid reaction. It has a purely acid taste.-The aconitates of the alkaline metals, magnesium, and zinc are freely soluble, the others insoluble or sparingly soluble, in water. Calcie aconitate is soluble in about 100 parts of cold water and in a much, smaller quantity of boiling water. Manganous aconitate crystallizes in rose-colored octahedrons, sparingly soluble in water. Argentic acoPitate is sparingly soluble in water, soluble in alcohol or ether, blackened by boiling with water.-Free aconitie acid is precipitated by mercurous nitrate, but not by most metallic salts until after neutralization. Aconitie acid is separatecd from Monkshood (Aconituni zcalpells), Larkspur (Delphiniun consolida), Equisetum, Black IIellebore, Yarrow (A chillea millefolium), and other plants, in which it exists as calcium salt, by evaporating the clear decoction to crystallize. The crystals of aconitate of calcium are dissolved and precipitated by acetate of lead, and the lead salt decomposed by hydrosulphurie acid. It is also separated from impurities by adding (to the dry mixture) five parts of absolute alcohol, then saturating the filtered solution with hydrochloric acid, and adding water, when aconitate of ethyl -will rise as an i22i SOLID ON- VOLATISLE A C'IDS. oily layer, colorless and of aromatic odor. This ether may be decomposed by potassa. Aconitic acid may be separated from Maleic acid by the more ready crystallization of the latter, and from Fumaric acid by being more soluble in water. 10. MALIC ACID. H 2CO4140,. ldentiled more especially by its deportment when heated (c); by the deportment of its lead salt when heated under water (b), and of its calcium salt in water and in alcohol (di ).- Sepacttecl from tartaric, citric, oxalic, and other acids by alcoholic solubility of the neutral malate of ammonium (c) and by its reaction with calcium in water solutions (d); from tannic acid, also, by aqueous solubility of calcic malate, and from formic, acetic, benzoic acids by alcoholic insolhbility of calcic mIalate (d ).-Determnined gravimetrically as lead malate (e). Crystallizes in four-sided or six-sided prisms, deliquescent in air; colorless, odorless, and of sour taste; freely soluble in water and alcohol, soluble in ether. The malates are mostly soluble in water, but insoluble in alcohol. Nitric acid oxidizes nmalic acid, and alkaline solution of permanganate is decolorized by it, but chromic acid acts on it with difficulty. Malate of silver darkens but slightly on boiling (Tartrate blackens). Concentrated sulphuric acid darkens malic acid very slowly after warming. I-ydriodic acid changes it to succinic acid with separation of iodine (the result being the same with Tartaric acid). Sodium amalgam changes malic to succinic acid. a. Free malic acid, heated in a small retort over an oil-bathto 175~ or 180~ C., evolves vapors of maleic and fumaric acids, which crystallize in the retort and receiver. The fumaric acid forms slowly at 1500 C., and mostly crystallizes in the retort, in broad, colorless, rhombic or hexagonal prisms, which vaporize without melting at about 200~ C., and -are soluble in 250 parts of water, easily soluble inf alcohol or ether. If the temperature is suddenly raised to 200~, the maleic acid;3 the chief product. M11A LC A (71). Maleic acid crystallizes ill oblique, rhomboidal prisms, which melt at 130~ and vaporize at about_1600, and are readily soluble in water and ill alcohol. The tes-tor malie acid, by heating to 175~ or 1800, may be made in a test-tube, with a sand-bath, the sublimate of fumaric and maleic acids condensing in the upper part of the tube. Malic acid melts below 1000, and does not lose weight at 120~; at the temperature of the test water-vapor is separated- maleic and fumaric acids both having the composition of malic anhydricle (C,H404). b. Solution of acetate of lead precipitates nmalic acid, more perfectly after neutralizing with ammonia, as a white and frequently crystalline precipitate which upon a little boiling melts to a transparent, waxy semi-liquid (a characteristic reaction, ob-' scured by presence of other salts). The precipitate is very sparingly soluble in cold water, somewhat soluble in hot water (distinction from Citrate and Tartrate); soluble in strong ammonia, but not readily dissolved in slight excess of ammonia (distinction from citrate and tartrate); slightly soluble in acetic acid. c. If the precipitate of malate of lead is treated with excess of ammonia, dried on the water bath, triturated anld moistened with alcoholic ammonia, and then treated with absolute alcohol, only the malate of ammonium dissolves (ldistinction fiom Tartaric, Citric, Oxalic, and many other organic acids, the normal ammonium salts of which are insoluble in absolute alcohol). Also, malic acid may be separated from tartaric, oxalic, and citric acids, in solution, by adding ammonia in slight excess, and then 8 or 9 volumes of alcohol, which leaves only the malate of ammonium in solution. cI. Solution of chloride of calcium does not precipitate malic acid or malates in the cold (distinction from Oxalic andcTartaric acids); only in neutral and very concentrated solutions is a precipitate formed on boiling (while calcic citrate is precipitated in neutral boiling solutions if not very dilute). The addition of alcohol after chloride of calcium produces a iwhite bulky precipi-. 2c4 SOLID.NONA- VOLATLTILE ACIDS. tate of calcic malate in even diltlte neutral solutions (indicative in absence of sulphuric and other acids whose calcium salts are less soluble in alcohol than in water).-Acetic, Formic, and Benzoic acids are left in solution and malic acid precipitated by addition of ohe or two volumes of alcohol, with chloride of calcium. In separation froml Tannic acid, both acids may be precipitated by chloride of calcium, with a slight excess of ammonia and alcohol; the nealate is then washed out of the precipitate -with water. Quantitative.-e. The alcoholic solution of malate of ammonium-prepared as directed in c-may be precipitated with acetate of lead, washed with alcohol, dried and weighed as malate of lead. PbC4IIO: ~12C4H40,::1: 0.3953. 11. ME9CONIC ACID. HC311H07. IdetZfied by its physical properties and precipitation by hydrochloric acid (a); its reactions with iron and other metals (b); and by its products when heatedl (c). It is sepcaratedfqro o2liumn through formation of the calcium salt or lead salt (c). c. Meconic acid crystallizes in white shlining scales or small rhombic prisms, containing three molecules of crystallization water, fully given off' at 1000 C. It is soluble in 115 parts of water at ordinary temperatures, less soluble in rwater acidulated with hydrochloric acid, more soluble in hot water, freely soluble in alcohol, slightly soluble in ether. It has an acid and astringent taste and a marked acid reaction. Its salts, having two atoms of its hydrogen displaced by acid, are neutral to test-paper. Except those of the alkali metals, the dimetallic and trimetallic meconates are mostly insoluble in water. MIeconates are nearly all insoluble in alcohol. They are but slightly or not at all decomposed by acetic acid. Solutions of nmeconates are precipitated by hydrochloric acid, as explained above. b. Solution of meconic acid is colored red by solution of ferric chloride. One ten-thousandlth of a grailn of the acid in 1JUEC0NIOC ACID.- 2 one grain of water with a drop of the reagent acquires a distinct purplish-red color (WORMLEY). The color is not readily discharged by addition of'dilute hydrochloric acid (distinction fiom Acetic acid), or by solution of mercuric chloride (distinctioni from sulphocyanic acid).-Solution of' acetate of lead precipi-. tates meconic acid or meconates as the yellowish —white meconate of lead, Pb3(CHO7)2, insoluble in water or acetic acid. —Excess of baryta water precipitates a yellow trimletallic mleconate.Solution of nitrate of silver in excess precipitates fiee mieconic acid on boiling, and precipitates meconates directly, as yellow trimetallic meconate; if free meconic acid is in excess, the precipitate is first the white dimletallic meconate; both m econates being soluble in ammllonia and insoluble in acetic acid.-Solution of chloride of calcium precipitates from solutions of meconic acid, and even from neutral meconates, chiefly the white mlonometallic meconate, CaH4(CTHO)2. 220, sparingly soluble in cold water; in the presence of free ammonia, the less soluble, yellow dimetallic salt, CaHl C O,110. H20, is formed. Both precipitates are soluble in about 20 parts of water acidulated with hydrochloric acid. c. At 1200 C. (2480 F.) dry meconic acid is resolved into comenic acid; at above 200~ C. the comenic acid is resolved into pyrocomenic acid and other products. The sublimate of comenic acid dissolves sparingly in hot water, not at all in abso-, lute alcohol. It crystallizes in prisms, plates, or granules. Solution of comenic acid gives a red color with ferric chloride, green pyramidal crystals with cupric sulphate in concentrated solution, and a yellowish-white granular precipitate with acetate of lead. d. The separation of mneconic acid from opikum is effected with least loss by precipitating the ilnfusion with acetate of lead (leaving the alkaloids as acetates with some excess of lead in the filtrate). The precipitate is decomposed, in water, with hydrosulphuric acid gas, and the filtrate therefrom is concentrated (mild acidulatecd with hydrochloric acid) to crystallize the meconic acid. '26 SOLID NOX- VOLAzTILE t ACIDS. The crystals are purified by dissolving in hot water and crystallizing in the cold after acidulation with hydrochloric acid. The calcium meconate, precipitated in concentrated solution by Gregory's process for preparation of morphia, as by the Br. Pharmacopceial preparation of morphike murias, is washed with cold water and pressed. - One part of the precipitate is dissolved by digestion in 20 parts of nearly boiling water with 3 parts of commercial hydrochloric acid, and set aside to crystallize the acid meconate of calcium. The crystals are purified from color and freed friom calcium by repeated solution in the same solvent, used just below 1000 C., and each time in a slightly diminished quan-; tity. The acid nmay be further decolorized by neutralizing with potassic carbonate, dissolving ill the least sufficient quantity of hot water, draining the magma of salt when cold, dissolving again in hot water and adding hydrochloric acid to crystallize. 12. DIGITALIC ACID. Digitaleic acid. Digitoleic acid. -A solid of a green color, crystallizing in slender needles, sometimes stellate, having a bitter taste and pleasant aromatic odor. It is sparingly soluble in water, freely soluble in alcohol and in ether. It reddens litmus and decomposes carbonates. The alkaline digitalates are soluble, forming soapy solutions with water; the other metallic digitalates are insoluble in water. Digitalic acid is obtained from the leaves of the fox-glove (digitalis purpurea) by exhausting with cold water, precipitating the solution with acetate of lead, decomposing the precipitate with solution of carbonate of sodium, and treating the somewhat concentrated filtered solution with hydrochloric acid, which precipitates crude digitalic acid. This is purified by crystallization from alcohol. 13. TANNIC ACIDS: Vegetable educts having an astringent taste and an acid effect on test-papers, mostly amorphous, TlA~NNIIC AACIDS. 27 ilot volatile or liquefiable, freely soluble in water and in alcohol, mostly but little soluble in dilute sulphuric acid; forming with ferric salts green or blue colors, and precipitating solutions of gelatin and albumen (distinctions from gallic acid). Attributed formulEa, C27H24018; C27O22017; C,14H,0~ (SCIIrF). The tannic acids are further characterized by forming in solutions of all the caustic alkalies a brown color bleached by oxalic acid, and in solutions of alkaloids a white precipitate dissolved by acetic and stronger acids. With exceptions hereafter named, they precipitate solution of tartrate of antimony and potassium; they precipitate basic acetate of lead, and form insoluble compoundcls with many heavy metals. They all absorb oxygen, especially in presence of alkalies, and act as powerful reclucingy agents -quickly decolorizing solution of permanganate, and reducing the heated alkaline copper solution. Tannic acids are more permanent in alcoholic than in aqueous solutions. If a very little starch-paste be tinged blue by a slight addition of hundredth-normal solution of iodine (1 part iodine dissolved with potassic iodide in 100,000 parts aqueous solution), on adding a liquid containing tannic acid the blue color of the iodized starch presently disappears-hydriodic acid and gallic acid being formed. On adding a crystal of potassic nitrite the blue is restored.* Also, if a drop of tannic acid solution is mixed with a few drops of iodine solution of the above strength, and afterward a drop of very dilute alkali be added, on evaporation to remove carbonic acid, a bright red color will appear.f By oxidation the tannic acids acquire a dark color, brown, black, green, or red. Gallotalnnic acid with alkalies in the air slowly forms tannoxylic acid, which precipitates acetate of lead solution dark-red. With lime-water it forms a white turbidity, becoming green and darker. Tannic acids form with molybdate of ammonium a red color removed by oxalic acid. The physiological tannic acid (WAGNER, 1866) or quercitan* GRIESSMAYER: Ann. Ch. Pharm., Clx., 40-56. + GRIESSMAYER: Zeitschr. Anal. Chem., x., 43, 28 SOLID.NON-VOLATILE ACIDS. nic acid is found in the bark of the oak,- pine, willow, and beech, in bablah (acacia fruit), in valonia (cups of the quercus oegilops), and in sumac. It is a glucoside, and it does not yield pyrogallic acid by dry distillation. The 2pathological tannic acid of Wagner, or gallotannic acid, is found in common or Turkish gallnuts and in Chinese and Japanese gall-nuts. It is a glucoside (being transformed by contact of a ferment or by sulphuric acid into gallic acid and glucose), and in dry distillation it yields pyrogallic acid. Ferric salts give blue to blue-black precipitates with gallotannic acid, quercitannic acid, and the tannic acids of poplar bark, birch bark, hazel-nut, uva ursi leaves, lithrum salicaria leaves, the bark of cornus florida and cornus mascula, and many other plants. Ferric gallotannate (ink) is bleached by oxalic acid. On digestion with nitric acid, a yellowish solution is formed, in which excess of almmonia precipitates ferric hydrate. Ferric salts give green precipitates with quinotannic acid, moritannic acid, caffetannic. acid, catechutannic acid, catechuic acid, cephaelic acid, the tannic acids of the barks of pines and fir and willow, the rhubarb root, the root of potentilla tormentilla, and of numerous other plants. Cephaelic acid with ammonia is colored violet to black by ferric salts. Gelatin does not precipitate Catechuic acid or Caffetannic acid. Tannic acids are removed from solution by digestion with oxide of copper, oxide of zinc, or animal membrane; or by precipitation Mwith solution of gelatin, sulphate of cinchonia, or acetate of copper.-They are separated as insoluble lead salts, according to the general method given under Acetic Acid. Quantitative.-The total tannic acids in solution are determined-by the specific gravity (a); by absorption in oxide of copper (b); by a volumetric solution of sulphate of cinchonia (c); by a volumetric solution of tartrate of antimony and potassium (in presence of chloride of anmonium to prevent the precipitation of gallic acid) (d). TA NNIC' A' 29 a. A twater solttion- of gallotannic acid at 17.50 C. (63.5(' F.) contains as follows (after HAGER): P.c. SPEC. GRAV. P.C. SPEC. GRAV. P. 0. SPEC. GRAV. 20 1.0824 13 1.0530 6 1.0242 19.5 1.0803 12.5 1.0510 5.5 1.0222 119 1.0782 12 1.0489 5 1.0201 18.5 1.0761 11.5 1.0468 4.5 1.0181 18 1.0740 11 1.0447 1 4 1.0160 1.7.5 1.0719 10.5 1.0427 1 3.5 1.0140 17 1.0698 10 1.0406 1 3 1.0120 16.5 1.0677 9.5 1. 0386 2.5 1.000 16 1.0656 9 1.0365 2 1.0080 15.5 1.0635 8.5 1.0345 1.5 1.0060 15 1.0614 8 1.0324 1 1.0040 3.4.5 1.0593 7.5 1.0304 0.5 1.0020 14 1.0572 7 1.0283 0 1.0000 13.5 1.0551 6.5 1.0263 When other substances besides tannic acid and water are present, the specific gravity of the solution is first taken; the solution is then deprived of tannic acid by digestion with animal memnbrane. Four to five parts of dried and rasped hide are added for one part supposed tannic acid. After digestion, the filtrate and washings are brought to the exact bulk of the original solution and to the standard temperature. The former specific gravity minus the latter, and plus one, equals the specific gravity indicating the per cent. of tannin. Gallic acid is not taken out by the membrane. —If pectous substances are present, they would also be precipitated by the animal membrane; hence they must be removed. before taking the specific gravity in the first place. This is accomplished by making an alcoholic extract.of the original material, then evaporating off' the alcohol and substituting water (HAMMER). —Instead of animal membrane, oxide of copper may be used to remove the tannic acid (and gallic acid), accordinc. to b. b. A weighed quantity of recently ignited oxide of copperabout 5 tines that of the tannin-is added to the prepared solution; the mixture is gently warmed for an hour and set aside for a day with frequent agitation, then filtered and the copper tannate and 30.$SOLID NOr- rOLATILE A CIDS. oxide washed, dried on the water-bath and weighed. The increase of weight is the amount of tannic (and gallic) acid (HAGER). c. 4.523 grams of good sulphate of cinchonia, with 0.5 gram sulphuric acid, and 0.1 gram acetate rosanilin or fuchsin, are dissolved in water to make one litre. Each c.c. of this solution precipitates 0.01 gram tannic acid. One gram of solid material is obtained in clear solution of about 50 c.c. measure. To this the standard solution of cinchona is added, the color being thrown down in the precipitate. When the tannic acid is all precipitated, the anilin color appears in solution. One gram having been taken, each c.c. of the volumetric solution indicates 1 per cent. of tannic acid. Gallic acid is not precipitated by cinchonia (R. WAGNER). d. One equivalent of tartrate of antimony and potassium, after drying on the water-bath (K SbO C4II406-325), is precipitated by one equivalent of tannic acid (C,27,24018=636); or, 0.002555 anhydrous tartrate is precipitated by 0.005 of the tannin. Dissolving 2.555 grams of anhydrous tartrate of antimony and potassiufl; iiawater to make one litre of solution, each c.c of the same corresponds to 0.005 of tannic acid. The prepared solution of tannic acid-which may contain pectous substances without interference with this method-is treated with chloride of ammonium, and the volumetric solution is added, with agitation, until turbidity is no longer produced. The precipitate separates well. Gallic acid is not thrown down when chloride of ammonium is present (GERLAND). 14. GCALLIC ACID. C(H,605; crystallizing with 11HO, An inodorous solid, having an astringent and slightly acid taste, an acid effect on test-papers, and crystallizing in long, silky needles or triclinic prisms. It is soluble in 100 parts of cold or 3 parts of boiling water, freely soluble in alcohol, moderately soluble in ordinary ether, and Lut slightly soluble in absolute ether, insoluble in chloroform or petroleum naphtha. Its non-alkaline metallic salts are insoluble in water but soluble in alcohol, and GA-1LLIC A 0D. 31. slightly soluble in officinal ether; they are decomposed by acids and by alkalies. Heated to 210~-215~ C. (410~-419~ F.), in absence of water, it is sublimed as pyrogallic acid and carbonic anhydride; at higher temperatures, other products are formed. Gallic acid is characterizec by its physical properties (as above given); by its reactions with iron salts (a), with alkalies (b), with tartrate of antimony and potassa and with alkaline arsenate in the air (c), and with molybdate of ammonium (d). It is distinzguishecd from the tannzic acids by negative results with gelatin, albumen, and starch (e); by not precipitating the alkaloids, and by its far weaker reducing power (f) (distinction from pyrogallic acid also).-Gallic acid is determized, if free from tannic acids, by absorption in recently ignited oxide of zinc, according to method b in determination of tannic acid. it is separated from tannic acids and determined by solution with carbonate of ammonium from the precipitate with acetate of copper (g). a. Ferric salts in solution give a deep blue color with gallic acid. Ferrous salts give a blue-black precipitate (distinction from gallotannic acid). b. Alkaline solutions of gallic acid turn yellow to brown and black in the air, from absorption of'oxygen and formation of tannomelanic acid, greatly accelerated by boiling. The latter acid, on neutralizing with acetic acid, precipitates acetate of lead, black. Solution of lime with gallic acid, forms a white turbidity, changing to blue and then to green. c. Tartrate of antimony and potassium is precipitated white in very dilute solution. A faintly alkaline solution ofarsenate of potassium or sodium, with gallic acid,}exposed to the air, soon develops an intense,green color, commencing at the surface. Dilute acids change the green to purple-red and a careful neutralization with alkallies restores the green color, but it is destroyed by excess of alkali.* * PROCTOR: JoTr.' CGhem. Soc., 1874, p. 509. 32 $,e OL ID ~O ArVO-:'L-, ATI.T7.ACH!DS. 1. Molybdate of amrlonium reacts as witl tannic acid. e. Gallic acid does not precipitate gelatin, albumen, or starchpaste, but it forms a precipitate with a mixture of' gum-arabic and gelatin. f. Gallic acid does not reduce alkaline copper solution, but redaczes salts of gold and silver, and quickly decolorizes permanganate solution. Quantitative. —y. The prepa red solution is fully precipitated with a filtered solution of cupric acetate; the precipitate washed and then exhausted with cold solution of carbonate of ammonium.n. The last solution, containing all.the gallate of copper with a -very little tannate, is evaporated to dclyness, the residue moistened with nitric acid, ignited, and weighed as oxide of copper. This weight multiplied by 0.9 gives the quantity of gallic acid (the full ratio being, 0.9126, but- allowance is made for solution of a little tannate by the carbonate of ammonium. The ratio between oxide of copper and tannic acid is 1.304). (MNethod of FLECK modified by SACKuRI and, WOLF.) 15. PYRIOGALLIC ACID. O.H00,, Pyrogalline, Pyrogallol.- Characterized by its physical properties (a); its peculiar avidity for oxygen (b); its reactions with alkalies, lime, iron, copper, etc. (c). It is distinguished from tannic acid )ry not precipitating gelatin or moderately dilute tartrate of antl mony and potassium or cinchonia, and by its dififrent reactions with both ferrous and ferric salts: from gallic acid by its greater solubility in cold water and its far greater reducing power (b). It may be determined gravimetrically as a lead precipitate (d), and volumetrically by permalnganate. ca. Pyrogallic acid crystallizes in long prismatic plates or needles, of a white or yellowish-white color, and an acid and very bitter taste. At 1150 C. (2390 F.) it melts, and at about 2100 C. (410~ F.) it sublimes with partial decomposition and formation of metagallic acid. It is soluble in three parts cold water, freely soluble in alcohol and in ether, not soluble in absolute chloroform. ]PYIiO' G )TALLC A1 CID. 33 b. It is permanent in dry air free from ammonia, bl.t in moist or ammoniacal aii it gradually darkens, and in water solution it turns brown to black, sooner if boiled, still more rapidly in presence of alkalies, absorption of oxy#ge~ taking place to an extent proportional. to the coloration, which is destroyed by oxalic acid. It quickly reduces the alkaline copper solution; also salts of the noble metals, and reduces acid solu, tion of permanganate with evolution of carbonic anhydride. c. With liEme solution, a purple-red color at first appears, afterward the brown color formed by alkalies as mentioned in b. With ferrous salts a blue color is formed; with ferric salts a red solution, brown when heated.- Acetate of copper gives a browngreen precipitate; acetate of' lead a white, curdy precipitate; both soluble in acetic acid. Quantitative. —d. The alcoholic solution of pyrogallic acid is precipitated with excess of alcoholic solution of acetate of lead; the precipitate washed quickly with alcohol, dried by water-bath and weighed. Pb(CGO,)0 3 2C6HI03:: 457 252:1: 0.55142, 16. QUIN0TiA:[LIC ACID. Cinchotannic acid. Kinotannic acid.-Sde6:Tannic acids (13) for appearance, taste, solubilities, and reactionhsiwith alkalies and with iron salts. It precipitates tartrate of antimony and potassium only in concentrated solutions. In oxidation,with alkalies it forms a red-brown color, due to cinchona-red, which dissolves in alkalies and in acetic acid, but not in water. Concentrated sulphuric acid changes quinotannic acid to cinchona-red and glucose. In dry distillation, phenic acid is formed, recognized by the odor. Quinotannic acid is removed from solution by acetate of lead, and from its lead precipitate by hydrosulphuric acid. For separation from Cinchona bark, see under Quinic Acid, d. 17. CATECIEUTAiN)NIC ACID. Has the properties of tannic acids in general, giving a grayish-green precipitate with 34 SOLID NON)- VOLA TILE ACIDS. ferric salts, and distinguished by not precipitating tartrate of antimony and potassium. It softens when heated, and by dry distillation yields an empyreumatic oil. The product of its atmospheric oxidation in water is red. Catechutannic acid is separcatedcfrom Catechu as follows: The aqueous infusion of catechu is heated with dilute sulphuric acid and filtered; the filtrate treated with concentrated sulphuric acid to precipitate the acid sought; the precipitate is washed on a filter with dilute sulphuric acid and pressed between paper. It may then be dissolved in water; the solution treated with carbonate of lead and filtered; the filtrate evaporated in vacuo. It may be farther purified by dissolving in alcoholic ether and evaporating off' the solvent. 18. CATECHUIC ACID. Catechucic acid. Catechin. Tanningenie acid.-A white, tasteless powder, or in fine, silky needles, melting at 217~ C. (423~ F.), and in dry distillation yielding an empyreumatic oil. Very slightly soluble in cold water, soluble in three parts boiling water, moderately soluble in alcohol, sparingly soluble in ether. With alkalies and metallic salts, and as a reducing agent, it gives the reactions of the (irongreen) Tannic Acids, from which it is distinguished by not giving precipitates with tartrate of antimony and potassium or with alkaloids, or with gelatin (the last-named being a distinction firom catechutannic acid). With strong sulphuric acid it forms a deep purple liquid. Catechuic acid may be selparated fyrom catechutanCeZic acid czcld the otfher constituents of catechu by its sparing solubility in cold and ready solubility in hot water. Bengal catechu is digested twenty-four hours in cold water, and the (slightly washe1d) residue is then exhausted with boiling water. When the solution cools, a yellow deposit of catechuic acid appears. This is washed in cold water. It may be decolorized by hot filtration through animal charcoal. It is dried on bibulous paper by aid of the air-pump. 1A AQYIUC _A CIPS. 35 19. MORINTANNIC ACID. C O.o0. Capable of crystallization; yellow, with great tinctorial power, and of an astringent, sweetish taste. MIelts at 2000 C., and at higher temperatures distils phenic acid. In reactions with alkalies, oxidizing agents, gelatin, tartrate of antimony and potassium, iron salts, etc., it behaves like other Tannic Acids (13). With ferric salts it gives a greenish precipitate; with acetate of lead a yellow precipitate; with sulphate of copper a yellowish-brown precipitate; with stannous chloride a yellowish-red precipitate. It is sepcrated from _Pustic by spontaneous deposition firom the concentrated decoction, 20. CAFFETANTNIC ACID. Caffeotanlic acid. Has in general the physical properties of the Tannic Acids, but is not incapable of crystallization. It melts when heated, and then gives the odor of roasted coffee, and in dry distillation yields oxyphenic acid as an oil which solidifies in the cold. With fixed alkalies in solution it turns yellow to reddish-yellow, by oxidation; with ammonia, forms a green color, due to viridic acid, which, when neutralized, gives with acetate of lead a blue precipitate. Warmed with concentrated sulphuric acid, it dissolves with a blood-red color. Distilled with dilute sulphuric acid and binoxide of manganese, it evolves quinone —a pungent and irritating vapor, condensing to a golden-yellow to dingyyellow, crystallizable substance, heavier than water, in which it is but slightly soluble when cold. Caffetannic acid gives the green color with ferric salts. It reduces nitrate of silver, in the specular form, when heatedl. It is distinguished from the larger number of Tannic Acids by not producing precipitates with tartrate of antimony and potassium or with gelatin, but it precipitates cinchonia and quinia (distinetion from Catechuic acid). It gives a yellow precipitate with barium salts. By gradual addition of acetate of lead, in decoction of coflee, it is precipitated next after (the very little) citric acid. Decom SOLID NONA I OTA 7'~I; A ( I)S;. posing the precipitate with hydrosulphurie acid, and evaporating the filtrate, it is obtained in impure, yellowish mass. 21. BOHEIC ACID. CH071O. Boheatannic Acid. Amorphous, pale-yellow solid, caking by exposure to the air, melting at 100~ C. to a waxy mass, very soluble in water and alcohol. Both aqueous and alcoholic solutions gradually decompose by evaporation in the air. It colors ferric salts brown. With baryta, in alcoholic solution, it forms a yellow precipitate, BaC17806. 1H20. With acetate of lead, in alcoholic solution, it forms a grayish-white precipitate, PbC7I,806. Ei20, which can be washed with alcohol and dried at 1000 C. It is se.)arated frogmn the qtercitannic acid,, iz black tea, by precipitating the latter with acetate of lead in the boiling decoction, filtering; after twenty-four hours filtering again, and neutralizing the clear solution with ammonia, when the yellow basic salt is precipitated, PbO.PbC7HI1O6. The latter may be decomposed in alcohol by hydrosulphuric acid, and the filtrate concentrated in vacuum or over oil of vitriol. 22. QUINIC ACID. C:I-H 0. Kinic acid. —ilentified by its physical properties and reactions (a); by its generation of quinone (b); by its reactions with a few metals (c). — Separatedc from cinchona bark, by crystallization from a solution fieed fiom quinovic acid (d); fiom cinchona bark, coffee, or bilberr y, by precipitating its calcium salt fromll a sufficiently purifiedl solution by adding alcohol (e); from substances forming insoluble compounds with neutral acetate of lead by the solubility of its normal lead salt.-Determined gravimetrically as calcium salt (c). a. Colorless, monoclinic prisms or prismatic tablets, melting at 1610 C. (322~0 F.), at higher temperatures evolving combustible gas, plienic acid, hydroquinone, etc. It is freely soluble in water, slightly soluble in alcohol, nearly insoluble in ether. Its solutions have a sour taste and redden litmus. It is deliquescent. Q lY.IVI'(.- (';l), b. Distilled with moderately dilute sulphuric acid and binoxide of manganese, it yields all abundant yellow crystalline subliimate of qttimone, recognized in very small quantities b)y its irritating odor, exciting tears. JFarther, aqueous solution of Quinone is colored brown by ammionia, and y-ellow —greenl by chlorine water; it stains the skin brown. c. Quinic acid decolmposes carbonates. Its mnletcllic salts are soluble in water, except the basic quinate of lead, but are insoluble in alcohol. It prevents the precipitation of many metallic oxides by alkalies. Quinate of silver is white, and bears the heat of the vwater-bath. The q7uinactte of catlciuml crystallizes well from water solution as Ca(C7,I110),. 5HO0, which loses a11 its water of crystallization at 120~ C. (248S F.) Or, it mnay be precipitated from solution of alkaline quinates by adding chlolide of calcium, amnmonia, and alcohol. The basic quinate of lead is precipitated by adding, to solution of alkaline quinate, basic acetate of lead, or normal acetate of lead with ammonia. It is somewhat soluble in solution of basic acetate of lead. It is variable and instable in composition. d. The aqueous solution obtained by macerating cinchona barlk two or three. days (and from which the alkaloids may have been removed by acidulating with hydrochloric acid and.then adding an excess of soda and, after a few hours, filtering) is treated with solution of a.cetate of lead to precipitate the quinovie and quinotannic acids, and filtered. The filtrate is evaporated to a syrupy consistence, to crystallize the quinic acid. If it be desired to separate the Quinovic acid, the solution of acetate of lead (as above) is not added to complete precipitation, and the precipitated quinovate of lead is decomposed, in Nwater, by adding very dilute sulphuric acid, drop by drop, -with great care, to avoid excess. The precipitate being removed, the filtrate is concentrated for crystallization of the quinovic acid. If the Quinotannic acid is to be obtained, the precipitation by acetate of lead is left incomplete, as directed next above, and the filtrate concentrated as previously directed for quinic acid. 8 (8 SO LID XON OLATIL - A 1'IDS. With the crystals of quinic acid there Nwill now finally deposit amorphous or oily quinotannic acid. This may be separated by washingo with ether; on evaporation of the ether the quinotannic acid is obtained. [Thesis of R. M. COTTON, Univ. of Mich., 1874.] e. After precipitating the alkaloids from decoction of cizChona barkt with lime, according to the United States Pharmacopceial preparation of quinie sulphas, the filtrate is concentrated to a small bulk, filtered if necessary, and then alcohol is added to precipitate quinate of calcium. Or, the filtrate is concentrated to a soft solid, washed repeatedly with alcohol, and dissolved in enough water to allow the quinate of calcium to crystallize. Fresh bilberry plcznt (vaccinium myrtillus), collected in May, is boiled with water and lime; the solution is evaporated, and alcohol added to precipitate the quinate of calcium, which requires puirification by recrystallizationl from water. Thoroughly dried or moderately roasted coffee becans, coarsely powdered, are exhausted by boiling with water; the decoction, mixed with milk of lime, is concentrated, filtered, evaporated on a water-bath to a syrup, and precipitated with alcohol as above. The quinlate of calciun, obtained from any of the above sources may be purified from tannic acids and some coloring matters by adding solution of neutral acetate of lead to the aqueous solution of quinate of calcium, filtering out the lead precipitate, and removing the excess of lead from the filtrate by hydrosulphuric acid, when the last filtrate may be concentrated to crystallize. Quinic acid may be obtained from quinate of calcium by precipitating the aqueous solution of the latter by basic acetate of lead, and removing the lead from the precipitate by hydrosulphuric acid. 23. QUINOVIC ACID. C3OI-48 0. Kinovic Acid. Qutinovin or Kinovin. Quinova bitter or Kinova bitter.-An amorphous solid, having a very bitter taste, nearly insoluble in water, very soluble in alcohol, slightly soluble in ether, soluble in chloroform. (According to DE VRIT, chloroform dissolves. G EATIA IC A (_ CID. 39 from "quinova bitter " a portion which he designates as "quinovin," leaving "quinovic acid" insoluble in that menstruum and little soluble in alcohol.) Dry hydrochloric acid gas, acting on a strong alcoholic solution of quinovic acid, transforms the latter into an acid and a sugar. The new acid has very nearly the same solubilities as the original acid, but a different composition (024113804), and forms definite salts with metals. Quinovic acid forms a soluble calcium salt, and hence it is dissolved fromn ciachosnc bark by boiling with milk of lime. From the solution, sufficiently concentrated, hydrochloric acid separates the quinovic acid, insoluble in water. It may be purified by crystallization from alcohol, or by repeated precipitation from alcohol by water. For the separation of quinovic, quinic, and quinotannic acids, each from the same portion of bark, see Quinic Acid, dc. In the manufacture of cinchona alkaloids, the acidulation of the' water by which the clecoction is made interferes with the solution of quinovic acid, which may be at least partly left in the residue. 24. COLUMBIC ACID. C42H140,13. Colombic acid.-An amorphous solid, precipitated in white flakes, left as a yellowish, varnish-like residue on evaporation of its solutions. -It is soluble in alcohol, nearly insoluble in water or ether, its solution being markedly acid. It is precipitated by neutral acetate of lead, as (PbO)3(C42144012) 2 when dried at 130~ C. Acetate of copper does not precipitate it. In colzimnbo root, columbie acid probably exists in combination with berberina and perhaps also with inorganic bases. It can be separated by exhausting alcoholic extract of columbo with water or lime-water, and precipitating with hydrochloric acid. 25. GENTIANIC ACID. 0C14tI003. Gentisie acid. Gentianin. Gentisin.-Light-yellow, tasteless, solid, crystallizing in slender needles, not decomposed at 2000 C., but carbonizing with partial sublimation at 300~ to 400~ C. It is soluble in 36 parts 40,OLT1);NOr I"OT)L-t 7'IL F A (JTI)S. water at ordinary temperature, readily soluble in alcohol, and moderately so ij ether. Its solutions are neutral to litmus. It dissolves in aqueis'ialkalies with a golden-yellow color. Strong sulphuric acid dissolvfes it yellow. Nitric acid, of specific gravity 1.42, and colorless, dissolves it green; on adding water, a green powder, dinitrogentianic acid, is precipitated. This, on addition of alkalies, assumes a fine cherry-color. Chlorine forms a yellow precipitate in alcoholic solution of gentianic acid. The barium salt, Ba C14I805. HtO, is an orange-colored precipitate. The lead salt is insoluble. Gentianic acid is separated from gentictn root as follows: The powdered root is exhausted of gentian-bitter by cold water; then pressed, dried, and exhausted with strong alcohol, and the alcoholic solution evaporated nearly to dryness. The residue is washedl with a little ether to remove fat, and repeatedly crystallized from alcohol to separate from resin. 26. CARMINIC ACID. COaoO00. Carmine. —A purple amorphous solid, fusible but not decomposed at 136~ C.; soluble in all proportions in water and alcohol, and in sulphuric and hydrochloric acids without alteration, the solutions having a bright purple-red color. Ether does' not dissolve it.-In alcoholic solution it precipitates alcoholic potassa red changing to dlark violet, and forms red precipitates with acetates of lead, zinc, Copper, and silver. It is turned blue by sulphate of aluminum, and yellow by stannous chloride.-Carminic acid is a glutcoside, boiling dilute mineral acids transforming it into carzinze-red and sugar. Carmine-red in mass is purple-red with a green reflection, soluble in water and in alcohol with red color, not soluble in ether. Carminic acid is separated from Cochineal by exhaustion with boiling water; the solution precipitated by adding slightly acidulated subacetate of lead short of excess, the precipitate washed -with water till the washings give no precipitate with mercuric chloride, then decomposed by hydrosulphuric acid and G A J O3 COfT' ( )A. C1 filtered. The filtrate is evaporated and ctried on the N-ater-bath, and the residue extracted with alcohol. 27. CHRYSOPHANIC ACID. Chrysophane. Rheic Acid.-A pale yellow or orange-yellow solid, crystallizing in sixsided tables or moss-like aggregates of scales, subliming with partial decomposition when heated.-Sparingly soluble in cold wa^ter, soluble in 1,l125 parts of 86 per cent. alcohol at 30~ C. (8GO F.), or 224 parts of the same alcohol boiling, soluble in ether, benzole, and turpentine oil, the solutions having a yellow color.-.It dissolves in aqueous alcalies with a very deep purple color, recognized in very dilute solution; the potassa solution upon evaporation deposits violet to blue flocks, which dissolve in water to a red solution.-It does not form stable salts. In alcoholic solution with alcoholic subacetate of lead it forms a reddishwhite precipitate, becoming rose-red when boiled with water. In ammoniacal solution it is precipitated lilac by neutral acetate of lead, and rose-color by alum. —Strong sulphuric acid dissolves it unchainged; strong nitric acid converts it into a red substance, containing chrysammic acid (prodreced from Aloes by nitric acid). Chrysophanic acid is sejcarateed from Rhubarl by exhausting the powdered root with alcoholic ammonia, precipitating with subacetate of lead and decomposing the lead compound by hydrosulphuric acid. From the Wall Lichen (Parmnelica ptarietinza), the alkaline solution obtained as above is precipitated by acetic acid, the precipitate washed with water, redissolved in alkali and reprecipitated by (hydrochloric) acid. From the Pumex, an ethereal extract is obtained, and repeatedly dissolved in alcohol and precipitated by water. A method of purification is to dissolve in boiling absolute alcohol and crystallize. 28. GAMBOGIC ACID. A resinous solid, hvyacinth-red in mass, yellow in powder. Insoluble in water, soluble in alcohol, ether, chloroform, bisulphide of carbon-its solutions showing the yellow color when very dilute, and having a strong 4a SO3LID VTOLA TILE -A 01C1)S. acid reaction. It dissolves in the aqueous alkalies, with red color, and in solutions of fixed alkaline carbonates with expulsion of the carbonic anhydride. From alkaline solutions it is precipitated yellow by acids.-The solution of gambogiate of ammonia forms with barium salts a red precipitate; with zinc salts, yellorw; lead salts, reddish-yellow; silver salts, brownish-yellow; and copper salts, brown precipitates.-It is bleached and decomposed by chlorine, and decomposed with formation of nitrophenic acid by nitric acid. It is dissolved with red color by cold concentrated sulphuric acid; addition of water precipitating it unchanged. 29. SANTALIC ACID. Santalin. —A fine red, tasteless, and odorless crystallizable solid, melting at 104~ C. Insoluble in water, vei'y soluble in alcohol, soluble in ether-the solutions having a blood-red color and acid reaction. Soluble in aqueous potassa, or ammonia, forming violet solutions, which precipitate alkaline earths.-The.alcoholic solution precipitates lead salts, but not salts of barium, silver, or copper. The lead and barium salts are violet. Santalic acid is sepcar.ated from Sandal-wood (red saunders) by obtaining, first, an ethereal extract, then from this an alcoholic extract, which is washed with water, dissolved agaiin in alcohol, and precipitated therefrom by alcoholic solution of acetate of lead. The lead compound is washed by alcohol, then decomposed in alcohol with dilute sulphuric acid, SOLID VOLATILE ACIDS. 30. BENZOIC ACID. HC07H502. I2demtefed by its physical properties, especially in sublimation (a); by its oxidation to nitrobelzole (b), and its deoxidation to bitter almond oil (c); by its reactions with metallic salts (d).-Doistinguishled fiom iEArZOIC A CID. 43 Cinnamic acid by the action of permanganate upon the latter (see 31, b); from Hippuric acid by distillation with potassa; from Salicylic acid by the color of its ferric salt (d).-ZSepcaratecl from non-volatile and highly volatile substances by sublimation (a); from Succinic and many other acids by the alcohol solubility of its barium salt (cd); froin SUCCinii and IHippuric acids by its solubility and extraction from water solutions by chloroform or ether (c)..-Gravimetrically cdetermined as lead salt (e). a. A white solid, crystallizing in lustrous scales or friable needles; odorless when pure, but frequently found having odor of benzoin, and rarely a urinous odor, of an acid and warm taste, and a strongly acid reaction. It is soluble in 200 parts of water at 15~ C. (590~ F.), in 20 parts of boiling water, in 3 parts of cold alcohol, in 25 parts of ether, in 7 parts of chloroform, and readily soluble in bisulphide of carbon, benzole, petroleum naphtha, and in fixed and volatile oils. MIost of the benzoates are soluble in water, and many of them are soluble in alcohol. Hydrochloric acid precipitates benzoic acid from solutions of benzoates, excess of the reagent not affecting the water solubility of benzoic acid as already given. Sulphuric acid dissolves benzoic acid. Benzoic acid decomposes carbonates. Benzoic acid melts at 121~ C. (250~ F.), and seblimes at 240~ to 250~ C. (464~ to 4820~ F.) The vapors cause a sense of irritation in the throat and coughing. When slowly condensed, the sublimate is crystalline in minute needles. Benzoates heated witll phosphoric acid evolve berzoic acid.-When mixed with 3 parts slaked lime and heated gradually in a retort, benzole (119) is distilled. b. If benzoic acid is boiled with concentrated nitric acid, the mixture evaporated to a small bulk, and then strongly heated in a test-tube, vzitrobenzole (120) is evolved, and will be recognized by its odor of bitter almond oil. c. When benzoic acid, dissolved or suspended in water, is warmed with a slip of metallic magnesium, and very slightly acidulated with sulphuric acid, so that hydrogen is evolved, 44;1 SOTD VOrI/ A'lt i1U.A AC'D)S. bitter almondoez oil (benzoyl hydride, C,l6,0bI) is produced, and recognized by its odor. ct. Basic ferric chloride solution precipitates benzoates almost completely, as a flesh-colored basic benzoate (ferric Salicylate is blue violet).-Acetate of lead and nitrate of silver give precipitates in solutions not too dilute.-Ammoniacal chloride of barium with alcohol gives no precipitate (distinction and separation from Succinic and many other acids). Magnesium benzoate is also soluble in alcohol (Succinate insoluble in alcohol). Quantitative. —e. Benzoate of lead, precipitated from neutral ben2zoate by acetate of lead, washed with cold water or alcohol aciclulatedl with one-half per cent. of acetic acid, and dried at; 100~ C., may be weighed for determination of benzoic acid: Pb(C,-HO),: 2H,-IC7HO: 1: 0.54343. 31. CINNAlVIC ACID. H109H7,02. Ccrcracterizedc by its physical properties and reactions in the dry way (c ); its reactions with oxidizing agents (b); its reactions with metallic salts (c). —istinguished from benzoic acid by action with oxidizing agrents (b), by the color of its ferric salt and by its precipitate with manganous salts (c).-Separatecl from non-volatile substances by sublimation (a); from substances soluble in water and in dilute acid by precipitation of cinnamates by acids (a); from substances insoluble in ether by the action of that solvent; from benzoic acid by manganous precipitation (c). a. A colorless solid, crystallizing (from vapor or solution) in monoclinic prisms or laminse, melting at 1290 C. (264~ F.), vaporizing at about 300~ C. (572~ F.) It is very sparingly soluble in cold, moderately soluble in boiling water, freely soluble in alcohol and in ether. The cinnamates of the alkali metals are soluble in water, those of the alkaline earthy metals sparingly soluble, the other cinnamates mostly insoluble, the silver salt nearly insoluble. It is precipitated by water from its alcoholic solutions, and by hydrochloric acid fiom water solutions of its salts of alkali metals. S UCC'INIt ACID. 4.5 When slowly distilled, cinnamic acid ev-olves cinnamene, having a persistent aromatic odor resembling that of' benzole and naphthalene together. Cinnamates subjected to dry distillation emit the odor of bitter almond oil. b. A saturated hot-water solution, acidulated with sulphuric acid, is treated with a few cubic centimetresi of a one per cent. solution of permanganate of potassium and warmed a few minutes. If cinnamic acid is present, the odor of bitter almond oil becomes apparcet.-Nitric acid with gentle heat, peroxide of lead in boiling solution, chromate and sulphuric acid with heat, evolve bitter almond oil (hydride of benzoyl) from cinnamic acid in most cases with. simultaneous production of benzoic acidc.-U-innzamctes with strong nitric acid give off odor of cinnamon oil and bitter almond oil. c. Ferric salts mwith cinnamates give a yellow precipitate; manganous salts with excess of cinnamates give a white precipitate (none with benzoates); copper salts, a greenish-blue precipitate; acetate of lead, aqprecipitate not soluble in water, Pb (C0t,,02)2, from which alcohol washes out a part of the cinnamic acid; nitrate of silver, a stable white precipitate, AgC,H,70,, insoluble in boiling water; baric and calcic salts, precipitates, easily soluble in hot water. 32. SUCCINIC ACID. H2C04H404. Chctrctcterized and identified by its physical properties (cc); its resistance to oxidation (b); its reactions with iron, manganese, lead, barium, calciuil, et6. (c)..-DistizgUis hed ~rom cinnamic acid by the color of its iron salt and by not precipitating manganous salts (31,f). —Sepctratecd from non-volatile materials by sublimation (a); from belzoic acid by insolubility of its barium salt in alcohol (30, c), and by its insolubility in chloroform or ether; from cinnamic acid by the solubility of manganous succinate (30, c). —Determined by extraction with ammonia from the ferric succinate (cd). ct. Crystallinnr in the monoclinic system, generally rhombic 46 SOLID FVOLA TILE.ACIDS. or hexagonal plates. At 130~ C. (266~ F.) it begins to emit suffocating vapors, at 130~ C. (3560 F.) it melts, and at 235~ C. (4550 F.) it sublimes as succinic anhydride (C41140,), which melts at 120~ C. (248~ F.) The succinic acid of commerce has usually more or less of yellow to brown color, and of the empyreumatic and slightly aromatic odor of oil of amber; when pure it is white, and at ordinary temperatures odorless. Succinic acid is soluble in about 13 parts of water at ordinary temperatures, in 24- parts of hot water, in 30 parts of cold or 20 parts of boiling alcohol, sparingly soluble in ether, not soluble in chloroform or benzole. —Succinic azhfycdrice is more soluble in alcohol, but less soluble in water than the acid.-The smuccin.atc; of the alkali-metals and magnesium are soluble in water;. of the alkaline earth-metals, and of most other metals in cliatomic salts, sparingly soluble; ferric succinate, insoluble. b. Nitric acid, chromic acid, and chlorine are without action upon succinic acid. Cold permanganacte solution does not afifet free sucCinic acid, but with free alkali oxalic acid is formed with deposition of binoxide of manganese. c. Ferric chloride, better if slightly basic, precipitates from solutions of succinates a brownish-red bulky precipitate of basic ferric succinate.- anganous salts do not precipitate succinates. -Acetate of lead and nitrate of silver, each, give white precipitates of normal succinates slightly soluble in water.-Arnmoniacal chloride of barium with alcohol produces a white precipitate even in dilute solutions. Quantitative.-c7. The ferric succinate is precipitated friom dilute solution of succinate by addition of ferric chloride, then acetate of sodium in excess, and then sufficient ammonia to nearly or quite -neutralize the mixture. After boiling one-fourth of a-n hour, the precipitate is filterecl out and washed, then boiled with excess of' a five per cent. solution of ammonia and filtered ancld washed with ammoniacal water. The filtrate is evaporated on the water-bath until it ceases to lose weight, and weighed,s NI4I1H1041. Or, for greater exactness, this salt while in. - IrERA TRLIC ACID. 47 solution is treated with a weighed quantity of recently calcineci magnesia, and the mixture evaporated and dried at 1500 C. (302~ F.) The increase of weight represents the succinic anhydride. 33. SALICYLIC ACID. C7HG003. (In most salts of this acid one atom of hydrogen, in a few salts two atoms, are replaced by metals.)-Crystalline, in monoclinic four-sided prisms or slender needles. M'Ielts at 125~ to 1500 C' (257~ to 302~ F.) and sublimes at about 200~ C. (392~ F.) Its vapor causes irritation in the throat: it has a sweetish-sour taste. It has a decided acid reaction upon test-papers. —It is slightly soluble in?cold, moderately soluble in hot water, fireely soluble ini alcohol and in ether. — The salicylates of the alkali, metals are insoluble in water; those of the alkaline earth metals sparingly soluble (that of calcium least); many of those of other metals not soluble. The dimetallic salts are less soluble than the monomletallic.-With ferric salts, salicylic acid forms a deep violet color. Distilled or heated with methylic alcohol and concentrated sulphuric acid, salicylate of methyl is evolved, having the odor of wintergreen oil. C t % r':.. 34. VERATRIC ACID. J911, 004, Crystallizes in slender speculmT or four-sided prisms, which effloresce at 1000 C. and mllelt at a higher temperature, then subliming without decomposition. It is sparingly soluble in cold, freely in hot water, soluble in alcohol, insoluble in ether-the solutions having a slight acid reaction. The alkaline veratrates are soluble in water and crystallizable;'the lead and silver salts insoluble. It dissolves in concentrated nitric acid, and when this solution, is diluted it deposits nitroveratric acid, soluble in alcohol, from which it crystallizes in yellow lamine. Veratric acid is separated fronm sebctcilla seecds (veratrum sabadilla) as follows: They are exhausted with alcohol acidulated with sulphuric arId, the solution is precipitated with milk of lime 48 SOLID VOLA TILE ACIDS. and filtered, the filtrate-containilng veratrate of calcium-is concentrated, treated with hydrochloric acid, and left in a cold place to crystallize. The crystals may be purified by dissolving in alcohol, and filtering through aninal charcoal. 35. PHENIC ACID. RC06H50. Purified Carbolic acid. Phenol. Phenylic alcohol. Coal-tar clreosote.- Cthcaraccterizecd and iclentfifed by its physical properties (ca); by its reactions with nitric acid (b), with ferric salts (c), with bromine (d) and chlorine (e), as a reducing agent (f), and with sulphuric acid (y).-D)itingyuished from Creosote by reacting with ferric salt in more dilute solution (c), by gelatinizing collodion, by greater solubility in ordinary glycerin, in bisulphide of carbon, and in ammonia water, and by crystallizing when pure (a). —Separated from Cresylic acid and other constituents of crude carbolic acid or from Fats by its greater solubility in water (hA); from solution (in a greater quantity of) water by saturation with common salt (i); from admixture with (a smaller quantity of) water or with other substances by treatment with chloroform or bisulphide of carbon (j); from Creosote, in part, by solution in water (hA); from soaps by successive treatment with acid, water, and chloroform (k); from fixed and volatile oils by hot water. c6. Phenic acid is a colorless-white solid, crystallizing iin long needles of the trimetric system, melting at 340 to 410 C. (930 to 106~ F.), and distilling at 182~ to 186~ C. (3590 to 367~ F.) It has a strong and persistent odor, resembling creosote but somewhat aromatic, a biting taste, and (when concentrated) a bleaching and shrivelling effect on the skin. It does not redden litmus. -It is soluble in 20 parts of water at ordinary temperatures, and dissolves two or three per cent. of water, being thereby liquefied -hence is deliquescent in the air. It is soluble in all proportions of alcohol, ether, chloroform, bisulphide of carbon, and glycerin (absolute or ordinary); in 20 parts of benzole; readily soluble in fixed oils and many volatile oils, and in aqueous solutions of potassa. and soda.-The last-named mixture* or compounds, P fHEY I C A CID. 49 sometiies termed phenates, are not of definite proportions, but are crystallizable, and are soluble in alcohol and ether. Phenic acid does not decompose carbonates, but mixes with aqueous alkaline carbonates. —It coagulates albumen and gelatin and collodion (ether-solution of gun-cotton). b. To a few drops (or a small fragment) of the material to be tested add a drop or two of concentrated nitric acid. Then add a slight excess of potassa, and if color has appeared dilute with water. The yellow color of nitrophenic acid (36, Ca) is apparent in 10,000 parts of water; of the potassic nitrophenate in 50,000 parts of water; the coluimnl having the depth of half aln inch.* The nitrophenic acid lnay be extracted fromn water by bcnzole or ether. c. Very dilute solution of ferric chloride gives a blue color with aqueous solution of phenic acid-the color being permanent (distinction from that of' Moiphia), but destroyed by boiling (distinction from that of Tannic acid). Oxalic acid destroys the color, and many organic substances prevent its formation; it is not extracted by benzole or chloroform. In this test, the result is distinguished from a similar one with Creosote by the following precautions (FLUCKIGER): 1st, take 1 part of solution of ferric chloride of specific gravity 1.34, and 9 parts of the liquid to be tested (with pure carbolic acid the mixture has a yellowish hue; with pure creosote, no color). 2d, add 5 parts of 85 per cent. alcohol (with pure carbolic acid, a clear brown -liquid; with pure creosote, a green solution). 3d, add 60 parts of water; with pure creosote, the result is a dingy brownish color; if phenic acid is present, a fine blue color appears. cl. Bromine water gives a yellowish-white precipitate in even very dilute solutions of phenic acid (the same with Creosote). e. Chlorine gas (from chlorate of potassium and hydrochloric aicid) forms a deep yellow color —chloride of phenyl. PRESCOTT; Proceedings Am. Phar. Asso., xix, 550, and Chem. News, ej0 SOLID tVOLA TILE A CIDS. f: Alkaline cupric solution is not redtuced by (pure) phenic acid (is reduced by crude " carbolic acid"). Mercury and silver salts are only slowly reduced by boiling with phenic acid (are reduced by impure). Permanganate solution is reduced by pure phenic acid, in solutions acid or alkaline, with separation of binoxide of manaanese. y. With sulphuric acid-equal parts of the concentrated acids at 290~ C. for a quarter of an hour furnishing the best rcsult-Sulphophenic acid is formed (37). Quantitative.-h. Cresylic acid and other admixtures (as fats) nearly or quite insoluble in water may be approximately separated and determined by solution with 20 parts of water. In a cylindrical graduate of - litre (or larger) capacity, place 10 c.c. of the carbolic acid or mixture under examination, add 200 c.c. of water, agitate, and set aside. Rcad from the bottom the number of c.c. of impurities. i. Phenic acid may be approximately separated from water solution by adding chloride of sodium as long as the latter dissolves. If the operation be performed in a cylindrical graduate, as above, the layer of phonic acid is read fiom the top. j. Phenic acid may be approximately deprived of water and the amount of the latter ascertained by mixture with chloroform or bisulphide of carbon. In a graduate of a little more than 20 c.c. capacity (a test-glass or test-tube may be graduated for the purpose), place 10 c.c. of the phenic acid under examination and add 10 c.c. of the chloroform or bisulphide of carbon, agitate, stopper, and set aside a few hours. Read off fiom the top the amount of.water separated.-Phenic acid may be separated fiom various mixtures in the same manner; for this purpose the mixture should be made neutral to test-paper, if not so already. The chloroform or bisulphide of carbon may be removed by evaporation in a warm place. k. In separation of phenic acid f''om soac))s, the latter is decomposed by digestinol( w-ith dilutte sulphuric acid and hot A-lNTit OOPI1E.I IC AG CID. 5 wvater; wlien coldl, the fat acid is separated, by use of a wet filter if necessary, and washed with water; and the water solution and washings exhausted with chloroform. The chloroform may be distilled from the phenic acid, and if necessary the distillation repeated. 36. NITROPHENIC ACID. HC6H2 (NO2)30. (Trinitrophenic acid.) Trinitrophenol. Carbazotic acid. Picric acid.Icent~,tflecd by its physical properties, especially its intense coloring effects (a); its precipitation of alkaloids (b); its reactions with special reagents (c). —Separatecl from water solutions by extraction with chloroform, etc. (a); by crystallization as a potassium salt (cl). —Determnined as salt of oinchonia (e). a. In bright yellow crystalline scales or in octahedrons of the trimetric system. It melts when slowly heated and afterward sublimes; when quickly heated it explodes. It has a very bitter and somewhat acrid and sour taste, and when heated a suffocating odor and effect. It reddens litmus. It is solhtble in 100 parts of water at 150 C. (59~ F.) and in 25 parts at 800 C. (176~ F.), less soluble in water acidulated with mineral acids, and freely soluble in alcohol, ether, chloroform, benzole, petroleum naphtha, and amylic alcohol. These solvents, which are not miscible with water, remove nitrophenic acid from water by aid of acidulation with sulphuric acid. The solutions have a yellow color, perceptible when very dilute; except solutions in benzole, petroleum naphtha, and dilute sulphuric acid, which are colorless. The colorless as well as colored solutions stain white paper, and more permanently stain the skin and fabrics of nitrogenous composition. The normal metallic picrates are all soluble in water, that of potassium being one of the least soluble, and requiring 260 parts of cold or 14 parts of boiling water for solution. This salt is insoluble in alcohol. —Many of the picrates explode more violently than the free acid, and oxidizable agents in intimate 52 SOLID VOLATILE ACIDS. contact facilitate explosion, which may occur by trituration or pressure. b. Solution of salts of most of the alkaloids precipitate nitro phenic acid or its soluble salts-the cinchona alkaloids, the opium alkaloids, except morphia and pseudomorphia, the strychnos alkaloids, veratria, berberina, colchicia, and delphinia, being fully precipitated from solution even when dilute and well acidulated with sulphuric acid. Morphia is precipitated from moderately concentrated solutions having little or no free acid. The precipitates are yellow, and are dissolved by hydrochloric acid. Compare 135, e. c. With ammoniacal cupric sulphate solution, nitrophenic acid forms a green precipitate.-Potassic cyanide, or potassic sulphide, or grape sugar, with nitrophenic acid and excess of potassa, in hot solution, gives a blood-red solution (yellow when greatly diluted) from formation of isopzpTrcate of potassium (the crystals of which are green by reflected light). —If ferrous sulphate is boiled in solution with nitrophenic acid, treated with excess of ammonia and filtered, the filtrate concentrated and acidulated with acetic acid, bright-red crystals of picramic acid are formed. Stannous chloride and several other reducing agents may be substituted for the ferrous salt. Picramic acid is nearly insoluble in water, but soluble in alcohol or ether. d. The graded solubility of potassic nitrophenate in hot and cold water and in alcohol (a) enables this salt to be almost perfectly removed from solution, in beautiful crystals, by gradual cooling of the hot water solution, with gradual addition of alcohol after crystallization has ceased in the cold water. Quantitative.-e. Nitrophenic acid or a soluble salt of this acid is precipitated by a solution of sulphate of cinchonia acidulated with sulphuric acid, the precipitate is washed with water, dried at a very gentle warmth, then heated (and melted) on the water-bath and weighed. CGoH,4N, (0C3H[NOH],O) 2H3C18I, (NO,)30:: 0.6123. LA CT'IC A CID. 53 87. SULPHOPHENIC ACID. 1CTirSO4, Phenyl sulphuric acid. Sulphophenylic acid. Sulphocarbolic acid. —Only preserved in its salts, which are stable and crystallizable compounds, decomposed by nitric acid with the formation of nitrophenic acids (35, b), and very gradually decomposed by boiling in solution with formation of sulphates and phenic acid."' Free sulphophenic acid evolves phenic acid when heated to the boiling point of the latter.-The sulphophenates are all soluble in water, and mostly soluble in alcohol. LIQUID NON-VOLATILE ACID. 38. LACTIC ACID. 11EC3H503. Characterized by its physical properties (a); by the solubility and crystalline form of its salts (b); by the extent of its reducing power (c).Seplarated from many acids by the solubility of its lead salt in water, alcohol, and ether (d); from glycerin, sugar, etc., by the insolubility of its zinc salt in alcohol (f); from tissues, etc., as below (e). —Determined by saturation with alkali (g); by weight of zinc or magnesium salt (h). a. Absolute lactic acid is a colorless, odorless, syrupy liquid, of a very acid taste. Pure, it has the spec. grayv. 1.248; when 75 per cent., the spec. grayv. 1.212. Not volatile without decomposition; not decomposed by heat below 130w C.; at 1450 C. vaporizes dilactic acid, at higher temperature lactide, both of which are converted to lactates by the alkalies -S-oluble in all proportions of water, alcohol, and ether; sl'ily soluble in chloroform. (Glyceric acid, CH604, which ensembles lactic acid, is insoluble in ether.) Concentrated sulpimric acid mixes with.lactic acid without blackening it. Heated nr platinum foil, it leaves a slight carbon residue which burns wholly away. * PRESCOTT: Chem. News, xxvi., 269. 54,1Q iQUID NYON- — VOLATIL rJ A4 (D. b. The metallic lactates are all soluble in Nwater, being, mostly sparingly soluble in cold, freely in boiling water. Calciumi2 lactate is soluble in 9-1- parts (sarcolactate in 121- parts) of cold water, soluble in alcohol, not in ether. Barimn lactate is soluble in water and alcohol, insoluble in ether. Zinc lactate is soluble in 58 parts: of cold, 6 parts of boiling water; insoluble in alcohol (sarcolactate in 6 parts cold water and in 2.2 parts cold alcohol). Silver lactate is soluble in water and in hot alcohol. Lead lactate is freely soluble in water, sparingly soluble in cold, readily in hot alcohol, slightly soluble in ether. (Glycerate of lead is but slightly soluble in cold water.) Calcium lactate (saturated with base) crystallizes in small white mammillated tufts, seen under the microscope to consist of delicate needles, some of which resemble a bundle of bristles bound midway between the ends. The acid lactate of calcium (supersaturated with acid) forms white hemispheres, compactly made of radiate needles, trimetric.' Zinc lactate crystallizes from concentrated solutions in shining crusts, from dilute solutions in four-sided prismatic needles; the,ciystals, Zn(CHO,)2. 3H20O, lose their water rapidly at 1000'C., and the salt decomposes above 210~ C. (Zinc Sarcolactate crystallizes in slender needles, Zn(CH50,)2.21H20, losing thei- crystal water very slowly at 1000 and giving off empyreumatic vacpor, telow 150~.) Silver lactate crystallizes from neutral soIiions, in slender needles, grouped in nodules, quickly blackening in the light. c. Lactic acid does not reduce the alkaline solution of sulphate of copper, but quickly reduces potassium permanganate from acid or alkaline solutions. d. Lactic acid may be separated from acids which form insoluble lead salts (and other insoluble bodies), according to the general method given at 40, g, either in alcohoolic or aqueous solution. In a similar manner it is removed from insoluble barium salts, as soluble barium lactate, after saturation with carbonate of barium. The barium is then removed fiom the filtrate by precipitation with sulphuric acid and filtration, and FOP -VI3 ACID. 55 the sulphuric acid is removed from the lactic acid in the last filtrate by repeatedly adding a mixture of 1 part of alcohol and 5 parts of ether and evaporating. e. Also, the fluid obtained by digestion and expression of tissues may be treated with sulphuric acid to fix albuminous matters, filtered, treated with alcohol and five times its weight of ether and again evaporated, filtering when necessary, till the sulphuric acid is removed. f. A (weighed) quantity of the material containing lactic acid, mixed with substances soluble in alcohol, is saturated in aqueous solution with oxide of zinc, the mixture evaporated to dryness, the residue digested in alcohol and filtered. The filtrate will contain the substances soluble in alcohol; the residue will contain zinc lactate, soluble in water. Quantitative. —g. In the acidimetry of lactic acid, onetenth equivalent, 9.000 being taken, the required number of cubic centimeters of normal solution of alkali equals the number per cent. of'HC13I0503. A. Saturating with oxide of zinc or oxide of magnesium, filtering and washing with water, crystallizing or evaporating, and drying at 1000 C.: Mg(C 110, ),: 2HCE0O1: 1:O0.8911. Zn(CHO,3)2 2HOIIC,0:: 1: 0.7402. LIQUID VOLATILE ACIDS. 39. FSORMIC ACID. HC1HO1. Identified by its odor (a); by its reducing power upon salts of the noble metals, permanganates, chromates, etc.-the radical CHO2 being oxidized to H=,O and CO,-(b); by the color of its ferric salt in solution (c); by the odor of its ethyl salt (d).-i-Se2arated from substances less a5n GI~Q UIL) VOLATILE ACI (DS volatile by distillation (f); from organic acids in general by the solubility of its lead salt in water (g); from acetic acid by the insolubility of its lead salt and its magnesium salt in alcohol (h).-Determined by acidimetry (j), or by oxidation to carbonic anhydride (k). a. The odor of formic acid is pungent, irritating, characteristic, slightly acetous, and -of an intensity varying greatly with the strength and temperature of its solutions. In contact with the skin, it causes intense irritation. b. Nitrate of silver in concentrated solution gives, with solutions -of formates, the white crystalline precipitate of formate of silver, not formed with free formic acid. The precipitate darkens upon standing a short time, and when warmed it is quickly reduced to metallic silver. In case the formic acid is free, or the formate in dilute solution, so that formate of silver is not precipitated, the reduction of metallic silver occurs slowly in warm solution. An excess of ammonia retards or prevents the reduction. ]Mercuric chloride in hot solution is gradually reduced by formic acid, more readily by formates, a white precipitate of mercurous chloride forming first, then a dark gray precipitate of metallic mercury. Alkaline chlorides and acetic acid retard or prevent the reduction. Solution of potassic permanganate is slowly decolorized at ordinary temperatures, and warm solution of chromic acid is gradually turned green, by sufficient formic acid or formates. Chlorine and bromine oxidize formic acid to carbonic anhydride and hydrazid. Nitric acid also decomposes it, likewise peroxide of mercury in boiling solution (removal from acetic acid, see i). c. Ferric chloride solution with formates produce a red solution of ferric formate. d. With alcohol and sulphuric acid, at a gentle heat, formic acid becomes formate of ethyl, C2H5CHO2, an ether having a strong, agreeable odor, like that of peach-kernels, and distilling at about 55~ C. iOR3tI( A CID. 57 e. Strong sulphuric acid, at a gentle heat, decomposes 1C1IO2 into O,20 and CO. Strong alkalies at a gentle heat convert formic acid into oxalates; at a higher heat carbonates are formed with liberation of carbonic oxide. f. Absolute formic acid distils at 1000; the aqueous solution, 77.5 per cent. of acid, at ordinary atmospheric pressure, boils at 107.1~, and mixtures containing larger or smaller proportions of water are reduced to this per cent. of acid and boiling-point by repeated distillations. A glycerin-bath may be used. Formic and acetic acids are not easily separated by fractional distillation. Dilute sulphuric acid is employed for the production of formic acid from formates. g. The formates are all soluble in water. Plumbic formate requires 40 parts of cold water or a smaller proportion of hot water for solution. Argentic formate is sparingly soluble in cold water, decomposed by hot water (b). Mercurous formate is the least soluble salt of this acid, requiring about 500 parts of cold water for solution. It is much more soluble by hot water, in which it decomposes.-In alcohol, the formates of lead, magnesium, calcium, and barium are insoluble, the alkaline formates soluble. Formic acid is separated from far the larger number of organic acids by precipitation of the latter as lead salts. With free acids, the method given for acetic acid (40, g) may be employed, avoiding the use of heat in any part of the operation. h. Formic acid is separated from Acetic acid by saturating with magnesia, or with lead oxide or carbonate, adding much alcohol, filtering and washing with alcohol. In the preparation of formic acid, acetic acid is approximately separated by the crystallization of plumbic formate from water solution containing also plumbic acetate. i. Formic acid is removed from acetic acids, or from other acids not very easily oxidized, by hot digestion with mercuric oxide, until effervescence ceases. HgO and 11CHO2, form HI2O and CO, and Hg. The filtrate will contain mercuric acetate if 5t8 LI'Q UZID VTOLA TILE ACIDS. acetic acid Nere present; in fact, the presence of mercury in the filtrate indicates some other acid besides formic. Acids forming insoluble mercury salts may be obtained from the residue, by treatment with hydrosulphuric acid, filtration, and dissipation of the excess of hydrosulphuric acid in the last filtrate. Quantitative.-j. Free formic acid may be determined by the ordinary methods of acidimetry. See 40, i, j. Or the acid may be saturated with pure carbonate of barium, and the formate of barium precipitated as a sulphate —BaSO,: 2H1CHO 2:: 1: 0.395. k. Formic acid is quantitatively separated from acetic acid by precipitation with alcoholic solution of plumbic acetate, washing the precipitate with alcohol. The formate of lead may be determined, after oxidation with chromate and an acid, as carbonic anhydride. The lead formate, with solution of bichromate of potassium, is placed in an apparatus for determination of carbonic anhydride (from carbonates whose bases form insoluble sulphates), and decomposed by nitric acid, gradually, as the dry gas escapes, in the usual manner. C02 HCHO2:: 1: 0.956. Or, the carbonic anhydride may be received in an ammoniacal solution of chloride of barium. BaCO ~;ECIIHO:: 1:0.233. 40. ACETIC ACID. rCIt,02. cIdentijfed by its odor (a), by the odor of its ethyl salt (b), by the odor arising from the ignition of its salts alone (c) or with arsenious acid (d), by the color of its ferric salt in solution (e), by the free solubility of its lead salt and the sparing solubility of its silver salt (f).-Separatecl from less volatile or more volatile substances, by distillation (h); from the larger number of acids, by the solubility of its lead salt (g). —Determined as free acid, or in salts of insoluble bases, by its saturating power (i, j). a. Aqueous acetic acid evolves the odor of vinegar, which is pungent in'proportion to the strength and temperature of the solution. Acetates impart the same odor in a very slight degree. At (.''EI Y,,1 C'ID. 9 b. The cacetate of ethyl, 0I-25 C,H202,, is obtained by warming acetic acid or its salts with sulphuric acid and a small proportion of alcohol. It is recognized by its pungent and fragrant odor, ethereal, refreshing, and obscurely acetous. It distils at 74~, and may be cleared from acids and from water by contact with dry carbonate of potassium. It is neutral to test-paper, and is soluble in about ten parts of water. c. When ignited in a tube closed at one end, nmost of the metallic acetates evolve acetone, C0H60, a vapor of an agreeable odor, readily burning with a white flame. Liquid acetone boils at 56~. d. If acetates are heated with fixed alkali and arsenious acid, the offensive odor of cacodyl is observed, As2(C.:5)2:20O. e. Solutions of ferric salts, with solutions of acetates (not with hydric acetate), form a dark red solution of ferric acetate, Fe2(C230,2)G, decolorized by strong sulphuric or hydrochloric acid (distinction from MIeconate), not decolorized by solution of mercuric chloride (distinction from Sulphocyanate), precipitated as basic acetate by boiling. f. The metallic acetates are soluble in water, argentic and mercurous acetates being sparingly soluble and forming as crystalline precipitates from concentrated solutions. Argenytic acetate forms white, fine, scaly crystals, soluble in one hundred parts of cold water and in a smaller proportion of hot water. Mercurous acetate forms scaly crystals, sparingly soluble in water, more soluble in dilute acetic acid. The normal and basic acetates of lead are freely soluble in water. In alcohol, mercurous and argentic acetates are nearly insoluble, mercuric acetate is slowly decomposed, normal lead acetate freely soluble, basic lead acetates sparingly soluble, the other metallic acetates soluble. Zinc acetate crystallizes in hexagonal plates, very soluble in water. g. The solubility of its lead salt enables (free) acetic acid to be separated from organic acids in general (not lactic, formic, butyric, valerie)-in qualitative or quantitative work-as follows: 60 L.Q UID V'OLA TILE A CIDS% Digest the acids in a closed flask at a gentle heat with sufficient oxide of lead, until the mixture is just alkaline to litmus; filter and wash. For complete separation from tartaric acid, or other acid having its lead salt appreciably soluble in water but insoluble in alcohol, the solution should be alcoholic and the washing wholly by alcohol, avoiding the use of much excess of oxide of lead. Residue (A): plumbic salts of organic acids (excess of oxide of lead). Filtrate (B). plumbic acetate (basic and not freely soluble in alcohol). Treat filtrate B, in a long-necked flask, with washed hydrosulphuric acid gas, to complete precipitation; filter and wash with water. Return the filtrate and washings to the flask, insert therein a glass tube and blow air from a bellows through the same until the hydrosulphuric acid is expelled. Filtrate (c): acetic acid (lactic acid; formic acid; butyric acid; valeric acid). Treat residue A with washed hydrosulphuric acid gas, until the residue appears wholly black, -as seen from beneath the vessel. Filter and wash, and expel the hydrosulphuric acid from the filtrate by a current of air from a bellows, as described above. Filtrate (D): acids whose lead salts are insoluble in water (or alcohol). h. Acetic acid boils at 119~. It may be distilled from a paraffin or glycerin bath. In distillation from sulphuric acid, the acetic acid is liable to be oxidized to a slight extent, with production of carbonic and sulphurous anhydrides, the latter condensing with the acetic acid. For the acidimetry of the distillate, acetates should- be distilled with phosphoric acid (or with hydrochloric acid, and the subsequent determination of the latter by standard solution of silver). Fractional distillation-with or without fractional saturation-may be employed in the separation of acetic acid from other acids more or less volatile than itself. (See, also, Valerie acid, c.) Quantitative. — i. Free acetic acid, in absence of other acids, may be determined by nteutralization with an ascertained quantity of alkali. Different alkalies have been used in standard solution for this purpose-as soda, potassa, sodic carbonate, lime dissolved with sugar, amnmonio-cupric sulphate. In the solid state, calcined magnesia, crystallized sodic carbonate, and potassic B UTY?'Ji [( 17 (i). 61 bicarbonate have been employed. Also barice carbonate, the barium dissolved as acetate being then determnined as sulphate. In testing colorless or slightly colored solutions with any of the standard solutions named above, except that of ammoniocupric sulphate, the point of saturation is indicated by litmus; but in case the acetic solution is colored somewhat, a little sul. phate of copper may be added, when the neutral point will be indicated by the cloudiness due to the commencing precipitate of hydrate of copper. With the ammonio-cupric standard solution, the solution determined must be very dilute, when saturation will be shown by the turbidity. In the use of calcined magnesia, saturation is indicated by the dissolving of the solid, as well as by the color of litmus. In the method with carbonate of barium, the acid is saturated with the pure carbonate; the acetate of barium filtered and washed from the excess of the reagent, precipitated by dilute sulphuric acid and weighed as barium sulphate. BaSO,: 2EB C2Ot2:0 1: 0.515. The most convenient standard of solutions of alkalies are the "1normal solutions," operating upon one-tenth equivalent of the acid —HC,21302 —6.000 grams of the material. j. The acetic acid producible from acetates of bases insoluble in water may be estimated vdlumetrically, as follows: To a solution of 6.000 grams of the acetate, add normal solution of alkali to complete precipitation, noting the number of cubic centimeters used. Filter and wash till the washings do not affect litmus-paper. To the filtrate and washings, add of a normal solution of acid to the neutral point. The number of cubic centimeters of alkali used, minus the number of cubic centimeters of acid used, expresses the per cent. of acetic acid sought. 41. BUTYRIC ACID. C4HI-702. Identified by its odor'(a); by the. odor of its ethyl salt (b); by'its liquidity, -solubilities, and the properties of its salts of lead, barium, and 6Q2 LIQ ~ TVO()LA TILE C:'lIDS. other metals (c).-Separated from acids having higher or lower boiling points by fractional saturation and distillation (d); from many acids by the solubility of its lead salt in water, and from other acids by the solubility of its lead salt in alcohol (c. See process g, under Acetic acid).-Determized by saturation (e); by ultimate analysis. a. The odor of butyric acid is like that of rancid butter, but somewhat less offensive, and obscurely acetous, closely resembling that given by slightly rancid butter when heated. It is a strong and persistent odor, not much diminished bydilution of the acid, but increased by warming it. The metallic butyrates are odorless, unless undergoing decomposition. b. _Butyric ether —C H C4H O.-is formed by warming butyric acid or a butyrate with alcohol and excess of sulphuric acid. It has the odor of pineapples, by which it is readily identified. It rises to the surface of aqueous mixtures, and may be decanted, and purified from acid by addition of chalk and from water by chloride of calcium. It is soluble in all proportions of alcohol and ether, very slightly soluble in water. It distils at 119~ C. c. Absolute butyric acid is a colorless, mobile liqwuic, solidified at very low temperatures, at 15~ C. having a specific gravity of.974. It is soluble in all proportions of water, alcohol, ether, and wood-spirit. It is not soluble in concentrated solutions of freely soluble salts. The mnetallic butyrates are all soluble in water; plumbic, argentic, and mercurous sparingly soluble; calcic freely soluble in cold water, but sparingly soluble in hot water. Plumbic butyrate is more soluble in alcohol than in water; argentic butyrate less soluble in alcohol than in water; baric butyrate very sparingly soluble in alcohol; potassic butyrate freely soluble in alcohol. Butyrate of lead is formed slowly on adding butyric acid to lead acetate as a heavy liquid which solidifies on standing. Alkaline butyrates, with lead acetate in moderately concentrated.olution, give a milky precipitate, which afterward solidifies in TALLRIC A. (-'ID. 63 a white semi-crystalline mass. A nearly saturated solution of butyrate of lead, left over sulphuric acid, deposits fine, silky needles which are anhydrous. Butyrate of silver is formed in shining scales by mixing moderately dilute solutions of nitrate of silver and alkaline butyrate. Butyrate of colpper forms bluegreen monoclinic crystals sparingly soluble in water (see Valerie acid, b). Butyrate of zinc crystallizes in shining scales. Butyrate of barium is formed by saturating butyric acid with hydrate of barium, and crystallizes in the cold in long flattened prisms containing 2 aq. Butyrate of calcinum, obtained in the same way, crystallizes in delicate needles, anhydrous.Butyrates of lead, barium, calcium, potassium, and some other metals, r otate rapidly when dropped in small firagments upon water. d. Butyric acid distils unchanged at 157~ C. Its separation from propionic, acetic, valerie, caproic, and other acids of contiguous boiling points, is best accomplished by fractional saturation and distillation. (43. Also, see Valeric acid, c.) Quantitative.-e. Butyric acid has been determined by saturation with (10 parts of dry) bismuth hydrate, and precipitation of the butyrate of bismuth with ammonia to obtain the oxide of bismuth, which is dried and weighed. Bi2O3: 611 C0H'02:: I: 1.1282. 42. VALERIC ACID. HC111902. *Identfeled by its odor and taste, the odor of its ethers, and the taste of its alkaline salts (a); by its consistence, boiling point, solubilities, and the properties of certain' of its metallic salts (b). —Sepaaratecd by fractional distillation (c); by solubility of certain salts of lead, copper, iron, barium, zinc (d).-Determined by acidimetry (e).; approximately, by solubility in water (f). a. The odor of valerie acid is that characteristic of dried valerian root and of common valerian oil, in part like that of decayed cheese and also of butyric acid. When not diluted, it has a sour, burning, and disagreeable taste alnd caustic effect. 64 LIQUID VI'OLA T'liLE A CINS. The alkaline valerates have a sweetish taste, with a pungent and alkaline after-taste, and when moist exhale some odor of valeric acid. Ethyl valerale, evolved on warming valerip acid or its salts with alcohol and sulphuric acid, has an agreeable, fruity odor. Amzyl valerate, formed by heating valerianic acid with a very little fusel-oil and sulphuric acid, is characterized by a pleasant apple odor. b. Absolute valeric acid (" monohydrate") is a transparent and mobile oily liquid, of sp. gr. of.937 at 15~ C., boiling at 175~ C. With water it forms a definite hydrate-HCO: OH 02. HI20 (" trihydrate ") —an oily liquid of sp. gr. of.950, boiling at 1650 C., but gradually dehydrated by distillation, the first distilled portion containing the hydrate mixed with water, after which the absolute acid passes over.-Absolute valeric acid is soluble in 30 parts of water at ordinary temperatures; the hydrated acid in 26 parts. It is almost wholly removed from solution by saturation with freely soluble salts, as chloride of calcium or of sodium. It is soluble in all proportions of alcohol, ether, chloroform, and glacial acetic acid. The valerates of the alkali metals, are deliquescent and freely soluble in water and in alcohol; of the alkaline earth metals, moderately soluble in water and in aqueous alcohol. Aluminum valerate is insoluble. Ferric valerate (basic) insoluble. Zinc valerate is soluble in 90 parts of water, and ill 60 parts of alcohol of. 80 per cent. Bismuth valerate (basic) insoluble in water; silver valerate, slightly soluble in water; lead valerate (normal) readily soluble in water, (basic) sparingly soluble in water; mercuric valerate, soluble; mercurous, slightly soluble; cupric valerate, moderately soluble. The lead valerate crystallizes in shining needles gathered in hemispherical groups; silver valerate in white, shining plates; copper valerate in green-blue monoclinic prisms; mercury valerate in slender white needles; zinc valerate in snow-white plates of pearly lustre. The sodium and potassium valerates melt at 140~ C., and solidify in amorphous cakes, white when pure. T.AE RIC' 1 CID. 65 Sodium valerate crystallizes, by spontaneous evaporation in waym and dry air, in cauliflower-shaped lmasses.-Many of the vaierates rotate upon the surface of water when dropped in small fragments upon it. Silver valerate is precijgitcted from solutions of valerates not too dilute in a white curd, turning black in the light.Solution of acetate of copper on agitation with concentrated valerie acid forms anhydrous valerate of copper in oily droplets, -which, after five to twenty minutes, crystallize as gtieenish-blue monoclinic prisms or octahedrons of hydrated cupric valerate, soluble in a moderate quantity of water and in alcohol. (Distinction from BZutyric ccic, which forms in solution of acetate of copper, not very dilute, an immediate precipitate or turbidity of butyrate of copper, bluish-green and finely crystalline in monoclinic prisms-LoRocQUE and IIRAUT.)-Valerates are cieco2mposecl by acetic, tartaric, citric, and malic acids; not by butyric acid. -Valerie acid decolors potassium permanganate solution. c. Valerie acid is easily separated from Butyric acid by fractional saturation'and.1 dCistillation of the latter, the butyrate being wholly decomposed at the temperature of the less volatile acid, which remains in the retort as valerate (41, d). With Acetic acid, hqwever, the more volatile acid is held by the base in the retort, while valerie acid distils over. In decomposing valerates for distillation of the acid, sulphuric acid may be employed, avoidinog a strong excess. cd. Valerie acid is separated from acids which form insoluble lead salts by the method given under Acetic acid, g. From acids forming soluble salts of aluminum, by the insolubility of aluminum valerate.-lf a solution of. a valerate made slightly alkaline to test-paper is fully decomposed by solution of ferric chloride, and after a short time filtered, the filtrate will be red if Acetic acid is present.' A solution of valerie acid in 50 parts of hot water, saturated with hydrated carbonate of zinc, yields a liquid which, when filtered and evaporated to 10 parts and 66' I.rIQ U.I.D IrOLA TILE' ACIDS. cooled, affords white pearly crystals of valerate of zinc. The mother-water, drained from these crystals, should not yield, by further evaporation and cooling, a salt crystallizing in six-sided tables and very soluble in water " (acetate).-Valerate of barium is soluble in 2 parts cold water, sparingly soluble in alcohol; Caprylate of barium in 120 parts water, nearly insoluble in alcohol; Caprinate of barium almost insoluble in water. Quantitative. —e. Free valeric acid, in absence of other acids, may be determnined by normal volumetric solution of alkali. Weighing 10.2, the number of cub. cent. of alkali solution equals the number per cent. of HCH9O,2; weighing 12., the number of cub. cent. equals the number per cent. of 1HC5HO92..H2O. f. A weighed quantity of the acid (1 gram in a tared flask) should require not less than 26 times its weight of water at 16~ to 180 C. for perfect solution (absence of alcohol, acetic acid, valerates, etc.), and should require not more than 30 times its weight for exact solution (absence of fatty acids, valeral, etc.)PDUFLOS. 43. ~Formic, Acetic, Butyric, and Valerie acids may be separated from each other by Fractional Saturation and Distillation, as follows: (This method is generally applicable in fractional distillation.)-l'o one-half of the material to be distilled add enough potassa or soda to neutralize, and then mix with the other half and distil-with a thermometer in the retort or generating flask to show the boiling point-receiving the distillate all together. If the boiling point has been constant, no farther separation can be effected by this method; if not, saturate half the distillate, mix with the remainder, and distil as before. Repeat the fractional saturation with alkali and distillation of the free acid of the receiver until the distillate has a constant boiling point. Now to the several retort residues add excess of dilute sulphuric acid and distil each; if their distillates do not show a constant boiling point, half saturate and distil, in each case, as before, until the boiling points are constant. Again T'OLA TILE IA T A CA(IDS. 61 decompose and distil the retort residues, as before, repeating the operations until the whole of the organic acids is obtained in separate distillates, each showing a constant boiling point. The work may be tabulated as follows: Fractional Saturation and Distillation. Mixture of acids, a, b, c, d, of different boiling points. Neutralize half the mixed acids and distil. IN RETORT: salts of c, d. Saturate with sulphuric acid and IN RECEIVER: a, b (boil. point distil. changes). (Boil. point- changes.) Neutralize half and distil. Neutralize half and distil. IN RETORT: salt IN RECEIVER: C. IN RETORT: salt IN REwCEIVER_: a. of d. of b. Saturate with sul- (Boil.pt. const'nt.) Saturate with sul- (Boil. pt. const.) phuric acid and phuric acid and IN RECEIVER: d. IN REcEIVER: b. (Boil.pt. const'nt.) (Boil. pt. const'nt.)1 44. VOLATILE FAT ACIDS of the Acetic Series. (Approaching towards these, in their properties, are the volatile acids of the acetic series which do not have a fatty consistence, though commonly termed "volatile fatty acids " —viz., FORMIC, ACETIC [PROPYLIC], BUTYRIC, and VALERIANIC acids.) CAPROIC ACID, HCc 1C11102, boil. at 200~C., melt. at 9~C. (ENANTHYC ACID, HC7 H11302, "1 " 2180C " below 200C. CAPRYLIC ACID, HC18 H1O2, " " 2360C., " at 15~C. PELARGONIC ACID, HCg E, 1702, " " 2600C., " " 100C. CAPRIC ACID, HC10192O,, " with decom., " 300C. C7taraccterized,by their pungent and unpleasant odors (when free), by the persistent and fragrant odors of their ethyl ethers, by their liquid and more or less oily consistence at ordinary temperatures and their capability of distillation, by their sparing 0()8 iSilFAT ACIDS, L[IQUID AND SOLID. solubility or insolubility in water and ready solubility in alcohol and in ether, by their acid reaction, by forming with alkalies salts soluble in water. Separated from each other by Fractional Crystallization, as barium salts, as follows: Add to the mixture (aqueous or alcoholic) sufficient potassa to neutralize, and add chloride of barium to decompose. Crystallize, removing the successive crops of crystals: FROM/ WATER SOLUTION. PlROB ALCOHOL SOLUTION. 1st crop-baric caprate, 1st crop-baric caprylate, 2d " " pelargonate, 2d " " cenanthate, 3d " " caprylate, 3d " " pelargonate, 4th " " enanthate, and caprate, 5th" " caproate. 4th " " caproate. The aqueous crystal-crops may be washed with hot alcoholthe washings containing the salts, successively, in order the reverse o'f their crystallization from alcohol. Thus, the third crop of crystals from water, when washed with alcohol, lose first caproate, then caprate and pelargonate, lastly cenanthate, with little loss of caprylate. Separated, also, by Fractional Saturation (43). FAT ACIDS, LIQUID AND SOLID. 45. VNON-VOLATILE EPAT ACIDS. Characterized by an oily consistence, leaving a permanent oil-spot upon paper, and melting at different temperatures, mostly between 140 C. and 80~ C.; by insolubility in water, upon which they mostly float (in oily drops or layers, liquid if the water is hot); by free solubility in alcohol, the solutions mostly having an acid reaction, and by solubility in ether; by the (soapy) solubility of their NOAN- VOLA JTILE FAT AC'IDS. 69 alkaline salts in water; by the waxy consistence of their lead salts, which melt and do not dissolve in water and have differing solubilities in alcohol and ether; by forming white, milky precipitates when their alkaline salts in water solution are treated with salts of metals not alkalies, or with acids, also when (as free acids) their alcohol solutions are diluted with water. The avidity of drying oils for oxygen is a characteristic of their acids. (See Fixed Oils.) The nine following are some of the more frequently occurring non-volatile fat acids, placed in order of their fusibility: 46. RICINOLEIC ACID. H C 18H330. Melts at 100 to 60 C. (140 to 21~ F.). Yellowish, syrupy, inodorous, of harsh and persistent taste; reddens litmus, and in alcoholic solution decomposes carbonates with effervescence; distils an illy-smelling liquid; its glyceride and all its metallic salts soluble in alcohol, its lead salt soluble in ether. When Castor Oil (ricinoleate of glyceryl) is heated on a sand-bath with a double volume of nitric acid of 25 per cent., until the nitric acid is all removed.; the residue saturated with concentrated solution of sodium carbonatethe characteristic odor of cenanthye acid is obtained. 47. OLEIC ACID. H C18H3,02. Melts at 14~ C. (570 F.), soft above 40 C. (390 F.) Colorless, limpid liquid of sp. gr. 0.808, odorless and tasteless, crystallizing from cold alcoholic solution in white needles; reaction neutral, becoming acid on exposure to the air, by which it finally turns brown and rancid. Its lead salt (lead plaster) is insoluble in alcohol, slowly soluble in ether (separation from palmitate, stearate, laurate, etc.) Distilled with nitric acid, all the volatile acids of the acetic series are found in the distillate. 48. LINOLEIC ACID. H:16H,02702 Melts at about 18S C. (64~ F.); faint yellow, limpid liquid of sp. gr. 0.921, of taste at first mnild and afterward harsh; faintly acid to test-paper; oxidizes in the air to a thick, viscid mass, its salts, also, being changed in the air. Mlost of the linoleates are soluble in alcohol; the lead salt is soluble in ether. 70 FAT ACIDS, LIQUID AN-D SOLID. 49. ERUCIc AcID. C2H4202. Melts at 340 C. (940 F.); crystallizes fiom alcohol inl shining needles; lead salt not soluble in ether (separation from Oleic acid). 50. LAURIC ACID. HC],2H2302. Melts at 430 C. (110~ F.); solidifies in scales and crystallizes from alcohol in white needles; slightly acid to test-paper; lead salt sparingly soluble in alcohol, insoluble in ether. 51. MYRISTIc ACID. H C4H0,O,. Melts at 540 C. (1290 F.); crystallizes in shining lamin.t; exceptional in being insoluble in ether; the alcoholic solution has an acid reaction; the lead salt is soluble in alcohol, but insoluble in ether; the barium salt nearly insoluble in alcohol. 52. PALMITIC ACID. H 16H3,102. Melts at 62~ C. (143~ F.); colorless, tasteless, odorless, showing an acid reaction; lighter than water; crystallizes, in congealing, in shining scales, from dilute solutions in slender needles; lead salt insoluble ii alcohol or cold ether; barium salt sparingly soluble in water or alcohol; calcium salt insoluble in water or ether, slightly soluble in warm alcohol. 53. STEARIC ACID. H C,18H,50. Melts at 700 C. (1590 F.); inodorous, tasteless, colorless in liquid and white in solid state; crystallizes from alcohol in needles or nacreous scales, having the specific gravity of water; its solutions distinctly acid to testpaper; lead salt insoluble in alcohol or ether, and not wetted by water and fusible at 1250 C.; barium salt insoluble in water, alcohol, or ether; magnesium salt insoluble in water, and slightly soluble in cold, more soluble in hot alcohol. [For the fusingpoints and modes of solidification of mixtures of Stearic with Laurie, lMyristic, and Palmitic acids, as determined by IHEINTz, see Watts's Dictionary, v., 414.] 54. CEROTIC ACID. H.C,7H5302. Melts at 790 C. (174~ F.); crystallizes in congealing in small grains, lighter than water; -when pure, is capable of distillation; soluble in hot alcohol and in ether, not soluble in chloroformi; solutions acid in reaction: lead salt insoluble in alcohol. iYNO.N- VOLATILE'A T ACIDS. 71 55. The non-volatile Rtt Acicds are separcated fiom neutral fats by saponification with fixed alkalies, limne, or oxide of lead, in each case effected by hot digestion in presence of water. Sometimes an alcoholic solution of alkaline salt is precipitated by alcoholic acetate of lead (the lead salt being insoluble in alcohol); in other cases, an alcoholic solution of lead salt is precipitated by alcoholic acetate of barium or of magnesium (such beings the solubilities of the respective salts). Then the purified salt is decomposed in water with dilute acid. As in manufacturing operations, the neutral fats may be decomposed by superheated steam, with separation of the fit acids together. 56. The fit acids are in some cases seplarated fronrt each other by fractionlal fusion of their glycerides, with pressure. The melting point of the glycerides (the neutral fats), is given in 59. The melting point of a mixture of free fatty acids is generally much below the mean melting point of its constituents, as shown by the tables of Ieintz mentioned inl 54, and hence in many cases no separation can be accomplished by fractional fusion. Thus, free stearic acid can be fieed from oleic but not from lauric, myristic, or palmitic acid, by this process. 57. The use of solvents in separation-of the free acids or of' their salts-is indicated to some extent by the statements of solubilities, given in this work or elsewhere, and more particularly by the various methods of prepCaraion of the acids in question, as found in Watts' Dictionary, Miller's Organic, Gmelin's Handbook, and in originall reports. Free fatty acids are separated from nteutral ldt oils (not firom castor oil), for commercial determinations, by extracting the oil with one or two volumes of 90 per cent. alcohol. The acid is then determined volumetrically with soda solution.* Also, by alkaline carbonates, which at ordinary temperatures saponify with fat acids but not with fats. Prepare a solution of * B UnS:TWN Zcitscri. Atcal. C!hem., xi., 23. 72 N-EUTiAL SUBSTA NCES, LIQUID 0R1 F~USIBLE. 10 grams crystallized sodic carbonate, 1 gram sodic bicarbonate;, and 30 c. c. water. Agitate, in a test-tube, equal volumes of this solution and of the oil, and set aside at ordinary temperatures. In absence of fat acids, the two liquids separate, more or less turbid; if fat acids are present, an emulsion is formed (from which a cream rises after some time). Old fit oils usually contain traces of fat-acids, scarcely indicated. in this test. 58. For the quanitcltive determination of free fat-acid in mixture with neutral fats, digest 10.0 grams of the oil with 2.5 grams of pulverized sodic bicarbonate and 25 drops of water, on a wrater-bath, with trituration, for an hour. When cold, extract with petroleum naphtha, stirring; evaporate the naphtha, and weigh the neutral fat so separated. Benzole is not applicable in this separation. NEUTRAL SUBSTANCES, LIQUID OR FUSIBLE. 59. FIXED OILS. Fats or Fat-oils. Glycerides of the non-volatile fat acids. (The following list includes those of most frequent occurrence in commerce.) a(. LIQUID AT ORDINARY TEMPERATURES. aa. DRYING OILS (NOT FORMIING ELAIDIN). Spec. gray. Congeal. pt. Hemp-seed,. 0.926 -25~ C., -13~ F. Greenish when fresh, afterward brownish-yellow; unpleasant odor and insipid taste. Grape-seed,..918 -13~ C., b~ F, Yellow to brownish; nearly odorless, of mild taste. Linseed,....934 -27~ C., -17~ F. Gold-yellow to brownish; strong odor and taste. Poppy-seed,.924 -18~ C., 0~ F. Straw-yellow; limpid; feebly plea-;' ant odor and taste. Walnut,...925 -18~ C., 0~ F. Slightly greenish or yellowish; thick; nearly odorless, of mild nutty taste. FIXED OILS. 73 bb. OILS DRYING TO A SLIGHT EXTENT AND SLOWLY FORMING A LITTLE ELAIDIN. Spec. gray. Congeal. pt. Beechnut,.920 -18~ C., 0~ F. Yellowish; nearly odorless and of a mild taste. Cotton-seed,...925 1~ C., 34~ F. Yellow orbrownish-yellow tocolorless; of mild taste. Croton,..942 Clear, slightly yellow; of a taste at first mild and then burning and persistent; causes pustules on the skin. Sesame,...921 0~ C., 32~ F. Yellow; of mild odor and taste. Sunflower,..924 -15~ C., 5~ F. Yellowish; limpid; nearly odorless and tasteless. CC. OILS NOT DRYING, BUT NOT FORMING ELAIDIN. Cod-liver,...930 below 14~ F. Clear yellow to red-brownl; acid reaction; characteristic fishy odor and taste. Whale,..... 925 0~ C., 32~ F. Brownish; of characteristic disagreeable bodor and taste. dd. NON-DRYING OILS, FORMING ELAIDIN. Almond,....918 -20~ C., 4~ F. Clear straw-yellow; limpid; inodorous, of a bland, sweetish taste. Castor,...963 -15~ C., 5~ F. Colorless or slight yellow; syrupy: odorless, of mild taste with acrid after-taste. (Sometimes classed among the slightly drying oils.) Colza,.....914 -64 C., 21~ F. Clear, yellowish; limpid. Hazel-nut,..920 -19~C., -2~ F. Lard,...915 10~ to 0~ C. Colorless or nearly so; slight odor of lard. Mustard (black),.915 15~ C., 5~ F. Yellowish; odorless, of mild characteristic taste. Mustard (white),.913 (not solidified). Similar to the above. Neatsfoot,. - (below 0~ C.) Yellowish; inodorous, of a bland taste. Olive,....916 5 C. to 2~ C. Greenish or yellowish; thick flowing; of slight pleasant or no odor and mild sweetish taste. Sperm,..875 - Limpid; nearly odorless. Rape-seed,...914 -6~ C., 2i~ F. Clear, yellowish; disagreeable odor and taste. 74 NEr UT1RAL S UBSTaNC~ES, LIQUID OR FUSIBLE. b. SOLID AT ORDINARY TEMPERATURES. Melting. Melting. Butter,...... 27~ to 30~ C. Tallow, Mutton,. 46~ to 50~ C. Cacao butter,... 25~ to 30~ C. Spermaceti,. 38~ to 47~ C. Lard,... 28 to 32~ C. Wax, Yellow (Bees'), 60~ to 63~ C. Tallow, Beef,. 36~ to 40O C. Wax, White,.. 65~ to 69~ C. 60. Fixed or Fat Oils are chacrccterizecl by their oily consistence and the physical properties stated above; by their solubilities (a) and cohesion-figures on water (b); by a neutral reaction; by saponification-forming soapy-soluble compounds with alkalies and waxy compounds with lead oxide (c); by giving reactions for glycerin (d); by the precipitates obtained from their soap-solutions (e); by either oxidizing to a viscid mass in the air (/), or forming elaidin with nitric acid (y); by their sensible reactions with special reagents (h). ca. Insoltble in water, upon the surface of which they float. Mostly insoluble or slightly soluble in alcohol; but Castor oil is soluble in all proportions of absolute alcohol, Spermaceti in 7 parts of boiling absolute alcohol, and Wax partly soluble in alcohol. Soluble in Ether and in Benzole, less freely soluble in petroleum naphtha and in chloroform. (Solid fats are slightly soluble in petroleum naphtha; liquid fats moderately soluble.) Miscible with volatile oils, not with glycerin. By violent agitation with water, fixed oils form milky mixtures (emnulsions) fromn which the oil quickly separates in drops; by agitation or trituration with water mucilages of gums, albumen, gelatin, sugar, and of salts, more perfect mixtures are formed, from which the oil slowly separates as a cream, still containing a little water solution and holding the oil in its characteristic microscopic spheres. b. If a drop of oil is let fall upon a still surface of perfectly pure water, the oil spreads in a film which breaks into a figure (cohesion figure) or succession of figures, characteristic of each oil-fixed oils not being distinguished from volatile oils otherwise than from each other. The formation of these figures con FIXED OILS. 75 stitutes a practicable means of' identifying the separate oils, and even to some extent of recognizing them when in mixture.* c. ScponifCCCtion is effected in presence of water by digesting with excess of alkali for some time, or with oxide of lead at 100~ C. for a longer time. The alkali-soaps dissolve in water, the solution being slightly milky, and becoming more turbid on dilution, andc dissolve in alcohol, but mostly refuse to dissolve in ether. The lead soaps of some of the fkt acids are soluble in ether; they are fusible, waxy compounds. See Non-volatile Fat Acids (45). d. The glycerin formed in saponlfication with oxide of lead or with lime, as above, when separated by the concentration of the clear water solution, renders evidence of its identity, by means of tests given under the head of glycerin (66). e. The alkali-soap solutions give white precipitcates with solutions of salts of metals not alkaline, and with acids give white precipitates soluble in alcohol. f. THE DRYING OILS are recognized by not forming elaidin, when treated as stated in the next paragraph; by drying to a resinous film when spread and exposed to the air, and by inducing elevation of temperature, and in many instances ignition, when diffused through a mass of wool or other porous material and exposed to the air. g. THE NON-DRYINoG OR ELAIDIN-FORMING OILS are known by reaction with peroxide of nitrogen. A concentrated solution of mercuric nitrate, or nitric acid of brown-red color, may be used. For the reactions given in the following table,t a little of the oil is taken in a test-tube, an equal volume of nitric acid of about 25 per cent. is added, the test-tube briefly shaken, a strip of copper turnings added, and the whole set aside at ordinary warm temperature, to be examined each quarter of an hour. * TOMLINsoN, MOFFAT: Chem. News, 1869. CRANE: Am. Jour. Phar., 1874, Sept. + HAGER'S Untersuchungen, ii., 506, 76 N~EU'~ITRAL SUBSTANVCES, LIQUID OR FUEIBLE. Tests for Elaidin. Oils. Result a fter J to 2 hours. Result after standing 8 hours to afls. Resultafter to 2hours.2 hourdays. Non-drying Oils. Almond: From sweet al-,White; cloudy. White or whitish mass, granumonds. lar after shaking. Appears homogeneous after 8 to 1' hrs. From bitter al- White or yellowish- Yellowish; only partly solidimonds. white; more or less fild, with a surface layer of turbid. semi-liquid, transparent oil. Bone,... Whitish-yellow. Nearly all solid; a clear-yellow oil layer, with a whitish crystalline finely granular precipitate. Castor,... Whitish. Whitish; solidifying after 8 hours or earlier. Lard,.... Whitish-yellow. Whitish or yellow-white; somewhat granular, with transparent spots; rigid; sometimes with a half-liquid surface Olive:: layer. Green,... White cloudiness, often White or yellowish-brownmodified by color of white solid, made granular the oil. by shaking. The mass appears uniform after 4 to 8 hrs. Yellow,... White or whitish cloud- White or yellowish-white mass, iness. granular after shaking. After 4 to 8 hours the surface Rape-seed: appears nearly uniform. Crude,.. Yellow-brown to red- Reddish-yellow; solidifyingafbrown. ter 16 to 24 hours and becoming brownish-yellow; somewhat granular after shaking, the granules enclosed in an oil layer. Refined,... Whitish-yol'w to br'wn- Reddish-yellow; solidifying afyellow. ter 16 to 24 hours and becomOils drying im- ing yellow; made granular or perfectly. pasty by shaking, the granules oil-coated. Beech-nut,.. Yellow or reddish-yel- Syrupy; nearly clear; after 2 low. days a just perceptible separation of elaidin. Cotton-seed,..iReddish-yel'w or br'wn- Pasty or syrupy; frequently ish. showing a clear brown-yellow oil layer of one-half to onethird the mixture. Appearance of a precipt. after I day. Sesame,... Red to dark red. Blackish yellow-brown or redbrown; opaque; pasty. After 1 day a transparent oil layer sometimes appears at bottom or top. FIXED OILS. 77 Tests for Elaidin- Conlimz ed. Oils. Result after to hours. Result after standing 8 hours to 02ls. lResult after J4 to 2 hours. 2 days. 2 days. Sunflower,.. Yellowish or faintly Brownish yellow. Pasty after reddish. 1 day. Drying Oils. Hemp-seed,.. Green. Yellow; liquid, nearly or quite clear. Linseed,... Scarcely changed. Reddish-brown; liquid and transparent. Poppy-seed,.. Scarcely changed. Reddish yellow-brown or reddish yellow; transparent, liquid. Walnut,...Scarcely changed. Yellow; clear liquid. Non-drying Oils notforming Elaidin. Cod-liver,.. Not changed. Yellowish-red or reddish-br'n; liquid and transparent. Croton, Unchanged or made Thick liquid; clear. clearer. If drying a.re mizixed witAh non-crying oils, the latter are easily detected; the former only with greater care. The elaidin mass remains partly liquid, or an oily layer separates from it. To detect an intermixture of' drying oil, proceed (with a weighed quantity) as above directed, leaving the mixture about two days, then set it aside at 22~ to 25~ C. (720 to 770 F.) for 12 hours, and return it, without agitation, to ordinary temperature. The drying oil will now be found more or less perfectly separated from the elaidin. (For ining the proportion of the drying oil, bring a tared roll of blotting paper into contact with the mass, while the temperature is S~ to 100 C. [46~ to 50~ F.] The increase in the weight of the paper or the loss in the weight of the mixture approximates the weight of the drying oil.) A. Sulphuric acid, Nitric acid, Phosphoric acid, caustic Alkali, and Nitrate of Silver are the chief of the special reagents for color-tests of' fixed oils. The test by stlphztric acid is applied as follows: About 8 drops of the oil are placed in a watch-glass over white paper, NEUTRAL SUBSTAN ~CES, LIQUID OR FUSIBLE. and then 2 drops of sulphuric acid of specific gravity of 1.820 to 1.830 (not more concentrated) are dropped near the edge of the glass so as to flow upon the oil. The results are tabulated below; Sulphuric Acid Test. OIL. WITHOUT STIRRING. AFTER A LITTLE STIRRING. Almond,.. Clear; yellow. Blackish-yellow. Castor,. A tinge of pale brown. Faintly blackish brown. Cod-liver,. First violet, then red. Brown-red, with violet rim, finally dark brown. Lard,... Brownish yellow. Brown. Linseed,.. Brown-red. Black-brown. Olive,... Yellow. Blackish-brown. Poppy-seed,. Yellow. Brownish olive-green. Rape-seed: Crude Greenish-blue. Greenish-blue. " Refined Brownish-yellow. Whale,. Red, afterward violet. Brown-red to dark brown. (~ Vp'/ >U 61. Prep2aractionw aGnd App1ication of Reagents for Identificationz of Fizxed Oils, according to the following table [CALVERT]:* (1) Soda- solutidn. Specific gravity 1.33. 4 parts of dry soda in 6 to 7 parts of water. One volume of this solution agitated with 4 to 5 volumes of the oil and heated to boiling. (The drying oils,. so treated, form soft soaps; the non-drying oils, mostly hard soaps.) (2) Sulpht/ric acid of spec. grayv. 1.475. Mixture of 10 parts of the acid of spec. grav. 1.840 and 7 parts of distilled water. One volume is mixed with 5 volumes of the oil and set aside for tenll minutes. (3) Sulphuric acid of spec. gravy. 1.530. Mixture of 10 parts of acid of 1.840 and 6 parts of water. Mix I volume with 5 volumes of the oil and set aside for five minutes. * Phar. Jour., xiii., 856. I;r ~XED) DI S'. I S. (4) Sulphuric acid of spec. gravy. 1.635. Mixture of 10 parts of acid of 1.840 and 4 parts of water. Applied like reagent (3). (5) Nitric acid of spec. gray. 1.180. Mix 1 volume with 5 volumes of the oil and set aside five minutes. (6) Nitric acid of spec. grayv. 1.220. Applied as directed for reagent (5). (7) Nitric acid of spec. gray. 1.330. Applied as directed for (5) and results noted; then an excess of the soda solution (1) is added and results noted again. (8) Phosphoric acid of syrupy consistence. (9) Sulplhzuric acid of spec. grav. 1.840 with equal measure of Nitric acid of spec. gravy. 1.330. One volume of the mixed acids for 5 volumes of oil. (10) Nitrohyci72&ocldoric acicl-from 1 volume of nitric acid of spec. grav. 1.330 and 25 volumes of hydrochloric acid. One volume of the mixture to 5 volumes of oil, noting the result. Then add excess of Soda solution (1), and again note the result. (1) (2) (3) (4) (5) (6) (7) () (9) (10) OILS. SODA. SULPHURIC ACID. NITRIC ACID. NITeIC ACID, then PHOS. SUL.&NIT.I AQUA hREGIA, then SODA. ACID. ACIDS. SODA. I.330 1.475 1.530 1.635 1.180 1.220 1. 1.30. Castor. White.... Dirty I White;.. BErownish-... Pale rose; white. l brous. red. fibrous. Cocoa-nut. Thick... Dirty Light Fibrous... Oran e... hite; 1- i white. white. brown. white. brous. Cod-liver. Dark red. Purple. Purple. Deep...... Red. Fluid. D'rkred. Darkb'wn. Yellow. Oran g ebrown. yel.; fluid. lIemp-se'd Bro'n-yel.; Bright Bright Bright Dirty gr'n. Greenish Greenish Lig'tb'wn; Green. G re en; Green. L'ht b'wn! thick. green. green. green. dirtyb'wn. dirtyb'wn. fibrous. then bla'k. fibrous. Lard. Pinkish- Dirty Dirty Light.... Faint yel. Fluid..... rown... Pink; fluld white. white, white. brown. Linseed. Yellow; Green. Dirty Green. Yellow. Yellow. Gr'n then Yellow; Br'wnish'G r e e n; Green-yel. O ran g e; fluid. green. brown. fluid. yel.-gr'n.lthen bla'k. fluid. Neatsfoot Dirty yel.- Yellow Br'wnish Brown. Light yel. Lightycl. Lig'tb'wn. Fibrous.... Darkb'wn.Slight yel.lBro'n-yel. white. tinge. dirty we fibrous. Olive. Slight yel. Green Greenish Light Greenish. Greenish. Greenish. W h i t e; S 1 i g 1 t Or an g e - W h i t e; tinge. white. green. fluid. green. yellow. fluid. Poppy-se'd Dirty yel.-... Dirty...... Ora'ge-yel. red. Light red;... Slight yel.... In t e n s e white. white, fluid. rose fluid. Rape-seed. Dirty yel.... Pink....... W te;... iDarkb'wn. Yecl. white; white. I I fluid. fibrous. Seal. Dark red. Light Bed. Bright Pink. Light red. Red. Fluid. D'rkred.lDarkb'wn.Slight yel. Orang e - red. brown. yel.; luid. Sesamoe. p Dirty yel.- Green yGreenish... Ora'ge-yel.l ed. Dark red. Red; fluid.... Gr'n; then Yellow. Ora n g e white. tinge. dirty w'e bright red. fluid. Sperm. |Dark red. Light Bed. |Iright Slight yel.iLlght yel. BRcd. Fluid. D'rk red. Darkb'wn. Slight yel. Or angered. brown. yel.;flid. IX,_A3~IINVA TIONX OF B UTTER. 8 1 62. TESTS WITII Nitrate of Silver. A two per cent. alcoholic solution of nitrate of silver is prepared 0.5 gram of crystallized silver nitrate being dissolved in 1.0 gram water and mixed with 25 c. c. of absolute alcohol. Now place 6 or 7 c. c. of the oil in a test-tube about 12 millimetres (0.47 inch) thick, add 2 or 3 c. c. of the silver solution, shake briskly to form a milky mixture, heat, without bringing the tube in contact with the flame, to boiling for a quarter of a minute, and set aside for an hour or two. A reduction of silver, with darkening of the oil layer to brown, red-brown, or black, results from this test with Almond oil, from bitter Malmonds-colored after several hours. Bone oil-brown to black. Cotton-seed oil-brown to black. Lard oil.:!. Linseed oil-darkens, red-brown. Rape-seed oil-brown-red. With the following oils there is no change: Almond oil, Cod-liver oil, from sweet almonds, Hemp-seed oil, Beech-nut oil, Olive oil,Castor oil, Sesame oil. 63. Special examination of Butter.-Separactionz of fats from non-fatty substances by melting (ac), by benzole (b). Identificatioon of hutyrin, etc., by etherization after saponification (see Butyric acid, 41, b). Distinction frSomn (mixtures of) lard by treatment with sulphuric acid (c), by treatment with ether at 18.50 C. (d), or with petroleum naphtha at 100 to 15~ C. (e); from foreign color by borax solution (f). a. About 10 grams of the butter are melted in a large testtube, by insertion in water of 50~ to 600 C. (122~ to 1400 F.) for about an hour. The fats separate from a subsident layer of water, casein, salt, lactose, (foreign colors). The volume of the latter may be approximately ascertained by linear measurement on the tube. The fat layer from unsophisticated butter is clear, 82 ~ NEUTRAL SUBSTANCES, LIQUID OR FUSIBLE. and has a yellow color of a tint somewhat deeper than that of the butter; while the bottom layer is white, or at most but yellowish-white. (The bottom layer may be i at most; from good table butter should not be over -.) b. In a large and strong test-tube place 5 grams of the butter, melt by dipping in water at 600 C. (140~ F.), add fully an equal volume of benzole, cork securely, agitate, and leave at about 400 C. (104~ F.) for an hour. The sediment separates more sharply and of thicker consistence than in a.-The sediment may be washed with benzole on a filter, and analyzed chemically and microscopically (see c, cl, e). For the separation by benzole, a graduated tube may be used, as follows (HoORN): A glass tube is prepared, 20 centimetres (8 inches) long, its upper two-thirds having a diameter of 2 cenltinetres (0.8 inch), its lower third narrowed and graduated to tenths c. c., and its lower end closed. In this tube 10 grams of butter are placed, melted by dipping in warm water; 30 c. c. of benzole are added, the contents thoroughly intermixed, and the tube set aside. After thirty to forty minutes, the benzole and fat will have separated from the water layer below —the amount of which may be read off. c. Take 2 c. c. of the fats separated by melting as in ca, bring the temperature to about 30~ C. (86~ F.), add about 3 c. c. of concentrated sulphuric acid, and agitate gently to a complete mixture. With butter alone, the liquid remains of a yellow becoming yellow-red color, clear and translucent, not darkening at ordinary temperature, and after half an hour becoming gelatinous and rather less translucent. If Tallow or Lard is present, the mixture after a short time becomes darker, by aid of the heat generated by the acid, so that after half an hour it is dark brownred or brown-black. d. The butter is melted over the water-bath, and after standing the liquid fat is removed from the subsident layer. This fat is mixed in an evaporating dish with four or five times its bulk of hot water and left two or three hours. The solidified fat is EI~~AYIJIALd-t 2TION OF B TTTER1. 83 dried on blotting-paper, introduced into a wide-necked flask, and covered with ether at a temperature of 18.50 C. (65.3~ F.) If the butter was pure, the fat fully dissolves to a clear, lemonyellow liquid. If the butter contained Lard, the fat is in some part insoluble in ether at this temperature, and the mixture is left milky or thick, depositing a (finely granular) sediment on standing. Tallow of beef or mutton gives the same results, the sediment being coarser than in the case of lard. The temperature of the ether is the important condition in this test, and it must not be disturbed by contact with the hand. (HORsLEY.)* By special apparatus, closer observations are made with this test (BALLARD) as follows: Select a test-tube 11 or 12 centimetres (4 or 5 inches) long and about ~2.5 centimetres (nearly 1 inch) wide; and prepare a section of glass tubing of 1.3 to 1.6 centimetres (a little over - inch) diameter, and 4 to 5 centimetres (1~ to 2 inches) long, each end being slightly rimmed outward, and the one (lower) end bound over with a bit of thin canvas. Weigh the little tube, with the covered end, and place in it 1.5 grams of the butter to be tested, and in the test-tube 5 c. c. of ether. Attach a thread to the small glass tube and let it down into the ether, then close the test-tube with a cork, so as to hold the thread, and bind the cork over with leather. Immerse the test-tube in water at exactly 18.50 C. (65.3~ F.) and leave it an hour at this temperature. The cap is now removed, the small tube drawn up out of the ether by the thread (without removing the cork), and left at same temperature to drain. The small tube is now taken out, and while the top is closed by the finger the liquid is absorbed as far as possible by blotting-paper, the tube exposed to the air till free from ether odor, and weighed. Wit, 5 c.c. ether. With 10 c.c, ether. From 1.5 grams pure butter, remained insoluble,....grins. 0. 14 grms. From 1.5 grams beef tallow,... 0.945 " From 1.5 grams lard,..... 0.9 " Farther, see Chem. News, Sept. 11, 1874, p. 135. 84 NTrIL, S]TSTus-ArNOES, LIQ UrID?OR IU1IBLE. From equal parts tallow and butter,. 0.6 grms. From i tallow and 4 butter,... 0.3 " 0.8 grms. From lard and - butter,... 0.15 " 0.8 " From lard and - butter,.... 0.67 " c. The fat of butter, separated according to a, is treated with 7 parts of petroleum naphtha at a low temperature-100 to 15~ C.-when the fat of butter dissolves, and tallow, or lard if over 10 per cent., remains in sediment. f. Boil gently, in a test-tube, 2 grams butter with 5 c.c. of cold-saturated solution of- borax, and set aside to cool and subside. Butter not sophisticated leaves the borax solution nearly or quite colorless (with white turbidity); artificially colored butter leaves the borax solution more or less brown. 64. TIIE FATS ARE DETERMINED it Milk-by separation with ether, from the milk (a), from the residue (b); by opacity of the milk (c); approximately and for comparison by the volume of cream (d). a. To 20 c.c. of milk add an equal volumre of 10 per cent. solution of potassa (to hold the casein i solution) in a cylinder, and repeatedly extrWs'jw it ether./ Dry the ether residue at 1100 C. [Farther, see Phar. Jour., 1874, Sept. 5, p. 188; also Wanklyn's Milk Analysis, New York, 1874, p. 24.] b. Evaporate 10 grams of milk-with 5 grams (~resh dried) charcoal powder or 15 grams (just ignited) ferric oxide or baric sulphate-at 1000 C., till the weight is constant (total solids). Extract the residue, while dry (it being very hygroscopic), with ether, and dry the ether residue at 1100 C. c. Use of Vogel's Lactoscope. A test-glass made of two semi-circular glass plates, set parallel and exactly 0.5 centimetre apart, to hold a liquid between. In a mixing glass, to 100.c. of water, add milk from a pipette, drop by drop, until the diluted milk, when examined in the test-glass, cuts off the light of a candle placed at 10 to 20 inches distance from the glass (the examination being made in a dark room). Dividing 23.2 by the number of c.c. of milk required (to obstruct the light),- then 3TILK. -G L YCERIN. 85 adding to the quotient 0.23, the sum is the per cent. of fats in the milk. d. The milk is set in a (wide) graduated cylinder until the cream has fully separated, when its volume can be read off. (The volume per cent. of cream in cow's:milk varies from 5 to 14.) For Quantitative Analysis of Milk, see, farther, 167 and 168. 65. FIXED OILS ARE SEPARATED front Volactile Oils by extraction of the latter with alcohol (not applicable in case of castor oil, which is soluble in all proportions of absolute alcohol or in 4 or 5 parts of 90 per cent. alcohol).- They are also removed from volatile oils by saponification with alkalies and water.-They are selparated from substances soluble in water by action of that solvent; from various solids by digestion with ether, bisulphide of carbon, benzole or petroleum naphtha; from emulsions by spontaneous separation in cream and melting of the latter, or by ether or benzole, with addition of alkali if necessary to prevent coagulation of the emulsifying substance. Fixed oils are in many cases separated from each other by fractional fusion, according to differences of melting point as stated in the list, this means of separation being subject to the same limitations mentioned as pertaining to Fat Acids (56).Drying oils are separated from non-drying by transformation of the latter into elaidin, as already directed. 66. GLYCERIN. CH6(I(O)3. Characterized by its physical properties (a); by the products of its decomposition when heated (b); by the limits of its reducing power and its interference with precipitation of metallic bases (c). —Separated from solids by its liquidity at low temperatures; from volatile bodies by their distillation; from sugar, gum, or gelatin by certain mixed solvents (a). Its proportion in mixture with water is determined from specific gravity, by use of a table. a. A colorless, syrupy liquid, of specific gravity 1.267 at 15~ C., not congealed at 18~ C. (0~ F.), mostly separating as a $ AEU2TRAL SUBSTANCES, LIQUID Ole FUSIBLE. liquid during the fireezing of' its water mixtures; distilling very slowly with steam at 1000 C., slowly giving off vapor with partial decomposition at 120~ C. (248~ F.), boiling with decomposition of the most part at 290~ C. (5540 F.) Odorless, and of a pure, sweet taste, and neutral reaction. Soluble in all proportions of water and of alcohol; only very, slightly soluble in ether, excess of which separates alcohol from it; not soluble in chloroform; soluble in a mixture of 2 volumes of absolute alcohol and 1 volume of ether (separation from Sugar, Gum, Gelatin, etc.); soluble in a mixture of equal weights of chloroform and alcoholl (separation from Sugr,:Dextrin, Gum, Extractives-the mixture not acid); not soluble in benzole, bisulphide of carbon, petroleum naphtha, or fixed oils. It dissolves nearly all organic sub. stances soluble in water and many of those soluble in alcohol, most salts of alkaloids, and all deliquescent salts of metals. It dissolves baryta, strontia, and lime, with combination, and potassa and soda with gradual decomposition. It holds salts of iron and copper in solution not precipitated by alkalies. It dissolves one-fifth per cent., each, of sulphur and phosphorus, 20 per cent. qf arsenious acid, 10 per cent. of benzoic acid, 15 per cent. of tannic acid (as a waxy solid melting at the temperature of the body), and dissolves and preserves hydrosulphuric acid. It strongly absorbs water from the air. It dissolves iodine freely without decomposition,?bromine sparingly with gradual decomposition, and is changed by chlorine and by nitric acid. It cornbines with strong sulphuric acid, without color or effervescence, as the instable glycerosulphuric acid. b. At its boiling point, as above, glycerin evolves sufocatinzg vapors of acrolein, etc., which vapors may be condensed by ice to a liquid, chiefly acrolein, with some acrylic acid, acetic acids etc. Acrolein is a very acrid body, boiling at 51~ C. (124~ F.), soluble in 40 parts of water. With acid sulphate of potassium, glycerin evolves acrolein at lower temperature. Decomposed and vaporized in an evaporating dish over a lamp or sandbath, only a slight carbon residue remains, staining the dish SOAPS. 87 (distinction from mixture of Sugar, Gums, etc., which leave a puffy carbon residue). c. Glycerin does not recduce hot alkaline sulphate of copper solution (distinction from Sugars, etc.); does not reduce nitrate of silver, even on addition of ammonia, if dilute and not heated (distinction from admixtures of Formic acid and certain empyreumatic matters), but on boiling it, does reduce ammoniacal nitrate of silver solution. (Acrolein, Butyric acid, etc., form white precipitates with silver nitrate, blackening on standing or heating.) At a boiling heat glycerin liberates iodine from iodic acid. d. As concentrated by evaporation l!i the air from a waterbath, glycerin retains about 5 per cent. of water. The U. S. Pharmacopceia requires spec. grav/ 1.25; the German Pharmacopceia spec. grav. 1.23 to 1.25. GLYCERIN P. C. aSP. GR. FREEZING. GLYCERIN P. C. S. 10 1.024 1V C. 60 1.159 20 1.051 2.5" C. 70 1.179 34 1.075 6~ C. 80 1.120 b 40 1.10.5 17.5~ C. 90 1.232 C. 50 1.127 31.34 C. 94 1.241 67. SOAPS. Alkcali salts of Fatty acids (and of Resin acids). —Characterlized by their peculiar touch and consistence, solid or gelatinous; if solid, by melting or softening when warmed, and more readily if retaining more water; by dissolving in water to a slightly cloudy solution, viscid if concentrated, and made more turbid by dilution, also dissolving in alcohol (the solution being often turbid from fats, alkaline carbonates, or other impurities); by their aqueous solutions.being precipitated by salts of metals not alkalies, or by acetic or stronger acids. In the last-named precipitation, the fatty acid will separate as a cream, and may be examined as provided under head of Fat Acids, and the base in solution determined by inorganic analysis. 8 NEUIZE UTRAL S UBSTANACES, LIQUID OR FUSIBLE. Soap solutions are precipitated, physically, by common salt, potassa soaps becoming soda soaps by double decomposition. The oleate of. potassa is (sparingly) soluble in ether; otherwise the alkaline: oleates, stearates, and palmitates are slightly or not at all soluble in ether. Quantitative.-a. In determining the water of soaps by direct evaporation, the fine shavings are exposed at first to a temperature of 400 to 50~ C., which is after some time increased gradually, so as not to fuse, to 1000 C., the latter continued until there is no longer a loss of weight. Stearates so treated still retain about 2 per cent. water.-A more satisfactory determination of the water is effected by dissolving I to 2 grams soap in the least sufficient quantity of strong alcohol, adding a weighed quantity of fine sand, just dried, then evaporating, with trituration, and drying at 1100 C.-The water is also estimated as remainder after finding the fat acids, bases (combined, free, and carbonated), glycerin, resin, salts, color-substances, and foreign matter. b. The amount of absolute soap is determined from the fat acids approximately (GREGER) as calcium precipitate after solution in alcohol. Ten grams of the soap, in fine shavings, are dissolved in 90 c.c. of 90 per cent. alcohol, the solution made up by addition of alcohol to 100 c.c., left to subside, and 10 c.c. of the clear solution are taken out, diluted with water, and precipitated with calcic chloride. The precipitate is gathered in a tared filter, washed, dried at 1000 C., and weighed. 100 parts of this precipitate indicate 101.5 parts of anhydrous soda soap. c. The fat acids also are determined gravimetrically, by weight as free acids, by intermixture with beeswax (HAGER), as follows: 10 grams of the soap are dissolved by warming in an evaporating dish in about 50 c.c. water, and the solution treated with 6 c.c. of hydrochloric acid of spec. gray. 1.124, or 9 c.c. of dilute (1 to 5) sulphuric acid, or enough to cause an acid reaction. Ten grams of pure dry beeswax are added, and melted, and the whole set aside to cool. The solidified mass is now carefully Q7TAlNTITA-TI rF ANAL,'YSTS OF SOA PS. 89 removed from the solution, dried with blotting-paper, and weighed; the weight being diminished by 10 grams gives the amount of fat acids [and resin]. 80 parts of fat acid indicate about 100 parts of good dried (soda) soap (HAGER); 11 parts fat acid represent an average of' 12 parts of solid fat.-According to JEAN (Chem. NEews, xxvi., 206) the fat acids are estimated from the combined alkali (i), 12.6 parts of which (soda) unite with 100 parts anhydrous fat acids. VOHL (Joe?'. Chem. Soc., 1872, 934) separates the fat'acids (and resin) by a limited quantity of petroleubnz caphttact. Ten grams of soap are dissolved in warm water, then decomposed by hydrochloric acid in a cylindrical vessel, and the solution, at 20~ C., extracted with about 10 grams of petroleum naphtha. This solvent is afterward evaporated in: a tared dish at 30~ C., dried at 1000 C., and the residue weighed as fat acids. As to Resins in this process, see g. cd. The fat acids may be capproximately determined by the volume of their supernatant layer, after acidulation, in a graduated cylinder (BUCrNER). 1 C.C. equals 0.93 gram. The weight of fat acid plus I- equals the weight of fat; and 1 00 parts of fat correspond to 155 parts average hard soap. e. PONs recommends a volumetric cletermilatiomn of fact acid by solution of calcium chloride; on which is based a valuation of the soap, taking average Marseilles soap-64 per cent. fat acids, 6 per cent. soda, and 30 per cent. water-as a standard or unit of value. One gram of this standard soap will precipitate 0.1074 gramn calcium chloride (or 0.2532 gram barium nitrate); or 10. of soap, 1.074 of calcium chloride, the latter quantity being dissolved to make 1,000 c.c. [1.074 of calcium chloride may be obtained by dissolving 0.9675 of pure calcium carbonate, the solution being obtained exactly neutral.] Ten grams of the soap (carefully averaged) are dissolved in 100 c.c. of 85 per cent. alcohol-insoluble material being removed by decantation or filtration, and washing-and distilled water is addedl to make the liquid measure 1,000 c.c. In a stoppered flask of 60 to 80 90 N:ElUTRdAL S U'lrBSTANU'S,% LIQYVID 01RZ FUESIBLE. c.c. contents, place 10 c.c. of the standard calcium solution, and add, from a burette measuring tenths c.c., the prepared soap solution, shaking after each addition until a foam remains on the surface (as in the soap test of hard waters). The number c.c. used contains as much soap as 10 c.c. of corresponding solution of standard soap would contain. Hence divide 10 by the number c.c. used, and the quotient expresses the value of the soap tested, as compared with the standard. For the separation of the fat acids from each other, a work of difficulty, see under Fat Acids (55-57). f. Ucombized cfat can be extracted from soap (previously dissolved as far as possible in water) by petroleum naphtha at the temperature of 20~ C. (Compare, under Butter, 63, d and e.) g. RIesin, can be extracted from dried and pulverized soap by means of belzole, which dissolves only traces of the soap.Or, the solution of fat acids in a little petroleum naphtha (a quantity equal to that of the soap)-as obtained by Vohl's process, given in c —contains the resin, which is now precipitated on diluting largely with petroleum naphtha. The precipitate subsides.-Also, when the fat acid (and resin) are treated with a mixture of water and a nearly equal volume of alcohol, the resin is dissolved out. h. Soap may be psecipitated from cold water solution by saturated solution of common, salt (free from earthy bases), and washed on a filter with the same salt solution, with but little loss, the uncombinecl alkali (and alkaline carbonate) and the glycerine being contained in the filtrate and washings. The total of alkali in this filtrate may now be determined by volumetric solution of acid, showing the uncombizned ctldkali of the soc9, izncludinzg alkalibze cabonate. — If the soap is dissolved in alcohol, cllcalinze cstrbonates remain undissolved and may be determined by adding volumetric solution of acid to the residue.-P-ree alkcali may be precipitated from alcoholic solution of soap by passing through a stream of carbonic acid gas. —A quactlitative QUrANTITATIV~E ANALYSIS OF SOAPS. 91 test for free alkcali or alkaline carbonate is mlade by adding mercuric chloride to the soap solution; a red-brown to redyellow precipitate indicates free alkali-the fat acid salts forming only white precipitates. i. Then, for volunetric deterqmination of the cobiinzed alkali of the soap, the soap precipitate is rinsed (with dilute solution of common salt) from the filter into a beaker, and decomposed by a five-times stronger than normal standard solution of' (hydrochloric) acid, added to beginning of acid reaction. After which the fat acid may be separated as a cake and weighed, according to c —a weighed quantity of beeswax or paraffin being added, if necessary to secure solidification. j. _Determiniatioqn of glycerin).. Take 10 grams of soap, dissolve in alcohol, add alcoholic solution of sulphuric acid until precipitation ceases, and filter. Add baric carbonate and filter again. Evaporate until all the alcohol is expelled, and weigh the sweet residue as glycerin (SExIER). Or, treat the filtrate from acid precipitation of the fat acids with basic subacetate of lead, filter, remove the excess of lead by hydrosulphuric acid and filtration, neutralize with hydrochloric acid and extract with a mixture of alcohol 2 vols. and ether 1 vol. Evaporate this solvent and weigh as glycerin (VOHL). k. A plant for cdetermination, of the constituents of soccp, viz.: (1) Carbonates and other salts, color substances and foreign matters; (2) Free Alkali; (3) Combined Alkali; (4) Fatty acids with resin; (5) Fatty acids without resin; (6) Glycerin; (7) Water.* For (1): Digest ten grams soap with alcohol (five or six ounces) on Mwater-bath, filter and wash with hot alcohol in a hot funnel. Dry the residue at 100~ C. and weigh. Analyze this residue by solution with water, by alkalimetry, etc. For (2): Through the filtrate of (1) pass a stream of carbonic acid gas; if a precipitate forms, continue until its formnaSENIER: "A' Process," etc., A m. Jour. Phar., 1874, 353. 92 ZFUSIBL NE. UTRAh L SlUBST.A NCES. tion ceases; filter and wash and determine the alkali in the precipitate by a volumetric solution of (oxalic) acid. (See h.) For (3): The filtrate from (2)-or if there was no precipitate in (2), the filtrate from (1)-after the addition of about an ounce of water, is evaporated on the water-bath to expel all the alcohol, and the (combined) alkali therein determined (as Soda or Potassa) by adding a normal solution of oxalic acid to acid reaction. (Compare i.) For (4): To the mixture left in (3) add a little sulphuric acid; then add ten grams of previously melted beeswax, heat on a water-bath to fuse the wax, cool, weigh the cake, and subtract the weight of the wax. (Compare c.) For (5): Dissolve 40 grams of soap in water, decompose by dilute sulphuric acid, cool at temperature below 14~ C., separate and weigh the fatty acids; then digest them for some time with a mixture of water with nearly as much alcohol, until the subsident liquid (when the mixture has cooled and the fatty acids again solidified) ceases to be milky. Weigh the fatty stratum again; subtract the previous weight, and divide by four-for the resin in 10 grams soap. (Compare q.) For (6): Proceed according to the first method underj. For (7): Estimate by difference; or by evaporation of another portion with alcohol and sand, as directed in ca. 68.'RESINS. Compounds of C, I, and 0. Vitreous and mostly brittle solids (when unmixed), softening and melting when gently heated, but not vaporizable (distinction from camphors); mostly heavier than water. The class includes some substances of pungent taste, some of poisonous effect, and some of intense color. Mostly insoluble or but slightly soluble in water: mostly soluble in absolute alcohol; by far the greater number soluble in ether and in benzole (means of separation from gums). Many resins are soluble in aqueous alkalies, by combination as resin-soaps; and in alcoholic solution show the acid reaction. RESI~NS. 93 The ~resins of commerce include, first, vegetable exudates, of which the Resins proper mostly contain some extractive matters; the Gum-resins being mixtures with gums; the Oleo-resins, mixtures with volatile oils (including the source of common resin or colophony); and the Balsams, mixtures with volatile oils and acids formed by oxidation of volatile oils. Second, resins extracted from plants by alcohol, including some of both the Medicinal resins and the Color resins: And, third, resins obtained from liquid plant juices which are dried as a part of the manufacture; these including two bodies insoluble in alcohol, Caoutchouc and Indigo. 69. The separation of resins from volatile oils is effected by distillation with water; from gums, by fusion and straining at 100~ C.; and from various bodies and from each other by action of the solvents applicable in the case. See Recapitulation, 99. Solution with alcohol and precipitation by pouring the solution into water is by far the most generally applicable process; solution with aqueous alkali and precipitation by acid may sometimes be employed. 70. THE RESINOUS MATTER OF ALOES is fusible on the waterbath; insoluble in cold water, partly soluble in boiling water, freely soluble in alcohol, partly soluble in ether, scarcely at all soluble in chloroform, benzole, naphtha, bisulphide of carbon, freely soluble in aqueous alkalies and in glycerin.-ALOES yields paracumacric Cacild, as follows: The hot ammoniacal water solution is precipitated with acetate of lead, the filtrate freed from lead by dilute sulphuric acid, and this second filtrate is boiled in presence of the (excess of) sulphuric acid-forming (from resin) paracumaric acid in solution. The latter colors ferric chloride dark gold-brown.-The'residue from an ammoniacal solution of mraterial containing aloes, when saturated with hydrochloric acid, yields the odor of aloes." Farther, see Aloin. 71. AMBER Resin. Amber contains Succinic acid, Volatile oil, and resin (two resins). Amber is a hard and brittle, more or less transparent solid, of spec. grav. 1.065; tasteless, aro 94 FUSIBLE SUBSTAN4~CES. matic when rubbed or warmed, of various colors, chiefly yellow or orange.-Subjected to gradually increasing heat, it softens; at 1100 to 2600 C., evolves a volatile oil colored blue by hydrochloric acid; at about 2350 C., evolves succinic anhydride; at 2870, it fuses; at higher temperatures, yields first a colorless oil, then a yellowish wax. —Amber resin is insoluble in water, alcohol (except I — which is soft resin), ether, benzole, bisulphide of carbon, petroleum naphtha, volatile and fixed oils, but soluble in fixed alkalies (except a slight residue) and in concentrated sulphuric acid (with a red color).-Fuming nitric acid changes it to a nitrogenous resin of musk-like odor and gelatinous consistence-" artificial musk." 72. AMMONIAC Resin. Ammoniac contains 72 per cent. resin and 22 per cent. gums, and a little volatile oil. Ammoniac is a solid, soft when warmed, brittle when cold, of specific gravity 1.207, whitish to yellow-brown and dirty gray, of a sweetishbitter and acrid taste and strong peculiar odor. Ammoniac is partly soluble in water, alcohol, ether, acetic acid, and aqueous alkalies. Ammoniac Rosin is wholly soluble in alcohol, in fixed and volatile oils, in sulphuric acid, acetic acid, and aqueous alkalies, and partly soluble in ether. 73. ASSAFETIDA Resin. Assafetida contains over 60 per cent of resin, about 30 per cent. of gums, and about 4 per cent. of volatile oil (whereon its odor depends). Assafetida is a solid, soft when warm, and brittle when cold, of spec. grav. 1.327, having an intense fetid and alliaceous odor and a bitter, acrid, and persistent taste. Its color is variegated and altered, being on fresh surfaces whitish to yellowish, becoming reddish to yellow-brown on exposure.-The volatile oil is separated by distillation with water, contains sulphur, and boils at 140~ C.Assafetida resin is readily soluble in alcohol, not wholly insoluble in water, nearly all soluble in ether, mostly soluble in alkalies. 74. BENZOIN RPesins. Benzoin or "benzoin-gum " consists o'f about three-fourths part resins, 10 to 15 per cent. of Benzoic RESINS. 95 acid, with a little gum and a very little volatile oil. Benzoin is a brittle solid, of spec. grav. above 1.062, melting and evolving benzoic acid when heated;. of variegated colors, fragrant bal.. samic odor, and little taste, with slight acrid after-taste when chewed. Benzoin resins (three have been identified) are all soluble in alcohol, in concentrated sulphuric acid (from which water precipitates them violet), and in strong potassa solution, but insoluble in water. Resin-a is insoluble in aqueous carbonate of sodium, or in ammonia, but soluble in ether. Resin-b has the solubilities above given for ca, except that it is insoluble in ether. Resin-c is sparingly soluble in ether and in volatile oils, and soluble in aqueous carbonate of sodium. The ether solution of c deposits a sediment which has been considered a fourth resin. —Dry distillation of benzoin, after removal of benzoic acid, gives a rose-red distillate. 75. CANAUBA WAX. Consists of myristic alcohol, resin, and other substance. It is a solid of spec. gray. 0.999, harder than beeswax, melting at 84~ C., and of a greenish-yellow color. It is insoluble in water; dissolves with difficulty in alcohol, in ether, and in bisulphide of carbon; dissolves readily in oil of turpentine, but not at all in linseed oil, and not in aqueous alkalies. It is not changed by sulphuric acid, but is stained deep yellow by nitric acid. 76. CAOUTCHOUC. Fusible at 120~ C. (248S F.); not vaporizable. The larger part soluble in ether, benzole, bisulphide of carbon, petroleum naphtha, or oil of turpentine; wholly soluble,in chloroform, and in a mixture of 100 parts bisulphide of carbon with 6 or 8 parts of absolute alcohol. Sparingly soluble in hot amylic alcohol. Not acted upon by alcohol or aqueous alkalies; slowly decomposed by concentrated sulphuric or nitric acid. 77. COLOPHONY. Resin of Turpentine. Common Resin or Rosin.-A pale-yellow to brownish-yellow, translucent, brittle, vitreous solid, of spec. grav. of 1.07 to 1.08; softening at 70~ C. and melting at 135~ C. At a higher temperature it suffers destructive distillation, forming ";essence of rosin" and then *9t FUSIBLE SUBSTANYCES. "rosin oil."-Insoluble in water; soluble in alcohol, ether, chloroform, benzole, petroleum naphtha (with much difficulty), volatile and fixed oils, methylic alcohol, aqueous alkalies (fixed and volatile), anilin, and hot aqueous carbonate of sodium. The three constituents-pinic, sylvic, and colopholic (or pimaric) acids-vary in solubility in certain solvents; cold dilute alcohol dissolving only pinic acid. 78. COPAIBA RESINS. Balsam of Copaiba consists of several resins and a volatile oil (a terpene). The most abundant of these resins, COPAIVIC ACID (the proportion of which is very variable), is a brittle- solid, crystallizable in colorless rhombs; soluble in strong alcohol, ether, benzole, petroleum naphtha, volatile and fixed oils, and aqueous alkalies. Its alcohol solution reddens litmus. Alcohol solutions of the alkaline copaivates, with alcohol solutions of'salts of non-alkaline metals, on adding water, precipitate white metallic copaivates, more or less freely soluble in alcohol. The silver precipitate is crystalline, and the lead precipitate slightly so.-The other 2resins are soluble in alcohol, ether, fixed and volatile oils, and aqueous alkalies. 79. COPAL. Spec. grav. 1.045 to 1.139. Brittle, softening at 500 C., more or less translucent, colorless to yellowish-brown. Consists of several resins. As a whole, it is imperfectly soluble in alcohol; slightly and slowly soluble in ether, bisulphide of carbon, ammonia; slowly soluble in oil of turpentine; readily soluble in oil of cajeput, or oil of rosemary, or " oil of caoutchouc." It is soluble in cold concentrated sulphuric and nitric acids, decomposing when these solutions are heated. Not soluble in alkalies; but combines with alkalies in boiling solution to form a soap soluble in water not containing free alkali. 80. DAMMARA Resin. Australican. Dammaric acid with Dammaran —that is, an acid and a neutral resin. —Bth resins are soluble in absolute alcohol, ether, turpentine oil, benzole, petroleum naphtha, and solutions of fixed alkalies. The acid resin is soluble, the neutral resin insoluble in aqueous alcohol.East Lhicarcn, damnlara (ordinary dlammara). Spec. gray. 1.04 RE, SINS. 97 to 1.09, brittle, melting when heated. Partially soluble in absolute alcohol, about 13% soluble in ether, fully soluble in fixed anld volatile oils, benzole, and bisulphide of carbon, and in concentrated sulphuric acid with a recl color. It is not soluble in aqueous alkalies. 81. DRAGON'S BLOOD. A brittle, dark-brown, opaque, odorless, and tasteless solid; soluble (vith red color) in alcohol, ether, fixed and volatile oils, and mostly soluble in alkalies. The alcoholic solution forms red or violet precipitates with metallic salts. 82. GAMBOGE Resill. Gamboge is over three-fourths resin; the rest mostly gums, with a little starch. Gamboge is a brittle, pulverulent solid, of spec. grav. 1.22, burning when heated; reddish-yellow in 1mass, bright yellow in powder; nearly odorless at ordinary temperatures, but giving a peculiar odor when heated; a slight first-taste but a sweetish-acrid and dry It is soluble in 60 to 90 parts of water, in all proportions CUREOSOTE. ANTIERACElE. ALIZARYIN. 117 of alcohol, ether, chloroform, benzole, petroleum naphtha, fixed and volatile oils, anhydrous glycerin, acetic acid, sulphuric acid (with combination andcl brown color), and in anl equal part of bisulphide of carbon. It is soluble in aqueous alkalies-forming instable salts. It dissolves (andcl: in commerce usually contains) about 3 per cent. of water, from which it is separated by mixture with a large quantity of benzole. Creosote resembles Phenzic Acid, in most of its physical properties, and in its reactions with nitric acid, ferric salts, bromine, gelatin, and albumen. It is dcisti2ngtishecd l on m Pleic accid by not crystallizing when pure; by gelatinizing collodion; by not giving a blue color w'th ferric salts in a slightly alcoholic and sufficiently dilute solution of ferric chloride, as specified under Phenic acid, 35, c (Fluckiger's test); by not forming a clear mixture with a double volume of 18 to 20 per cent. ammonia, or with 5 volumes of ordinary (slightly aqueous) glycerin, or with a greater volume of bisulphide of carbon; adc by more sparing solubility in water. 117. ANTIIRAC. ENE. C141110. A colorless solid, crystallizing in the monoclinic system, often in four or six-sided tablets, having spec. grav. 1.147, melting at about 212~ C., sublimingc slowly from the solid, and distilling rapidly at 3000 C. When pure, the crystals show blue or violet fluorescence. It is tasteless and( odorless, but its vapor at the distilling point is disagreeable and irritating.-It is insoluble in water, sparingly soluble in cold, moderately soluble in hot alcohol, soluble in ether, benzole, and oil of turpentine.-It is not affected by alkalies is acted on by nitric acid, and dissolved with green color by sulphuric acid. With picric acid, in saturated alcoholic solution, it forms a salt crystallizing in red needles. 118. ALIZ;ARIN.,14318O04. A yellow to red-yellow solid; by sublimation (at 215~ C.) crystallizing anhydrous in red prisms, and friom solutions, crystallizing in golden scales of. the 118 NEUTRAi SU'BSTIANl ES, LIQUID OR FUSIBLE. hydrate. Slightly solucble in water; soluble in alcohol and ether (with yellow color) gand in concentrated sulphuric acid (with brown color); soluble in aqueous alkalies and alkaline carbonates (with purple color); these solutions being precipitated (orange) by acids, in good part even by carbonic acid gas. The ammoniacal solution, with salts of magnesium, iron, copper, and silver, forms purple and iridescent precipitates; the potassa solution is decolorized by lime-water, and the alcohol solution is decolorized by'alumina with formation of a red precipitate. 119. BDENZOLE. C065H with traces of its homologues. Coal-tar naphtha. Benzene.-A colorless limpid liquid, of about 0.85 spec. grav., crystallizing at 0~ C., melting at 5.5~ C., boiling at 800 or 81 C. (176~ or 178~ F.), and of a characteristic pleasant odor, reminding of rose and of chloroform. It burns with a bright, smoky flame. It is not perceptibly soluble in water (to -which, however, it imparts odor), but is soluble in all proportions of alcohol, ether, chloroform, petroleum naphtha, etc. It dissolves sulphur, phosphorus, iodine, fixed and volatile oils, camphors; many resins (see 99, f); many alkaloids (not cinchonia) (133). It is cdistingzuished from Petroleum Naphtha by its generally greater solvent power (by dissolving hard pitch), and, more accurately, by its formation of nitrobenzole and products of the latter, as follows: Equal volumes of nitric acid of spec. gray. of 1.5 or of concentrated nitric acid containing nitrous acid, and of the liquid tested for benzole, are digested in a test-tube by immersion in hot water. The nitrobenzole rises in droplets, and is recognized by its odor of bitter almond oil and by its giving anilin with reducing agents, as stated at 120. Or, for more delicate test-as in presence of Volatile Oils: A few drops of the liquid to be tested are mixed in a cooled tube with four times their volume of fuming nitric acid; the mixture is agitated and left a quarter of an hour; then mixed w-ith ten times its bulk of water (which separates drops of nitro. be-nzole). Agitate with ether, w-hich takes up the nitrobenz(oe; P'ETR OLEX 1~1 NAPIIHTHtA. T!'1 OBEN3'ZOLE. 119 decant the ether solution, filter, quickly distil the ether from the filtrate. To the residue add 1 or 2 c.c. of acetic acid and a particle of iron (filings), and distil over a very small flame. As soon as the liquid is nearly evaporated, add 2 or 3 c.c. of water and distil again. Mix the distillates (if acid, neutralize with slaked lime and filter), and test with chlorinated lime for anilin (violet color) (125, a). 1191-. PETROLEUMi NAPtHTHA. Gasolene. "Benzene."-'The rectified distillate of petroleum, having a boiling point of about 49~ C. (120~ F.)-specific gravity about 0.665. Consists chiefly of C5HIlH, I with a little C06H11H and other homologues.- CTiaracterized by an agrecable odor and anesthetic effect; by a wide range of solubilities; and by resisting the action of alkalies and most acids, while decomposed by heating with nitric acid.-Distizqnguisied from _Benzole by a lower specific gravity (even when both are of the same boiling point), land, more accurately, by not forming nitrobenzole (119). 120. NITROB:ENZOLE. C6 H(NO,). "Essence of Mirbane." "Artificial oil of bitter almonds." Nitrobenzene.-A yellowish, oily liquid, of spec. grav. 1.21, crystallizing below 3~ C., and boiling at 220~ C. (428~ F.) It has the odor of bitter almond oil, with equal persistence; a very sweet taste, and a highly poisonous effect taken by inhalation or through the mouth.-It is insoluble in water, freely soluble in alcohol, ether, chloroform, fixed and volatile oils.-It is identified by its odorcoinciding with its reaction for anilizn. When a few drops are digested in a test-tube with zinc, acetic acid, andl iron or magnesium wire, and the mixture extracted with ether, the residue of the latter gives reactions for anilin. See Benzole (119) and Anilin (121). Or a few drops are digested and shaken with zinc and dilute sulphuric acid, the mixture filtered through a wet filter, and the filtrate tested (with chlorate of potassium) for anilin. Both the above methods arc, applicable in presnce of 120 B2ASES, V'OLA:TILE. Bitter Almond oil; also the following: Two or three cubic centimetres of the oil to be tested for nitrobenzole are agitated with about half its weight of fused potassa. If nitrobenzole is present; a reddish-yellow color appears, quickly turning to green, and if water is added there is separation of an upper layer of green, turning red the following day. Finely-divided zinc or iron, alone, digested at 1000 C. for a day or two, reduces nitrobeuzole to anilin.-Nitrobenzole is cdistimguished from bitter almond oil and other Volatile Oils by its specific gravity. BASES: LIQUID AND SOLID. 121. ANILIN. (06H5)1HN2. MIonophenylanmin. — Pure anilin is a colorless, limpid, oily liquid, of spec. grav. 1.028, vaporizing slightly at ordinary temperatures, boiling at 182~ C. It is neutral to litmus, of bitter, burning taste, and vinous, aromatic odor. It is slightly soluble in water-the solution having a faint alkaline reaction; also it dissolves a little water. It is soluble in all proportions of alcohol, ether, chloroform, and most fixed and volatile oils, and in about equal volumes of bisulphide of carbon or benzole, but not perfectly in greater volumes of either. It is sparingly soluble in glycerin. 122. The ANILIN OIL OF COMMERCE contains more or less Toluidin, with traces of benzole, phenic acid, nitrobenzole, acetic acid, acetone, etc. " IKuphanilin " contains about 90 per cent. of phenylamin, and has a boiling point of 180~ to 1900 C. "Baranilin" is mostly toluidin, with a little cumidin and cymidin, boiling at 195~ to 215~ C.* * (Mono)phenylamin,.. (C6 H ) 2 N. Toluidin,.. (C7 H7) H2 N. XyliliH,... (Cs T9 ) H N. Cumidir,... (C H) H3. 123. Phenzylnamii n wvitth acids fornms salts, ciystallizable, soluble in water and in alcohol, many of them soluble in ether. The oxalate is sparingly soluble in cold absolute alcohol, insoluble in ether; the hydrochlorate is soluble in ether, not in cold chloroform. Anilin salts are readily decomposed by fixed alkali, when the anilin may be separated by ether. In the cold, anilii is displaced by ammonia; with heat, ammonia is displaced by anilin. 124. TOLUIDIN has, with most solvents, nearly the. same solubility as phenylamlin. It forms few salts; the oxalate is sparingly soluble in water. 125. Anilim is icdentiQiecd, through formation of Anilin Red (rosanilin, fuchsin, or matenta), by chlorinated lime ol chlor-a ated soda (a), by ferric chloride (b), by binoxide of manganese. and sulphuric acid (c); and by its reaction with chlorate of potassium and hydrochloric or sulphuric acid (d), and with mercuric chloride (e). It is distingyutished from Allcaloids (including Conia and Nicotia) by giving no precipitates with potassio mlercuric iodide solution, or with iodine in iodide of potassium solution, or picric acid in presence of sulphuric. It coitcides with Alkaloids in giving precipitates with phosphomolybdate (f), and with tannic acid (y).-It is characterized by a moderate reeCcizng power (h). Anilin is examined as regards its pooportion of Toluizdin, as explained in a. It is separated from benzole, nitrobenzole, and other associated impurities by fiactional distillation. Alzilin Red is a term for various salts and compouinds of ROSANILIN (C20I,,3. IO0). This is a triatomic base which is colorless when pure —in the air becoming rose-red, or if formed in part from toluidin becoming brown, also dissolving freely in alcohol with a red color. It is nearly iinsoluble in water and insoluble in ether. Ittforms mono-acid salts having an intense crimson color (in solution), and tri-acid salts of yellowish-brown color.-As formed from commercial anilin, by oxidizing agelts, rosanilin has a rich violet-purple color, change, to i-ed by acids, and restored to violet-purple by alkalies. In proportion as M125 BASES, VOLATILE. formed from toluidin, the color becomes brown. Ether extracts the brown, leaving a blue. ra. A water solution of anilin or its salts, with a little solution of chlorinated lime or chlorinated soda gives a purple-red color, changing to brown-red by exposure to the air, or to rose-red by addition of acids. The color passes into a brown; if the mixture be shaken with ether, the latter rises to the surface as a brown layer, leavingr a blue liquid below. b. To a small portion (10 c.c.) of a very dilute solution of anilin, strongly acidulated with hydrochloric acid, add of a concentrated solution of ferric chloride two or three drops, or enough to give a yellowish tint, and heat gradually to boiling. The color becomes darker to opaque violet-brown. When a precipitate separates, filter and wash with water; then treat the precipitate with G0 per cent. alcohol, when the violet color is dissolved. The aqueous filtrate, shaken with chloroform, forms two light red layers. c. A diluted solution of anilin, acidulated with sulphuric acid, on agitating with binoxide of manganese, quickly gives a blue to purple-red color, more intense after warming to 500 or 600 C. c. Chlorate of potassium with hydrochloric or sulphuric acid, when strong, forms a red resinous sub)stance; when dilute, a violet color. e. Mercuric chloride, in the solid state, gently heated with anilin, converts it into a dark-purple mass which gives a red solution in alcohol. f. Phosphomolybdate of sodium with solutions of anilin acidulated with sulphuric or oxalic acid, gives a blue precipitate becoming yellow (with Nicotia, the precipitate is yellowish at first). Addition of ammonia of 18 or 20 per cent. dissolves the anilin precipitate with deep blue color (the Conia precipitate is left blue but undissolved by ammonia). g. Tannic acid, with solutions of anilin not very dilute and not containing free acid or free ammonia, a white precipitate of tannate of anilin. A. Anilin reduces permangainate solution, but not potassio cupric sulphate. COn;lA- TREIIE'PL-IilAII. 1A23 126. ALKALOIDS. Volatile and No'n-volatile. — The volatile alkaloicls are composed of C, H, and N, without 0; and, in their consistence, vaporization, and other physical properties, resemble the volatile oils, but differ from them by approaching the character of ammonia. They are expelled from their salts by fixed alkalies and heat. The most important are the five following. (For Solubilities, see 133; Separations, 134; Comparative reactions, 131 and 135 to 143.) ANILIN (121). 127. CONIA.* C8H15N. A colorless liquid, of spec. grav. 0.89, wasting slightly at ordinary temperatures, distilling almost wrholly with steam at 1000 C., boiling at 160~ to 1800 C. It has millouse-like odor, sharp tastB, and strong alkaline reaction. It resinifies, yellowish, in the air. Its administration causes enlargment of the pupil. It is a strong base; its salts being soluble in water and alcohol, not in ether. It coagulates albumen. 128. LOBELINA. An oily, volatile liquid, of alkaline reaction. Its administration dilates the pupils. 129. NIcoTIA. CIH,N. A transparent, oily liquid, of spec. gray. 1.048, distilling with steam at 1000 C., or slowly alone at 146~ C., boiling at 243~ C. It has an ethereal, tobacco-like odor (when pure), and (in dilute solution!) an acrid taste. In reaction it is strongly alkaline. It resinifies in the air. 130. TRIMETHYLAMIA. C(H9N. Propylainin. Secalin. —A colorless liquid below 50 C., its vaporizing point. (Soluble in water and alcohol.) It has an odor of herring iland of ammonia, a sharp, bitter taste, and an alkaline reaction. Its salts are crystallizable, and soluble in water and (mostly) in alcohol. Its hydrochlorate is soluble in absolute alcohol (separation from Ammonia). Its water solution precipitates aluminum salts and then dissolves the precipitate (distinction from Ammonia). Its solution in equal weight of water is combustible. " The termination a is given in this work to all the alkaloids, but the terminal n is used by many writers, 131. Comparative Reactions of the Volatile Bases. (F. F. MAYER.) (W. indicates water-solution; S., salts or solution with acid.) AMIMONIA. TRIIETHYLAMIA. ANILIN. NICOTIA. CONIA. LOBELINA. Iodine in so- W. Decolorized. W. & S. Orange-yel- Brown solution: W. & S. Brown-red W. & S. Pale brown- W.& S. Brown-red lution of S. No change. low precipitate. precipit. forms precipitate. red precipitate. precipitate. KI. slowly or not at all. Tannic acid. W. No precipitate. In neutral or alkaline No precipitate. White precip., sol. in White precipitate, White precipitate, S. Precip. in cone. solution, white,cur- acids. soluble in tannic sol. in ammonia solution. dy precipitate. and other acids. and in tannic ac. Mercuric W. Whiteprecipitate. W. White precipit. No precipitate. W. White precipit. W. White precipit. W. No precipitate. chloride. Potassio S. No precipitate. S. Pale yellow preci W. White precip., W. & S. Yellowish W. & S. The same as W.& S. Pale yell'w Mercuric W. Yel.-white pre- pitate, cryst. and sol. in excess precip., not easily Nicotia. precipit., slightly iodide. cipitate, soluble in decomp. by much and in KI. sol. in excess, sol. sol. in excess. acids. water. W. Precip., in potassa. sol. in excess. Subacetate............. W. White preci-....... of lead. pitate. Nitrate of W. Brown precipit., W. Grayish precip., No precipitate. W. At first no pre- W.White precipitate, W. White precip., silver. solubleinammonia. sol. in nitric acid. cipit., then brown- turning brown, sol. soluble in ammoish-black precipit. in ammonia, at first nia and in nitric (after warming). sol. in nitric acid. acid. Chloride of W. Reddish-yellow W. Gray-yellow pre- W.No precipitate. W. Yellowish, curdy W. Whitish precip., W. Pale yel. precigold. precipitate. cip., sol. in H C1. precip., insoluble in insoluble in H Cl. pitate, insoluble, I C1. in H C1. Platinic........ Slight precip., soluble S. Yellow; solub. in chloride. I on warming. alcohol. (See 142.) Solubility in Very soluble. Very soluble. Slightly soluble; Sparingly soluble; Iparingly sol.; floats Sparingly soluble; water, and floats on water. sinks in water, on water. floats on water. spec.grav. COlrPOSITIOXAr; CR YST'4L.LINSE FOR3f; COLORI. 1]25 132. Non-volatile Alkaloids and accompan.ying Glucosides. (For Solubilities, 133; Separations, 134; Reactions comlmon to alkaloids, 135, 142, 143.) (For Determinations of Quantity. 135a, 142, 143.) ACONITA. CIH 4,7NO7,.-Glacial mass or white powder. Crystallizes with difficulty.-136 (135, e, f). ATROPRIA. C, 23NO,.-Prisms; stellated tufts; white powder; DATURIA. fusible at 900 C. —136, 135. BEERBRINA. C 1 9NO (1,(H2O) 5. —Light-yellow silky needles, or grouped prisms.-136, 138. BRUcIA. C023 H26N204.-Colorless; delicate needles; four-sided prisms. —136, 137, 138, 140, 139. CAFFEINA. C.4H1N2O.-White, silky needles; fusible at 1780 C.; subliming at 185~ C.-136, 140 (135, a, e, y). CINCHONIA. C20-IN2420.-Four-sided prisms or needles; fusible at 165~ C.-136. CINCHONIDIA. C,2024NO20.-Hard rhombic prisms, with striated faces. Melts at 175~ C. CODEINA. C0H N21RO3. Rectangular octahedrc ns; or (in presence of water) trimetric.-136, 138, 139. COLCHICIA. C,II79NO,.-Colorless:prisms or needles; yellow-. ish-white powder; glacial. —135, 136, 138, 140. DAPHNIN. C31381.0 1-Rectangular prisms. Odorous abovev 1000 C.; above 2000 C., Daphnetin. —138, 141. DELPHINA.-Amorphous; powder white with yellow tint. Melts to resinous mass.-136 (135, e). DIGITALIN. C01011804.-Diffieult to crystallize. A Glucoside.136 (135a) (142). EMETIA. C30,o44N 204.-Yellow-white powder. Melts at 500 C.-130, 138 (135, e). ERGOTINA. C501H52N203. —Red-brown powcler.-136. I-IYDRASTIA.-Colorless, shining, four-sided prisms. Above 100~ C., melts.-136, 137, 140. HIYOSCYAMIA. C15,,s 23 FO3.-Stellate groups of silky needles; amorphous and pasty. Fusible.-136. JGASURIA.-Colorless, lustrous prisms. Fusible. —130, 138, i40. I 26 yNOX- VOLATILE ALiKALOIDS. MORPHIA. C171H19NO(1120). - Short, transparent, trimetric prisms. Anhydrous at 120~.-136, 138, 141. NARCEINA. C23H129NO9. —Colorless. delicate needles. Fusible.136, 137, 138, 139. NARCOTINA. C I-I3,NO,. —Colorless, rhombic prisms. Fusible. -136, 138, 139. OPIANIA. C 6H2NO. —Right rhombic prisms. —138, 139. PAP AVERINA. C20H2 1NO4.-Colorless, acicular crystals.-136, 138. PAYTINTA. 21H24N2O.-Colorless crystals. PHYSOSTIGMIA. C,023113 30. - Amorphous, brownish-yellow; solutions, red to blue.-136, 140. PICROTOXIN. C21H14O,.-Needles; stellate; laminre. Reduces cupric hydrate.-137. PIPERIN. C07,19 N03.-Colorless, monoclinic prisms. MIelts at 1000 C.-136, 138. PSEUDOMORPIIIA. C1 7H19NO4. —Fine, lustrous crystals.-136, 138, 141. QuINIA. C2H 24N2 0.-HI-ydrate, in fine needles. Solutions, blue-fluorescent.-136, 140. QUINIDIA. C020H24N12 0.-Transparent, nmonoclinic prisms, efflorescent. —136, 140. RmCEADIA. C2H2IlNO6. —Small, white prisms. ]Melts at 232~ C. -Purple-red with acids. SABADILLIA. C20H26N205,. —Cubic crystals (Needles?). Reacts with sulph. acid like Veratria (136) 135, e. SALICIN. CH,1 8,.- Tabular or scaly crystals.- Melts at 120~ C. A Glucoside. —136.. SAPONIN. C3,1214018.-Amorphous. Aromatic odor, sweet taste, burning after-taste. A Glucoside. SOLANIA. C 439 N1O,. —Silky needles; right, four-sided prisms. A Glucoside. —136, 138. STRYCHNIA. CH2 4N2 0.-Four-sided prisms, trimetric, white. Fusible.' —-136, 137. rI'IEnAINA. CH 11 NO3.-Thin, square tablets of silvery lustre. Fusible.-136,, 138. So L UrBlEITIF. fI S 27 TIIEODROMINA,. C7H8N402.- icroscopic, trimetric crystals; in club-shaped groups.-136, 140. VERATIRIA. C22H1 N'O. —White or greenish-white crystallized powder. Warmed with ICI, violet. —136. 133. Solubilities of the Alkaloids. —In alcohoTtlltey are generally freely soluble, the following being the only important exceptions and notices to be made: Caffeina —in 30 parts" strong alcohol. Morphia —in 30 parts boiling or 50 parts cold absolute; in a somewhat smaller quantity of 90 p. c. alcohol. Narceina —easily in hot, in 950 parts cold 85 p. c. alcohol. Narcotina-in 25 parts boiling or 100 parts cold 85 p. c. alcohol. Opiania-slightly in hot, scarcely at all in cold alcohol. Pseudomorphia-l-nearly insoluble. Solania —in 150 parts hot or 500 parts cold alcohol. Strychnia-difficultly soluble in absolute, soluble in 115 parts of 9 p.. c., 125 parts of 90 p. c., 130 parts cold or 15 parts boiling 75 p. c., 250 parts cold or 25 parts boiling 50 p. c. alcohol. Theobromina — in 50 parts hot or 1500 cold alcohol. The solubilities given for ether in the table refer to ether nearly or quite free from alcohol. Benzole (of coal-tar), as used below, distils at 60~ to S0~ C. (140~ to 176~ F.), leaving no residue. Amylic alcohol dissolves 0.1568 part of Codeina, 0.0026 part of Morphia, 0.0032 part of Narcotina, 0.0130 part of Papaverina, and 0.0167 part of Thebaina (KUBLY). Ether dissolves fronm- acid solutionZs-Colchiiln, Digitalin, Picrotoxinl-in general not the (other) alkaloids. Petroleutm NaCpIhtlha, as used below, distils at firom 40~ to 600 C. (104~ to 1400 F.), leaving no residue. Amylic Alcohol should be strictly free from ethylic alcohol. The acid used with chlorofor1n, benzole, etc., is sulphuric acid, added just to an acid reaction, and forming sulphates of the alkaloids, Glucosides have the termination N. The * refers to explanation given below for the alkaloids, alphabeticallI [Fixed Al- Ammonia Chloro- Petroleum Water. k ali wfith with Ether. Chloro- Benzole. Petroleum form with Benzole Naph.with Amyl. Alc. water. water. form. JNaphtha. acid. with acid. acid. with acid. Aconitia. Sol.Opts. (As wter) Spar'g. sol. Sol. pt. Sol. 2.5 pts. SInsoluble. Insoluble. Slight. sol. Atropia. In60 pts Soluble. Soluble. Sol. 30 pts. Sol.4 pts. Sol. 50 pts. Insoluble. Insoluble. Insoluble. Insoluble. Slight. sol. boil.: I Berberina. Spar'g sol. Soluble. (As water) / Insoluble. Slight. sol. Insoluble. Slight. sol. Insoluble. Soluble. 13rucia. In 500 pts. (As-water) Soluble. |Insoluble. Sol.4pts. Sol.6O pts. Sol.2l pts. Inso lble. Slght.ol boil. I Caffeina. In 90 pts. Solubl. Soluble. Sol.50 ptS. Sol. S ptoluble. Insol S olubl e. Insoluble. Soluble. cold. Cinchonia. In 2500) pts. Insoluble. Insoluble. Sol.400 pts. Sol.60 pts. Soluble. Near. insol Insoluble. boil....... Cinchonidia. In 2000 pts. So1.O150 pts. Insoluble. cold. ~ Codeina. In 75 pts. (As water) (As water) Soluble. Solublce. Sol. 12 pts. Slight. sol. Insoluble. Insoluble. In Insoluble. Insoluble. cold. Colchicia. Soluble. Soluble. Soluble. Soluble. Spar'g. sol. Insoluble. Soluble. Soluble. Insoluble. Soluble. Conia. In 100 pts.* Soluble. Sol.Gpts. Soluble. Soluble. Soluble. Insoluble. D)atphnin. Spar'g. sol.' Soluble. Soluble. Near. insol DIelphina. Insoluble. Soluble. Soluble. Soluble. INear. insol Slight. soi.jSoluble. Insoluble. Soluble. |Digitalin. Slight. sol.I.-Soluble. Slight. sol. Spar'g. sol. ------ Soluble. Soluble. Insoluble. Soluble. i I Emetia. Spar'g. sol. Soluble.' Spar'g.sol. Near.ins'l. Soluble. Soluble. Soluble. Insoluble. Insoluble. Insoluble. IErgotina. Soluble. Insoluble. Ifisoluble. Ilydrastia. Insoluble. Spar'g. sol. Soluble. Ityoscyamia. Sol. hot. I (As water) (As water) Soluble. |Soluble. Soluble. Insoluble. Insoluble. Insoluble. Insoluble. Insoluble. Igasuria. Spar'g.sol.lSpar'g.sol.i Spar'g. sol. Soluble. Lobelina. Slight. sol Soluble. Soluble. t-Morphia. InS-OO,b'il.*- Soluble. Slight. sol. Insoluble* Sol. 90Opts. Insoluble. Insoluble. Insoluble. Insoluble. Insoluble. Insoluble. NI arceina. In200,b'il.* (Aswater) Slight. sol.l Insoluble. ISpar'g.sol.lSlight.sol. Insoluble. Soluble. Insoluble. Soluble. iNarcotina. In7i000,b'l.' Insoluble. Insoluble. Sol.120pts*; Sol.pts. Sol. 25 pts. Near. insol Soluble. Insoluble. Insoluble. Spar'g. sol. __ _. ___ I~~7~! — - ____. naol_ ____......__ ___ Fixed Al- Ammonia - Chloro- IPetroleuml |W ater. kIlali with, with Ether. Chloro- Benzole. Petrolleumo form withl Benzole Nlaph.with Amyl.Alc. water. water. form. Nlaphtha. acid. with acid.1 acid. with acid. N~icotia. Soluble.* iSoluble. S Spr'oluble. S ol Soluble. Inuble. InsInsoluble. Insoluble. Opiana. Slight. sol. (As water) (As water) |o| hot. i i Papaverina. Insoluble. |Insoluble. Insoluble. Slight. sol. Soluble. Sol. 40 pts. Sol. warmInsoluble. Insoluble. Insoluble. Physostigmia Slight. sol. (As water) Spar'g. sol. Soluble. Soluble. Soluble. Insoluble. Insoluble. Slight. sol. Insoluble. Spar'g. sol. Picrotoxin. Sol. 50 pts.oluble.'Soluble. Sol.250pts. Soluble. Soluble? Soluble. Soluble. hot. I J, Piperin. hot. - - _________ Soluble. Soluble.. Piperin. N ear.insol. (Decomp.) Sol. 90 pts. Soluble. Soluble. Soluble. Soluble. oluble Pseudomor- Insoluble. Soluble. Insoluble. Insoluble. Insoluble. I phia. Quinia. In1800;pts.* Insoluble. Soluble. Soluble.*5 Sol. 50 pts. Soluble. Soluble. Insoluble. Insoluble. Insoluble. Insoluble. Quinidia. In'750 pts. Sol. 30pts.lSoluble. Soluble. Insoluble* Insoluble. Insolube. Insoluble. Insoluble. O |Rheadia. Insoluble. Insoluble. Insoluble. Sol.1300 pts Spar'g. sol. Spar'g. sol. Sabadillia. Spar'g. sol. Soluble. nsoluble. Salicin. Soluble. Soluble. Insoluble. N ear. Insol Near. insol Soluble. Saponin. Soluble. Soluble. Soluble. Insoluble. Solania. In8000,boil Soluble. Insoluble. Sol.4000pts Insoluble. Slight. sol. Insoluble. Insoluble. Insoluble. Insoluble. Strychnia. In 6500pta. Insoluble. Spar'g.Iol. Insoluble SpaSol. 7 pts. Sol. 160ipts.jSol.350 pts.llnsoluble. Insoluble. Insolubl.. lInsoluble. Thebaina. Ins'l.(c'ld) Insoluble. Insoluble. Soluble. Spar'g. sol. Sol.18pts. Soluble.!Insoluble. Insoluble. Insoluble. Theobromina In 750 pts. Soluble. ISoluble. Near. insol Spar'g. sol. Slight. sol. insoluble. Soluble.!Insoluble. Insoluble. Soluble. Veratria. In 1000 pts. (As water) Spar'g. sol. Sol. 12 pts. Sol. 2 pts. Slight.so. Insoluble. Spar'g.sol. hot. * Conia-less soluble in hot seater than cold (distinction from Nicotia). *Morphia-nearly insoluble in seater at 10" C., soluble in traces at 20~ C. Sparingly soluble in etiher, when both nas ud amorphous. Narceina-soluble in 375 pts. water at 14~ C. " Narcotina-soluble in 2500 pts. cold woater. Soluble in cold Acetic acid. Soluble in 50 pts. of boiling ether.' Nicotia-soluble alike in cold or hot water.' Quinia-owater solubility in the table at 15~ C.; at 20~ C., 1650 parts; at 100~ C., 1900 parts. It requires about 5.te ether for solution. Of the alkalies, least soluble in soda solution;dissolving in 2200 parts lime-water. Strychnia-in absolute ether, insoluble; in ether of spec. grav. 0.725, soluble in 1809 parts; an ether of spec. in 1200 parts. According to Wormley, soluble in 1400 parts of absolute ether. et 1 O0 NON TVrOLA TI-L E A LAl L OIDS. 134. Separation of Alkaloids from (solid) Albumenoid, Fatty, and Extractive Matters.-(1) The alkaloids are dissolved out, as salts (tartrates, sulphates, or acetates) by alcohol, heat; the filtered solution is evaporated to dryness, 3idue dissolved as before, etc. For removal from esidue is dissolved in slightly acidulated water; the (filtered) solution evaporated and the solution repeated, etc.The residue, in which the alkaloid is a salt, is washed with ether, as long as the ether removes anything (OTTo'S modification, 1856). The washed residue is treated with alkali, in presence of ether, which dissolves the nascent alkaloid. The residue from the' ether solution is, if necessary, purified by extraction with alcohol, or acidulated water, or each, as required (STAS' method, 1851). Also, this method is adapted for volatile as well as fixed alkaloids. [The extraction with ether may be followed by use of chloroform.] (2) A somewhat more simple method upon the same principle, for non-volatile alkaloids only, with use of chloroform insteadl of ether, and with carbonization by sulphuric acid (RODGERS and GIRDwooD, 1856). Designed, by its authors, for strychnia only; but applicable for all alkaloids soluble in chloroform and not decomposed by concentrated sulphuric acid at 100~ C. (3) The use of amylic alcohol (as in Otto's and Stas' method) to wash the acid solution of alkaloids clean of all matters soluble in amylic alcohol, and, after saturating with alkali, dissolving the alkaloid in the same solvent. Then, the amylic-alcohol-solution of alkaloids is washed with acidulated water, whereby the alkaloids are removed from the former solvent and taken up by the water as salts. This is repeated until purification is complete. The method is applicable bnly to those alkaloids not soluble in amylic alcohol from acid-see Table, 133 (USLAR and ERDMANN, 1801). (4) The use of animal charcoal to withdraw an alkaloid (strychnia) fromn a solvent; after which the alkaloid is extracted IfET'TODS OF S'EPAIRAIYIOX 131 from the charcoal by a more effective solvent. (GRAIAHAM and IHOFMANN, 1853.) (5) Dialysis of the alkaloids, as salts, from colloid matters (GRAIIAM, 1862). (6) Separation of Alkaloids from each other, as-well as firom indeterminate matters, etc. The use of petroleum naphtha, benzole, chloroform, and amylic alcohol, each first in acid and then in alkaline solutions-extracting back to acidulated water (as in method of Uslar and Erdimanm) Awhen necessary to purify. Division of the alkaloids into about eight groups. (DRAGENDORFF, 1868.) (7) Separation of alkaloids from each other and fi'rom associated Glucosicdes, by an extension of the nmethod last named. (8) Separation of alkaloids from, each other by their solubility in alkali. (9) Separation of pure alkaloids from each other by successive use of ether, water, and chloroform. (PRESCOTT.) (1) Otto's and Stas' lifethod.-An aliquot part of the material is finely divided if solid, or concentrated if liquid, and subjected to digestion, at about 60~ C. (140~ F.), with a double weight of 90 per cent. alcohol, with addition of 0.5 to 2.0 grams tartaric acid (or oxalic acid). This extraction is completed by expression and digestion with another portion of alcohol, repeated two or three times.-The filtered liquid is now concentrated to a small bulk-by use of gentle heat, or in vacuum [or heat with partial vacuum from condensation by use of two connected flasks*], or by gentle heat in a stream of air with use of a tubulatedl retort. Fat is separated by filtration through a -wNet filter, and the filtrate evaporated nearly or quite to dryness, in vacuum or over sulphuric acid. —Maceratc the residue. in absolute alcohol (for 24 hours), and evaporate the filtrate at a heat not above 40~ C. (104~ F.)-AMoisten the residuei with water, aild * PRESCOTT: Chem. Tews, xx., p. 222. (1870, Jan ) 1 2 A LKA-L OLIDS. add bicarbonate of sodium or potassium as long as there is effervescence. —Add three or four volumes of ether (free from oil of wine and not heavier than 0.725 s. g.) and agitate. Evaporate a portion of the clear ether upon a watch-glass; a residue in oily streaoksj,`llecting into droplets, having a pungent odor and alkaline reaction, gives evidence of volatile alkaloids. If volatile alkaloids are present, the material is farther treated for a short time with a little strong potassa solution, and then extracted in a flask or large test-tube with repeated portions of the ether. Acidulate the ether solution with dilute sulphuric acid, stopper tightly and agitate, and remove the ether layer. (Ammonia, anilin, nicotia, picolin, as sulphates, are not soluble in ether; conia sulphate is slightly soluble in ether.) Evaporate the ether, at ordinary temperature, and test for Conia.-To the acid watery residue add excess of potassa or soda, and extract with ether as before. Evaporate the ether at low temperature, and test the residue for volatile alkaloids (126). —For non-volatile alkaloids, unite this residue with any fixed residue left by that portion of ether taken after adding bicarbonate, and treat as follows: For nzoz-volatile alkaloicds, evaporate the (first) ether-extract, dissolve in a very little very dilute sulphuric acid (leaving a decided acid 1reaction) and wash with eth]er (absolute or nearly so) as long as anything is washed away.-Now add fresh ether, then add excess of concentrated solution of carbonate of sodium or potassium and extract thoroughly with several portions of the ether. —The residue from the ether ]may be purified by extraction wvith wcater acidcizfied by sulphuric acid; then the concentrated aqueous sulphate is treated writh carbonate of potassium in excess and extracted with absolzte alcohol. -At each evaporation the appearance of crystcls is watched. Crystallization firom ethereal solutions is greatly promoted by adding alcohol. (2) Rodgeers and Gird'vood's method. —The material is digested.with dilute 71ydrochiloric acid at a moderate heat for about two hours; the filtered extract evaporated to dryness on the water-bathl; the residue extracted with water and filteredl; SEPARATION BY SOL TVET~S. 133 and the filtrate supersaturated with ammnonia and then extracted, in a flask, with chloroform. —The solid residue from the chloroform is moistened with concentrated sulphuric acid and left on the water-bath for half an hour or longer to carbonize foreign organic matters. When cool, it is then extracted with water.The water solution is saturated with anzmonia and again extracted with c7loroform. If the residue of (a portion of) the chloroform blackens on warming with sulphuric acid, the (whole) residue is again treated with sulphuric acid on the water-bath, extracted with water, and the aqueous solution with ammonia and chloroform. (3) Zetlhod of Uslar and Erclmnann. — Digest the material, brought to the consistence of a thin paste and acidified with hydrochloric acid, for an hour or two, at 600 to 80~ C. (140~ to 176~ F.), and strain and press through wet linen, washing the residue with water acidified with hydrochloric acid.-Evaporate the united solutions, with addition of clean sand and of ammonia in excess, and triturate to a powder. Boil the residue, repeatedly, with amylic alcohol, and filter the extracts hot through paper moistened with amylic alcohol. The filtrate is usually yellowish, and holds fatty and coloring matters, with the alkaloids, in solution.-Transfcr the filtrate to a cylindrical vessel, add ten or twelve times its volume of water acidified with hydrochloric acid and nearly boiling, agitate v-igorously and set aside. Remove the amylic-alcohol-layer with a pipette. (This should be nearly or quite free from all those alkaloids not soluble in amylic alcohol with acid —the only ones considered in this process. See Table, 133. This amylic alcohol, however, may well be washed with one portion of hot acidulated water.) Wash the water-acid liquid with several portions of amylie alcohol.Concentrate the water-acid liquid, add ammonia in excess, and repeat the extraction with hot amylic alcohol.-If the liquid is colored, or if the residue of a few drops is blackened by a drop of sulphuric acid, again extract by much hot acidulated water, and then by amylic alcohol. 134 A IT LA L O1-DS. (4) lMfethod with Animinal Charcoal.-Shake two ounces animal charcoal in half a gallon of the aqueous, neutral or feebly acid, liquid; let the mixture stand 24 hours, with occasional shaking; filter; wash the charcoal once or twice with water; then boil half an hour with 8 ounces of alcohol of 80 to 90 per cent. (condensing and returning the evaporated alcohol.) Filter and evaporate the filtrate.-(Devised by its authors for separation of strychnia from beer.) (5) Dialysis.-The aqueous liquid or suspended material is acidified with hydrochloric acid, and floated, in the dialyzer, over pure water. The dialyzed liquid usually contains foreign matter; still to be removed by some other process. (6) Use of Na77htha, Benzole, Cllorofo~rm, and Aylic Alcohol, each in? Acid and in3 Alkalize Solutions. Dragen. cldoff's Afethod.-The finely-divided material is extracted several times with water acidulated with sulphuric acid, digesting several hours at a temperature of'40~ to 500 C. (If it is desired to examine for the glucosides, colchicin, digitalin, solanin, the digestion should be made at ordinary temperatures. Piperin may be in part undissolved.) The filtrate is treated with sufficient calcined magnesia to leave only a slight acid reaction, and evaporated over a water-bath to the consistence of a syrup. This is placed in a flask, treated with three to four parts of 70 to 80 per cent. alcohol, acidulated with sulphuric acid, and digested with fiequent agitation, for 24 hours, at about 300 C. When cold, the liquid is filtered, the residue being washed with alcohol. The filtrate is evaporated to remove all the alcohol, and diluted with water: solution A. Solution A is digested and washed in. a flask with petroleum naphtha (see 133), at about 350 C. Fats, colors, etc., and, if present, Pij)erin are dissolved: solution B. —The watery-acidl residue from solution B is digested and washed with benzole at about 45~ C. If a small portion of the decanted benzole gives a perceptible residue, the whole is nearly neutralized with, magnesia or ammonia (leaving a distinctly acid reaction) and then SEPJRA PITIO~A BY SO,OL ST'I~ETS. 135 thoroughly extracted with the benzole: solution C. This bcnzole solution is evaporated in glass dishes, for examination of the residue. It may contain Caffeina, Coichicim, Cubebin, Delphiza, Digitalin (and traces of Berberin, Physostigmin, and Veratria). See also under (7), 134.-The watery-acid residae from solution C is now extracted with amylic alcohol: solution D. In this solution there may be Berberin (traces in C), cNatrcotina (perhaps only in part), Physostigmia (traces in C), Thleobromina, Vteractria (and traces of Aconitina and Atropina).-The watery-acid residue friom solution D is now extracted with chloroform: forming solution E. This may contain Papcveria, Nacrcotinia (if not wholly in D), Thebaina, and perhaps Veratria left firom the benzole of C. The watery-acid residue of E is now made slightly alkaline by ammonia, and extracted at about 350 C. with petroleum naphtha.-If a little portion of this solution gives a colored residue, the whole of it is thoroughly washed with muchl water acidulated with sulphuric acid, thus transferring the alkaloids to. watery-acid solution, firom which they are again extracted by making alkaline and washing with petroleum naphtha. This, solution F, in petroleum naphtha, may contain Brucia, Cozia, E2metia, Nicotia, Quinia, Strychnia, and remaining traces of Veratria.-Two of these are volatile and liquid alkaloids, soluble from the residue in cold water. Evaporation of the naphtha leaves quinia and strychnia crystalline; brucia, emetia, anld veratria, amorphous. Quinia, emetia, and veratria are soluble in absolute ether; brucia and strychnia insoluble. The watery-alkaline residue of F is now extracted several times with benzole, at about 40~ C. If a portion of the benzolo leaves a colored residue, the whole is extracted with acid-water and again taken up with benzole for purification, as directed above for naphtha. Solution G (in benzole) contains Aconzitia, Atropia, Cicwhonzia, Codeinca, I1yoscyamicct, P/lysostigmica, Quinidia.-These alkaloids are all soluble in ether, cxcept cinchonia. If the residue of the others is dissolved in >Twater 1 36 ALIKALOIDS. acidulated with sulphuric acid and then supersaturated with ammonia, aconitia and quinidia are precipitated; while atropia, codeina, hyoscyamia, and physostigmia are (for a brief time) dissolved. The aconitia and quinidia precipitate being dissolved in hydrochloric acid, platinic chloride precipitates only the quinidia. The watery'alkaline residue of G is now acidulated with sulphuric acid and washed at about 55~ C. with amylic alcohol; then made alkaline with ammonia and extracted w-lth amylic alcohol at the same temperature. If the residue of a portion of the solvent is colored, the alkaloids are extracted from the whole by acidulated water; and again extracted by amylic alcohol in presence of alkali (as directed for F and G). Solution HI (in amylic alcohol) contains l1ozpTiaN, actrceina, Solanict.-Narceina is dissolved from the residue by warm water. The watery alkaline residue of HI, which ]nay be termed solution I, may contain Ctcrarin, and traces of Berberina (Digitalin) and Narceina. The solution (I) evaporated to dryness, with pulverized glass, yields its alkaloids to alcohol, (7) SeparatioN of Alkaloids andcl Glucosides from ecach other. 9Dragendoo7ff's scheme. Use of the solvents and operations employed in (6). A. Benzole dissolves, from acid (sulphuric) aqueous solutions -Caffeina, Colchicin (incompletely), Colocynthin, Cubebin, Delphina (incompletely), Digitalin, Elaterin, Narceina, Piperin, Syringin — and traces of physostigmia and veratria. u. Benzole dissolves, from cllacclize (ammoniacal), aqueous solutions-Aconitia, Atropia, Brucia, Cinchonia, Codeillna, Conia, Delphina, Elmetia, T-Iyoscyamia, Narceina (imperfectly), Narcotina, Nicotia, Papaverina, Physostigmia, Quinia, Quinidia, Strychnia, Thebaina, Veratria. c. Benzole factils to dissolve, more than traces, from alkaline solutions —Morphia, Salicin, Solania, Syringin, Theobromina. D. 3Benzole does not dissolve, either from acid or alkaline water' solutions-Curarin, Pierotoxin, Salicin, Theobronlina. SEP A RlTION DY $)01,I TVU.Y'. 18 7' E. Benzole, Petroleum Naphtha, Amylic Alcohol, and Chloroform, all fail to clissolve, from acid or alkaline solutions, Curarin. r. Amylic alcohol dissolves, friom acid (sulphuric) water solutions, more readily when warm —Aconitia (very sparingly), Berberina (in greater part), Brucia (in traces), Caffb.ina, Cantharidin, Colchicin, Cubebin, Delphina, Digitalin, Narceina (sparingly), Narcotina, Picrotoxin, Piperin, Salicin, Santonin, Theobromina, Veratria. G. Petroleum Naphtha leaves lzdissolvec, firom acid or alkaline solutions-Aconitia, Berberina, Caffeina, Curarin, Narceina, Salicin, Syringin, Physostigmia, Theobromin. _,. Petroleum Na'phtha dissolves from acidC (sulphuric) w-atery solutions-Piperin, Populin. I. Petroleumn Naphtha cdissolves from alkcalin?,e (ammaoniacal) solutions-Brucia, Conia, Emetia, Nicotia, Papaverina, Quinia, Strychnia, Veratria, and traces of aconita, berberina, cinchonia, delphina, narcotinza. J. Petroleum Naphtha does not dissolve, from alkaline solution —Caffeina, Colchicin, Delphina. x. Chloroform dissolves from the acid (sulphuric) water solution —Caffeina, Colchicia, Colocynthin, Cubebin, Delphina (sparingly), Digitalin, Narcotina, Papaverina, Piperin, Picrotoxin, Santonin, Thebaina, Theobrollina. L. Chloroform dissolves from the alkaclinze (amlmoniacal) water solution-lAconitia, Atropia, Berberina (sparingly), Brucia, Caffeina, Cinchoni a, Codeina, Colchicin, Conia, Cubebin, Delphina, Digitllin, Emcetia, Iyoscyamia, Morphia (sparingly), Narcotina, Narceina (sparingly), Nicotia, Papaverina, Piperln, Quinia, Strychnia, Thebaina, Theobromina, Veratria. (8) Seplaration of certain alkacloics fro?7, each other by solubility inL alkali. A. Solutions of Fixed Alkalies precipitate, and by excess redissolve, in dilute solution-Atropia, Bcrberina, Codeina, i138 A4LK ALOIDS. Conia, I-Iyoscyamia (:artly), Morphia, Nicotia, Solania —Colehicin being decomposed, Most of the other well-known alkaloids are left in precipitate by excess of fixed alkali. B. Of those not redissolved by fixed alkalies, Ammonia in strong excess dissolves from precipitate-A conitia, Colchicin, HIyoscyamia, Physostigmia, Strychnia. (9) Separatioz by successive use of Ethler, TVater/ (and Ctgdorofor2).-The alkaloids are previously obtained pure, as bases, and-in the solid state finely divided. The ether used is absolute, applied in proportion of 40 to 60 parts to one of the solid, with agitation and digestion in.stoppered flask. The water is applied hot, and in proportion of fully 100 parts to one of solid. The Chlorofor2n, should be nearly or quite free fi-om alcohol, and 20 to 40 parts used. Alkaloids which are appreciably divided by the solvents have their names placed in parentheses. ALKALOIDS. Treat with Ether and filter. Evaporate Filtrate.(a) to resi- Residue (b). due (a). TIeatresidue (a) iwith water. Treat Residue (b) with water. Filt. (A) Res. (B). Filtrate (c). Residue (D) Evap. to res. Evap. to residue (c). (A). Treat (c) wZith chloroform. T:,eat (D) with chloroform. Filt. (C). Res. (D). Filt. (E) Res. (F). Evap. to resid. Evap. to res. (C) (E). (A) (B) (C) (D) (E) (F) Sol. in Ether. Sol. in Etherl. Izs. in Ether. Ins. in Ether. Ins. in Ether. In2s. i Ether. " Water. Izs. in Water. Sol. in Water. Sol. in Water. " Walter. " Wates. " Chl'm. Ins. in ChI'm. Sol. in Chl'm7. " Chl'm. Aconitia. Delphina. (Berberina). (Berberina). Cinchonia. (Digitalin.) Atropia. (Hydrastia). Brucla. Ergotina. (Digitalin). PseudomorCd eina.; (Lobelina). Caffeina. (Narceina). (Hydrastia). phia. Colchicin.`Narcotinf() Emetla (Salicin). hMorplia. Solania. Conla. Paytina. (Igasuria). (Saponin). (Narceina). (Theobromina). Hyoscyamia. Physostigmia. (Narceina). Papaverina. (Igasuria). - Piperin. (Picrotoxin). Rhccadia. Nicotia. Quinia. (Salicin). Strychnia. (Picrotoxin). Quinidfa. (Saponin). (Theobromina) Thebaina. Veratria. GENVERAL REAGENTS. ] 1 9 135. [Detection and separation of alkaloids as a class. The material is obtained in solution, and free from albumenoid, gelatinoid, gummy, coloring, and "extractive " substances. Also, the presence of inorganic acids, bases, or salts which:react with the several reagents, must be avoided. Then, tlhe alkaloids ctre precipitated-by potassio mercuric iodide (also a means of volumetric determination) (a); by phosphomolybdic acid (permitting a division of alkaloids by subsequent use of ammonia) (b); by metatungstic acid (c); by potassio cadmic iodide (d); by picric acid (with distinguishing exceptions) (e); by tannic acid (with exceptions and peculiarities) (f); by solution of iodine with iodide (q). a. The potassio mercuric iodide reagent is prepared by adding to solution of mercuric chloride enough potassic iodide to dissolve the precipitate first formed. It gives precipitates in even dilute solutions of nearly all alkaloids except Cafreina, Colchicin, Digitalin, Tlheobrominai; the precipitates' being mostly yellowish-white. For the reactions with the Volatile Alkaloids and Ammonia, see 131. The precipitates are insoluble in acids (distinction from ammonia), or in dilute alkalies, but soluble in alcohol and (in many cases) in ether-also, in many cases, soluble in excess of the precipitant.- For the extraction of the alkaloid from the precipitate, triturate the latter with stannous chloride and enough potassa solution to give a strong alkaline reaction, then exhaust with ether or chloroform, or, if the alkaloid is not soluble in these, add potassic carbonate instead of potassa and extract with strong alcohol. For the voluimetric determinationz by potassio mercuric iodide (MAYER), the reagent is prepared with 13.55 grains mercuric chloride, 5? grams potassic iodide, and water to one litre. Of this standard solution, 1 c.c. precipitates, of each alkaloid, the quantities stated below; Aconitia, 0.0268 gram. Cinchonia, 0.0102 gram. Atropia, 0.0145 " Conia, 0.0042 " Brucia, 0.0233 " Morphia,- 0.0200 " 140 ALKALOIDS. Narcotina, 0.0213 gram. Quinidia, 0.0120 gram. Nicotia, 0.0040 " Strychnia, 0.0167' Quinia, 0.0108 " Veratria, 0.0269 " The volumetric determination is somewhat unsatisfactory, by reason of the slowness with which the precipitate subsides. The alkaloid solution is slightly acidulated with sulphuric or hydrochloric acid; after each addition of the reagent the mixture is strongly shaken and left to subside; then a drop ofthe clear liquid is placed on a blue or black glass plate, and treated with a drop of the reagent-to learn whether filrther addition is necessary. b. Phosphomolybdic acid solution * —SoNNENSCIEIN's Reagent —gives amorphous and mostly'yellow precipitates with the alkaloids, as below. The alkaloid solution should be neutral or slightly acid, as alkalies dissolve the precipitate in most cases. The reaction with ammonia should be noted ten minutes after its addition. PRECIPITATE. WITH AMMONIA. ON BOILING. Aconitia. Yellow. Blue solution. Colorless. Anilin. Blue, then yellow. " " Atropia. Yellow. Blue to colorless sol. Colorless. Berberina. " Blue solution. " Brucia. Orange. Yellow7green solution. Brown. Caffeina. Yellow. Colorless solution. Cinchonia. Whitish-yellow. " " Codeina. Brownish-yellow. Green solution. Orange-red. Colchicin. Yellow. Bluish solution, in X hr. greenish. Conia. Yellow-white. Bluish or greenish pre. Colorless. * The yellow precipitate formed on mixing acid solutions of molybdate of animoniuml and phosphate of sodium-the phosphomolybdate of ammonium-is well washed, suspended in' water, and heated with carbonate of sodium until completely dissolved. The solution is evaporated to dryness, and the residue gently ignited till all ammonia is expelled (sodium being substituted for ammonium). If blackening occurs, from reduction of molybdenum, the residue is moistened with nitric acid and heated again. It is then dissolved with water and nitric acid to strong acidulation; the solution being made ten parts to one of residue. It must be preserved from contact with vapor of ammonia. GENERAL REAGENYTS. 141 PRECIPITATE. WITH AMMONIA. ON BOILING. Delphina. Gray-yellow. Digitalin. Yellow, on warm- Blue solution. Green, then ing dissolv's gr'n. colorless. Emetia. Yellowish. Ergotina.. (A precipitate.) Morphia. — Yellowish. Dark blue sol., in YI hr. a blue residue falls. Narceina. Brown-yellow, becoming resinous. Narcotina. Brown-yellow. Nicotia. Yellow. Blue solution. Papaverina. In dilute sol., no precipitate. Physostigmia. Yellow. Blue precipitate. Piperin. Brown-yellow. Colorless solution.. (Piperidin. Clear yellow. Blue solution.) Quinia. Yellow-white. Whitish precipitate. Quinidia. 46. " 4 Solania. Yellow. Colorless solution. Strychnia. Yellow-white. " " Theobromina. " Veratria. Yellow. Colorless precipitate. c. Metatungstic acid precipitates alkaloids from very dilute solutions (SCHEIBLER). The reagent may be prepared by adding phosphoric acid to a solution of ordinary tungstate of sodium as long as a precipitate is formed and redissolved. The precipitates are white andcl flocculent. This test is more delicate than that with phosphomolybdic acid. Scheibler states that a distinct turbidity is produced in a solution of one part of quinia or strychnia in 200,000 of-water. cd. Potassio cadmic iodide solution (prepared like potassio mercuric iodide*) (MARME'S test) gives gray-yellow to yellow precipitates with the alkaloids. The solution of alkaloid should be feebly acidulated with sulphuric acid. The precipitates are easily soluble in alcohol, insoluble in ether, soluble in excess of the reagent, and decompose on long standing. Precipitates are obtained with * Dissolve 20 parts iodide of cadmium and 49 parts iodide of potassium in 120 parts of waters 142 ALKzAL OIDS. Aconitia, Delphina, Piperin, Atropia, Emetia, Piperidin, Berberina, Hyoscyamia, Quinia, Brucia, Morphia, Quinidia, Cinchonia, Narceina, Sanguinarin (red), Codeina, Narcotina, Strychnia, Conia, Nicotia, Thebaina, Curarin, Papaverina, Veratria. Cytisin, Physostiginia, No precipitates are obtained (in dilute solutions) from Colchicin, Solania, Theobromina, or fiom other known glucosides and neutral substances.-The alkaloids are obtained fiom their precipitates by adding an excess of carbonate of sodium, drying, and extracting with ether, chloroform, or benzole, according to the solubility of the alkaloids sought. e. Picric or Trinitrophenic acid precipitates firom water solutions the larger number of the alkaloids, especially as sulphates. Presence of free sulphuric acid generally promotes these precipitations and enables them to be formed in more dilute solutions. On the contrary, they are dissolved by hydrochloric acid. No precipitates are formed by picric acid, in acid sulphate solutions of Anilin, Caffeina, MIorphia, Pseudomorphia, Solania (unless by long standing), Theobromina, and the Glucosides.Aconitia and Atropia are not precipitated except in concentrated solutions.-Atropia and Morphia are, however, precipitated in neutral solutions.-SabacTilliac in 150 parts of water is not precipitated. Full precipitates are obtained from the strongly acid sulphates of Berberina, Colchicin, Delphina, Emetia, the Cinchona alkaloids, the Opium alkaloids with the exceptions above given, the Strychnos alkaloids, Veratria, etc. The following results are obtained by treating about a grain of a water solution of (neutral) salt of the alkaloids with an alcoholic soltution of picric acid (WORMLEYr): GENER'At L REA 1GE'NTS'. 143 Least quantity of alkaloid Precipitate. showing precipitate. Aconitia. Yellow, amorphous. 1 grain. Atropia. Yellow, crystalline. 00 Brucia. Yellow. o o Codeina. Yellow, amorphous. -2 Conia. Yellow, crystalline. 1 o" Morphia. Yellow, amorphous. Narceina. " " Narcotina. Nicotia. TSolania.- Strychnia. Yellow, crystalline. Veratria. Yellow, amorphous. The alkaloids may be extracted fro2m their picrates by addition of an alkali and chloroform, benzole, or other suitable solvent. (Alcohol does not dissolve potassic picrate; but it takes up the excess of potassa.) f. Tannic acid-in solution with 8 parts of water and 1 part of alcohol —gives whitish, grayish-white, or yellowish precipitates with nearly all the alkaloids. In the larger number of instances these precipitates are easily soluble in acids, frequently dissolving in excess of the tanllic acid; on the contrary, some of the alkaloids are precipitated by tannic acid only in strong acid solutions. Aimmonia dissolves the tannates of the alkaloids..NAo precipgitates are obtained with Piperin, Salicin, or Saponin. Dilute acetic acid dissolves the precipitates of tannates of Aconitia, Brucia, Caffeina, Colchicin, Morphia, Physostigmia, Quinia (if the acid is not very dilute), Solania, Veratria. Cold dilute hlydrochloric acid does 2,ot dissolve the precipitates of tannates of Aconitia, Berberina, Brucia (slightly dissolves), Caffeina, Cinchonia, Colchicin (dissolves slightly), Delphina, Digitalin, Narcotina, Papaverina, Thebaina, Solania, Strychnia (dissolves sparingly), A cratria. 144 ALKAlLOIDS. Cold dilute szblphp/7uic acid does nzot dissolve the precipitates of tannates of Aconitia, Physostigmia, Quinia, Solania, Veratria. Precipitates are formed in neutral solutions (not very dilute), but not in slightly acid solutions, yet completely formed inz solutions stronzgly aciclulated ~wuit]h sulphuric acid, by Aconitia, Physostigmia, Solania, Veratria. Concerning the reactions of the Volatile Alkaloids with tannic acid, see 131. Alkaloids are separctated fromn their tannates by mixing the moist precipitate with oxide or carbonate of lead, drying the mixture, and extracting with alcohol, ether, or chloroform. g. Water solution of iodine in iodide of pota:ssium precipitates the alkaloids in general. The solution is made of' 3 parts of iodine, 5 of iodide, and 50 of water. (WORMLEY: 1 Of iodine, 3 of iodide, and 60 of water. )-The precipitates are yellow, orange-yellow, reddish-brown, and broiwn.-No precipitates are obtained with (Ammnonia), Caffeina (in neutral solution), Digitalin (or but slight turbidiess), Solania, Theobromina.-.Yellow precipitates are given by Atropia (sparingly saturated), HIyoscyamia, Physostigmia, and Trimethylamia (orange-yellow). Bed- brown precipitates are obtained with Aconitia, Codeina, Conia, Lobelina, Morphia, Narceina, Narcotina, Nicotia, Quinia, Strychnia, and Veratria. 136. Concentrated sulphuric acid gives characteristic reactions with some of the alkaloids; and a greater number of good indications are given by FRnI-DE'S reagent, which consists of 0.01 gram molybdate of sodium dissolved in 10 c.c. of concentrated sulphuric acid (and so prepared freshly each time it is required). For these tests the alkaloids must be almost absolutely free from impurities not alkaloids. One or two miligrams of the alkaloid are dropped upon 15 drops of the acid. CONC. SULPHURIC ACID. FRCEHDE'S REAGENT. Aconitia. Slight yellow to yel.-br'n. Yellow-brown; colorless. Amygdalin, Light violet-red. Atropia. Colorless solution, Colorless. REA CTIOYO S WVITHI SULPHURIC ACID. 145 CONC. SULPHURIC ACID. FRfIHDES -REAGENT. Berberina. Dark olive-green. Greenish-brown to brown. Brucia. Pale rose. Red; yellow. Caffeina. Colorless. Colorless. Cinchonia. Colorless. Colorless. Codeina. Colorless. Green; blue; yellowish. Colchicin. Yellow. Yellow. Colocynthin. Cherry-red (slowly). Colombin. Orange, turning red. Conia. Colorless (pale reddish?). Pale yellow. Cubebinll. Bright red, then crimson. Curarin. Lasting blue. Delphina. Brownish. Red-brown. Digitalin. Brown to red-brown. Orange; cherry-red;br'wn. Elaterill. Red. Yellow. Emetia. Brownish. Ergotina. Red-b6vown. Hesperidin. Yellow-red. Hydrastia. Colorless; after heating, purple. Hyoscyamia. Brownish. Igasuria. Rose-color: yellowish; greenish. Limonin. Yellow-red. Meconin (Opianyl). (With heat, blue to purple). Morphia. Colorless. Violet; green- yellow; violet. Narceina. Brown to yellow. Yellow-brown; yellowish; colorless. Narcotina. Yel.; purple after warm'g. Green; yellow; reddish. Nicotia. Colorless. Yellowish; reddish. Ononin. Red. Papaverina. Violet; blue. Violet; blue; yel'w; colorless. Phloridzin. (Slowly) blue. Physostigmia. Yellow; olive-green. Piperin. Pale yellow; brown. Yellow; brown. Populin. Red. Violet. Pseudomorphia. Olive-green. Quinia. Colorless. Colorless; greenish: —. Quinidia. Nearly-colorless. Colorless; greenish. Salicin. Bright red. Violet; cherry-red. Sarsaparillin. Deep red, then violet, then yellow. Senagin, Yellowm-red. 1443 fi ALIKALOIDS. CONC. SULPHURIC ACID. FR(EHIEYS REAG'T. Smilacin. Yellow-red. Solania. Reddish-yellow. Cherry-red; red-brown; yellow. Strychnia. Colorless. Colorless. Syringin. Blood-red, then violet-red. Tannic acid. Purple-red. Thebaina. Blood-red; yellow-brown. Orange. Theobromina. Colorless. Colorless. Veratria. Slowly to crimson red. Yellow; cherry-red. 137. Sulphuric acid and bichromate of potassium: the solid alkaloid being dissolved in the acid and a very minute fragment of the bichromate being brought into contact with the liquid. With Str/'cl/tmja, a brilliant play of changing colors, blue turning soon to violet and then red-violet, then slowly fdcling — (delicate and distinctive). With Brucia, an orange or brownish-orange color. With Narceina, a dirty-red mixture. With Hydrastia, a brick-red to carmine-redccolor; with Picrotoxin, red-brown. With anilin, a yellowish to greenish tint first appears, slowly passing into blue, which after half an hour or longer becomes nearly or quite black. With Curarin, a play of colors similar to strychnia (compare 1736). With aconitia, atropia, codeina, conia, morphia, narcotina, nicotia, solania, veratria, and many other alkaloids,-there is only the slowly formed greenish color of chromic oxide. This, the strychnzia test, may be made with substitution of other oxidizing agents for the bichromate, the crystallized permanganate of potassium perhaps giving the best results. SoNNENSCHEIN advocates the use of ceroso-ceric oxide. 138. Concentrated Nitric acid, of spec. gray. 1.42, gives a red or reddish-yellow color with the greater number of the alkaloids. Brucia, In the solid state, is dissolved by nitric acid with intense blood-red color-solutions of the alkaloid giving the same with less intensity or a reddish-yellow color. On wairmlug, or standing, the color chaiges to yellow: if now a (lrop of RIEA-CTIONO-S WITH NITR2IC Al C~II). 147 solution of stannous chloride is added, a purple color appears. The purple is discharged by either: nitric acid or excess of stannous salt. Igasuria gives nearly the same reaction, both with nitric acid and stannous chloride; the violet to purple color with the last-named reagent being characteristic of brucia and igasuria..forphia in somewhat concentrated. solutions is colored yellow to orange-red-the color is either not changed or is altered toward the yellow by stannous chloride (distinction from brucia). -Codeina, Tarceina, and Papaverinca are colored red to orange-yellow by nitric acid; and Narcotina, Pseudomzol)hia, Og9ania, Thebainac, and Rhwaadia, yellown. Enbcliat is changed to a yellow, resinous mass, with partial decomposition. Colchici?, is colored violet by nitric acid: the most concentrated nitric acid, containing nitrous acid, forming an intense blue-violet color. The color changes to brown, and finally to yellow-these tints being more distinct in proportion as the violet is deeper. If the chloroform solution of colehicin is treated with concentrated nitric acid, a violet-red color is formed anfd taken up by the chloroform layer.=-CVurarin is colored purple by nitric acid. Nitric acid _produces no color with Atropia (brown tint, fading), Caffeina, Cinchonia, Conia (sometimes yellowish), Quinia, Quinidia, Solania (becoming faint rose~red with bluish rim), Theobromina. Berberinna is colored brown by nitric acid. Daphnin is colored red. Piperin becomes greenish-yellow, orange, then red, and resinous. 139. Concentrated sulphuric acid followed by nitrate of potassium (solid), with Narcotinco gives a deep blood-red color (delicate and distinguishing). The color is discharged by much excess of nitric acid. —In the same test, Brucica gives an orangered, and Opicaznia a scarlet-orange color. C'odceina becomes first greenish, then reddish. Nlarceina turns reddish-brown. 140. Chlorine water followed by ammonia,-QuiniaC (or 148 ALKAL OIDS. Quinidia) treated first with fresh chlorine w-ater and then with ammonia, gives a green flocculent precipitate which by excess of ammonia dissolves to an emerald-green solution (characteristic). On neutralization with an acid, the color changes to light blue, which becomes violet or red on supersaturation with acid, returning to green with addition of excess of ammonia. Addition of solution of red ferricyanide of potassium to the ammoniacal green solution produces a red color (with Qui2zidic a bulky precipitate). A better result is obtained by adding the ferricyanide after the chlorine and before the ammonia. The impure chlorine obtained by addition of hydrochloric acid to chlorate of potassium serves the purpose of this test. C'olchicim, when treated with chlorine and ammonia, gives an orange solution.- cffceina and Theobromina, treated with chlorine water (or nitric acid), then evaporated to dryness, on addition of ammonia give a purple-red color. CTlorine, alone,. -with BGruciic and with Iyasuria gives a light red color; with Hydrcaslia, blue fluorescence. Physostigmia, with solution of chlorinated lime, gives an intense red color, turning nearly black by farther addition. 141. Solution of Ferric chloride (dilute) colors solid lIofrp7zi, and Pseudomorpphia blue. Also Dac)lnib blue in the cold, turning yellow when warmed. If~or2hia separates iodine from iodic acid. 142. Platinic chloride solution precipitates the greater number of the alkaloids, even dilute solutions (those in 2,000 or 3.000 parts of water)-the precipitates being yellow, whitishyellow or grayish-yellow, and some of them being soluble in cold hydrochloric acid.-Anilin, Digitalin, Physostigmia, and Solania, are qzot precipitated; and Aconitia, Atropia, Codeina, ilyoscyamia, Narcotia, Nicotia, Sabadillia, and Veratria only from concentrated solutions.-The alkaloids next named give precipitates; each precipitate, after ignition, leaving a weight of pure platinuml bearing a fixed ratio to the wveight of the alkaloid -in accordance with the formula given. Solubility in P. C. Pt in precip Color, etc. cold HC1. Berberina, (CoH7NINO4.H C1)2PtC1,. 18.1 Yellow, needles. Soluble. Brucia, (C23H26No204.H C1),PtCl4. 16.5 (Like Strychnia.) Caffeina, (C0Ho N 0. Cl)2PtCI. 24.5 Orange-yellow, granular. Insoluble. Cinchonia, C20H24N20(H C1)2PtC1 27.4 Light yellow. Insoluble. Cinchonidia, C20H24NO2(H C1)2PtC14 27.4 Pale orange. Codeina, (C 81121NO0.H C1) PtC14 19.2 Yellow. Colchicin,.... (Like Morphia.) Conia, (C8H11N.H C1)2PtC14 29.4 (Dissolves in alcohol, yellow.) Delphina,...... 17.4 Gray yellow, flocculent. Soluble. Emetia,..... Yellow-white. ~ ilyoscyamia,...... Brownish, flocculent. ~ Morphia, (C,,H,,,NO.HC1) 2PtC14 19.5 Yellow, curdy; after 24 Insoluble. hours, crystalline. Narceina, (CoH tINO.IHCl)2PtC14 14.6 Yellow, crystallizable. LNarcotina, (C22H2N07.HC1)2PtC14. 15.9 Yellow. > Nicotia, C0oH 4N(H C1),PtC14.. 34.2 Orange-yellow (see 131). Soluble. Papaverina, (C20H2,N0.H C1l)2PtC14. 17.8 Yellow-white. Soluble. Quinia, C20H24N202(H C1)2PtCl4, dried at 100 C...... 26.8 Whitish. Insoluble. Quinidia, C20H24N202(H C1)2PtCl4. 26.8 Whitish. (Dry at 1500 C.) Strychnia, (C2,HN12202.1 Cl)2PtCl4 18.3 Yellow, crystallizable. Insoluble. Thebaina, (C0l9H2NO,.H C1)2PtCL4.IH2 18.7 Light yellow. Theobromina, (C0H8N402.H C1)2PtC14. 25.5 Brownish, floe. to cryst. 150 ALKA L OIDS. 143. Auric chloride gives precipitates in water solutions of salts of the greater number of the alkaloids, as follows. Many of the -precipitates are soluble in alcohol. Some of them, on standing, separate the gold. The dried and ignited precipitates yield fixed quantities of metallic gold, according to the formulw and percentages given: P. C. Au in pre. Color, etc., of the pre. Aconitia, C,0H:7N7O.H C1.AuCl, 22.1 Lightyel., reduced after a time. Atropia, C1H23:NO3,.H C1.AuCl1. 31.3 Light yel. Berberina, C0H 7:NO4.H C1.AuCl2. 29.1 Dark yel., insol. in HC1. Brucia,....... (Like Strychnia). Caffeina, C8HIN,40.H Cl.AuOl,. 37.0 Lem.-yel., cryst'e. Cinchonia,...... Yel., (like Quinia). Cinchonidia, C20H1124N2O(H C1)2AuCl,. Yel., amorphous. Codeina, no precipitate,... (in concentrated solutions a brown precipitate). Colchicin, Slowly, yel. flocks; becom'g redluced. Delphina,...... Light yel. Digitalin,...... Slowly, a yellow cryst'e precip. Emetia,..... 9.7 Light yel., amorp. Ivoseyamia, 31.2 Yel.-white. Morphia,...... Light yel., dark'g, insoluble in cold H C1. Narceina,.. -.. Yel., becom. red'd. Papaverina,...... Dark yel. Physostigmina,.... Red'ish-blue color, with reduction. Quinia,..... Light yel., amorp. A IJSINTHIZN, 1'5 I P. C. Au in pre. Color, etc., of the pre. Quinidia, C,2H,24N2O,(H Cl)2(AuCl)2 39.1 (Like Quinia) dry first in vacuo, then at 100~ C.; melts at 1150 C., or in boil. water. Solanla, no precipitate. Strychnia, C21H122N202.H C1.AuCl. 29.2 Yel., amor., sol. in cold H Cl, slight. sol. in Awater, insol. in ether, sol. in alcohol, from which it cryst. orange. Thebaina,...... Red-bron. Theobromina,..... Slowly, slight, needle-form, crvst. Veratria, C32H52N2O8 C1.AuC1,. 21.0 Clear yel., amorp. GLUCOSIDES AND OTHER NEUTRAL BODIES: SOLID. 144. ABSINTHIN. CH 12O". A hard and obscurely crystalline solid of very bitter taste. Slightly soluble in water, very soluble in alcohol, soluble in ether, and soluble in aqueous alkalies. It is precipitated by tannic acid, not by subacetate of lead. When treated, dry, with concentrated sulphuric acid, and the mixture slightly diluted with water, a blue-violet color. It does not reduce potassio cupric sulphate, but reduces anilonio nitrate of silver to a mirror-coating. 145. ALOIN. C1EC,O. A crystallizable, pa.e yellow T152o GCLU-COSIDES ANDt) O7'TiiER _XUTkrIL SOLID),S'. solid, of neutral reaction and a taste at first sweet and thein very bitter. It bears 100~ C. without change. It is slightly soluble in cold water or alcohol, moderately soluble in the same when hot, and soluble (with a yellow color) in the alkalies ald their carbonates.-Chlorine gas, in a solution of aloin, for iht yellow precipitate (chloraloil). Bromine also gives:i/ow prccipitate.-Concentrated nitric acid transforms aloin into chrysammic acid. Cltr ysanzmic acicd, CH2(NO'2)20, is a yellow or greenishyellow powder, of bitter taste and acid reaction, sparingly soluble in water, readily soluble ini alcohol and in ether. It detonates when heated. Boiled with solution of stannous chloride it is precipitated as a deep violet powder. Chrysammalnte of calcium is a dark red insoluble powder. 146. AM:YGDALIN. C0,,HNO;l. IV white, pulverulent, and crystalline solid, neutral, without odor, and with sweet anild bitter taste. Soluble in 11 parts of water; sparingly soluble in: cold, moderately soluble in hot alcohol; insoluble in ether.Concentrated sulphuric acid colors it light violet-red. By boiling dilute sulphuric acid, it is transformed into oil of bitter almonds, glucose, and formic acid; by fermentation writh emulsin, into bitter almond oil, hydrocyanic acid, and glucose. (16 parts of anhydrous amygdalin, as dried at 110~ to 120~ C., or 20 to 24 of ordinary commercial amygdalin, gives 1 part hydrocyanic acid and 8 parts of bitter almond oil.)-Permanganate of potassium forms cyanie and benzoic acids. 147. ASPARAGIN. C4IN03,O,(HO). HIard and brittle right rhombic (trimetric) crystals; inodorous and of slight taste. Soluble in 11 parts cold or 5 parts of bloiling water (with sliglht:tcid reaction), insoluble in absolute alcohol, insoluble in- ether, soluble in alkalies and acids. By fermentation with accompanying extractive substances, or with casein, succinate of ammonium is formed (sometimes with the intervening formation of aspartate of ammonium). CA TI~AR ID IV- C UBL'lIV. 15 3 148. CANTHARIDIN. COHIO2O. Ai colorless, odorless solid, crystallizing in rhombic tables or il needles, not volatile at 400 C., slightly volatile with water at 1000 C., fusing and subliming at about 200~ C. It acts as a vesicant on the skin. Insoluble in cold or warm water, sparingly soluble in alcohol, moderately soluble in ether, freely soluble in chloroform and benzole, soluble in oil of turpentine and in olive oil. Cantharidin has the relation of an acid of very weak power. Its potassium compound is soluble in 25 parts cold or 12 parts boiling water, in 3,300 parts cold or 110 parts boiling alcohol, insoluble in ether and chloroform. The barium cantharidate is insoluble in water and alcohol, as well as in ether and chloroform.-Cantharilin separations may be effected, first, by solution in aqueous potassa; then, after acidulating w-ith sulphuric or phosphoric acid, by solution in chloroform. 149. CATHARTIC ACID (of senna-laves). CATIIARTIN. -An amorphous brown to black solid, soluble in aqueous alkalies and precipitated from this solution by acids. In its natural condition, partly combined with calcium and magnesium, it is soluble in water and insoluble in; alcohol. Boiling dilute acids, in alcoholic solution, convert it-as a glucoside —into glucose and cathartogenic acid, a browsn-yellow powder, insoluble in water, alcohol, and ether. 150. COLUMBIN. Clt,2O1. Cololmbo bitter.-A colorless solid, crystallizing in trimletric prisms, neutral, inodorous, and extremenly bitter. It is sparingly soluble in cold water, alcohol anld cther; more freely in aqueous potassa, being precipitated from the alkaline solution by addition of acids.-Strong sulphuric acid dissolves it with orange color, chanlging to deep red, and the addition of water to this solution causes a brown, flaky precipitate. 151. CUBEBIN. C,, HO 1. A whito solid, crystallizing 154.LUCOSIDE2T A NAl) OTtHER ArTRA L SOIURDS. in small needles, inelting at 120~ C., inodorous, and tasteless. Slightly soluble in water and in cold alcohol, more soluble ill boiling alcohol, soluble in 26 parts of ether and in acetic acid. It is precipitated from alcoholic solution by potassa. Concen. trated sulphuric acid colors it bright red, soon changing to crimson. 152. ELATERIN. A colorless solid, crystallizing in hexagonal tables, fusible; insoluble in water, fieely soluble in alcohol, sparingly soluble in ether. Precipitated from alcoholic solution by acetate of lead and nitrate of silver. Soluble in sulphuric acid as a red liquid, giving a brown precipitate on dilution with water. 153. FRAXIN. (C,0H,18010)H20. A white solid, crystallizing in tufts of needles or right-rhombic prisms, of a slight acid reaction, inodorous, slightly bitter and astringent to the taste. It melts at 320~ C., to a red liquid, solidifying amorphous, and dissolving in water with an orange color. At a higher heat it yields a crystalline sublimate, the aqueous solution of which, with ammonia, shows a yellow fluorescence. Sparingly soluble in cold, fireely in hot water, moderately soluble in alcohol, slightly soluble in ether. The dilute aqueous solution has a blue or blue-green fluorescence, favored by alkalies but prevented by acids. The alcoholic solution is likewise fluorescent. It is turned yellow by fixed alkalies in aqueous solution, or by vapor of ammnonia acting on the crystals; in aqueous solution ferric chloride causes a green color, followed by a yellow precipitate. Acetate of lead gives a yellow precipitate. Boiling dilute acids rlsclve it (as a glucoside) into fraxetin and glucose. Fraxetin, with strong nitric acid, shows successively dark violet, garnetred, rose-red, and yellow colors, then becoming colorless. 154. LACTUCIN. A yellowish, fusible, bitter solid; crystallizable in rhombic plates; soluble in 80 parts of cold water, PIT4,ORIDZ.I: POP ULX.v Q UA NsxI. 15 I5 moderately soluble in alcohol, sparingly soluble in ether, soluble in acetic acid. Strong sulphuric acid turns it brown. 155. PHLORIDZIN. C02H1240. Crystallizes in silky needles or tufts, slightly bitter. Soluble in water, sparingly when cold but freely when hot; soluble in alcohol and methylic alcohol; insoluble in ether; soluble in aqueous alkalies. Dry phloridzin, treated with ammonia gas, on standing in the air, becomes, successively, orange, red. and blue (formation of phlorizein). Strong sulphuric acid colors it red. Dilute sulphuric acid, by prolonged contact, changes phloridzin to glucose and phloretin. The latter is an easily oxidizable substance, dissolving in ammonia, the solution soon depositing yellow scales. 156. POPULIN. C20H,1208. A colorless solid, of a sweet taste, crystallizing in silky needles (with 2H,0), which become anhydrous at 1000 C. and melt at 1800 C. Populin dissolves in 2,000 parts of cold or 70 parts of boiling water, in about 100 parts of absolute alcohol, scarcely at all in ether, freely in moderately dilute acids, also in alkalies. It is precipitated from its acid solutions by alkalies, from its alkaline solutions ))by acids, and from its water solution by common salt. With concentrated sulphuric acid it forms a deep-red solution, from which water precipitates a redcl powder, soluble in water not aciclulated but reprecipitated by acids. Frhbdle's reagent colors populin violet. Boiling dilute mnineral acids convert populin, as a glucoside, into benzoic acid, saligenin, and glucose. Boiling with hydrate of calcium resolves populin into benzoic acid and salicin. 157. QUASSIN. C,10H,11O A colorless, inodorous, and very bitter solid, crystallizing in opaque, white, co]umnar prisms, melting when heated. It is soluble in about 200 parts of water of medium temperature; freely soluble in alcohol, slightly soluble in ether. Coldl concentrated sulphuric acid dissolves it as - colorless liquid, from which water precipitates it unchanled. G6 L UCOSIDES A NI) OTHER VNEUTRA.L SOLIDS. Tannic acid precipitates it, both from aqueous and alcoholic solu tions, but lead salts and mnercuric chloride do not affect it. It does not reduce ammonio nitrate of silver. 158. SARSAPARILLIN. A colorless solid, crystallizable in needles; soluble in water and in alcohol, soluble in ether and in -volatile oils. The solutions froth when shaken. Strong sulphuric acid dissolves it with deep red color, changing to violet and finally to:wi-llow. From this solution water precipitates it unaltered. 159. TARAXACIN. Crystallizes in warty masses, of a pleasant bitter taste, fusible, and soluble in water, alcohol, ether, and in concentrated acids. 160. VANILLIN. C101602. Crystallizes in long, colorless, four-sided prisms, melting at 76~ C. (or 82~ C.), distilling with vapor of water, and subliming in part at 150~ C. It is neutral in reaction, and has the characteristic odor of vanilla. It is nearly insoluble in cold, moderately'soluble in hot water, freely soluble in alcohol, ether, and volatile oils. It dissolves in strong sulphurlic acid and in potassa. 161. Separation of the Glucosides and Neutral Compounds-described in 144-160-by Water, Alcohol, Ether, and Aqueous Alkalies (recapitulation): a. Water dcissolves Absinthin (sparingly), Aloin (hot, sparingly), Aimygdalin, Asparagin, Cathartin, Columbil (sparingly:), Cubebin (slightly), Fraxin, Lactucin, Phloridzin, Populin (sparingly), Quassin (sparingly), Sarsaparillin, Taraxacin, Vanillin (slightly). —Water does not dissolve Cantharidin, Cubebin (except slight portions), Elaterin, Vanillin (except slight portions). b. Alcohol dissolves Absinthin, Aloin, Amygdalin, Cantharidin (sparingly), Colombin (sparingly), Cubebin (sparingly), Elaterin, Fraxin, Lactucin, Phloridzin, Populin (sparingly), Quassin, Sarsaparillin, Taraxacin, Vanillin. —Alcohol does ynot dissolve Asparagin, Cathartin. A i J IlUll-rENoIDs. ] 57 c. Ether dissolves Absinthin, Aloin (sparingly), Cantharidin, Cubebin, Elaterin (sparingly), Lactucin (sparingly), Sarsaparillin, Taraxacin, Vanillin. —Ether does not dissolve Amygdalin, Asparagin, Fraxin (except slight portions), Phloridzin, Populin, Quassin (except slight portions). d&. Aqueous alkalies dissolve Absinthin, Aloin, Asparagin, Cathartin, Colombin, Phloridzin, Populin, Vanillinl; do 9not dissolve Cubebin. [For Dragendorff's elaborate process for separation and identification of Foreign Bitters in Beer, see Arch. Pharm. (3), iii., 295; iv., 389; or Jour. Chem. Soc., 1874, p. 818; or Prescott's Exam. Alcoholic Liquors, N. Y., 1874.] NITROGENOUS NEUTRAL BODIES. 162. ALBUMENOIDS. Varieties of' Albumen, Fibrin, and Casein.- Characteerized as infusible, non-volatile, amorphous solids, neutral in reaction and indifferent to combination; in natural condition, soluble in water containing alkalies or containing certain salts of alkalies; rendered insoluble in water by acids, and generally by leat in absence of dissolving agents, andl by salts of certain heavy metals. Farther, they give a reaction for nitrogen (a), and color-tests with strong hydrochloric acid (b), and with mercuric nitrate in nitric acid (c), and act as reducilg agents (d).-Albumenoids are distinguished and partly separcttewc from Gelatin, Gums, and Dextrin, by their coagulation wvit heat or with mineral acids; they are separated from starch by dissolving in solution of alkali too dilute to affect the starch (see 176,f). ca.. Mix the well-dried substance with dry soda-lime, introduce into a hard-glass long-necked matrass (or long and narrow test-tube), place a slip of red litmus-paper in the mouth, and heat, gradually, to incipient carbonization. Production of ammonia (this base being' absent in the substance) indicates a nitro 14)8 -A L ft U.\ENOIDS. genous organic body.-Albumenoids, on boiling with potassa solution, yield ammonia; a farther quantity being obtained by adding permanganate (WANKLYN). b. Strongest hydrochloric acid dissolves albumenoids to a yellowish color, which becomes blue or violet by exposure to the air. c. Acid mercuric nitrate solution-prepared by dissolving one part of mercury in two parts of nitric acid of spec. grav. 1.42 -on digestion with solid albumenoids, at 600 to 1000~ C. (140~ to 212~ F.), gives a deep red color. If the substance tested is in solution, it should be concentrated, and used in such small proportion that the reagent is not much diluted. cl. Alkaline cupric solution is turned violet by albumenoids, and on warming the cuprous oxide is quickly reduced. Solution of permanganate is also reduced by albumenoids. Uier' thee Microscope, albumenoids are turned yellow by iodine, and purple-violet by sulphuric acid with sugar. 163. OVALBUMEN. Soluble in water with some turbidity and suspension of skinny particles; this solution being rendered nearly clear by alkalies or alkaline carbonates or common salt.Chemically neutral water solutions are coctgtdated by heating to a very little above 63~ C. (145~ F.); by alcohol, carbolic acid, and creosote; by ether (but not completely), by nitric acid (quickly and completely), by hydrochloric acid (slowly redissolving when the acid is strong), and by sulphuric acid (slowly). Salts of silver, mercury, etc., coagulate it; also alum. Acetic and tribasic phosphoric acids do not coagulate it, but (by neutralizing the natural alkali) they render its pure water solution still more turbid. Tannic acid coagulates it quickly.-Strong potassa, or soda, gelatinizes albumen. Jibr weighinlg, albumen is precipitated from slightly acid-ulated solutions by boiling, washed with water, and dried first below 500 C. (122~ F.), then at 100' C. (So treated, it is not rendered insoluble.) 164. SERALBUMEN. Dissolves in water w\ith somne turbidity, DETERMINJA TIO7'NS IN MHILf. 159 Coagulatecl at 750 C. (1670 F.), or, in presence of alkaline salts, at a higher temperature, while in presence of acetic acid a lower temperature suffices. Coagulated by dilute mineral acids, slowly or if heated quickly; redissolved by strong nitric acid and (readily) Ey hydrochloric acid. Coagulated by alcohol; not by ether (distinction from Ovalbumen). —Coagulated by salts of mercury and silver.-Aqueous alkalies dissolve coagulated sermalbumen. 165. CASEIN. In natural condition, dissolved clear by water. Coagulated by rennet (separation from milk albumen); by moderately dilute acetic acid (separation from ovalbumen, seralbumen, milk albumen); by ether and by mineral acids and mercuric chloride. Not coagulated by dilute alcohol or by boiling (separation from seralbumen and from ovalbumen). Alkalies and strong acids, even stronllg acetic acid, dissolve coagulated casein. [Farther, see Phar. Jour., 1874, Sept. 5, p. 188.] 166. MILK ALBUMEN. (0.3 to 0.5 per cent. of healthy cows' milk; found as high as 3 to 10 per cent. in diseased milk and in the colostrum.)-Not coagulated by rennet, but coagulated by boiling, after the slightest acidulation with acetic acid (two means of separation from Casein). Coagulated by mineral acids and salts of heavy metals; the coagulum being soluble in alkalies. 167. Determination of Casein and Albumen in Milk.a. Take 50 grams of ]nilk, add an equal quantity of water, add rennet,set aside at 40G to 50~ C. Gather the precipitate (the casein with most of the fats) in a tared filter, wash with water, then with alcohol, then with ether thoroughly, dry at 1100 C., and weigh as Casein. —To the filtrate from the curd (and first water washings), add 4 or 5 drops of acetic acid and boil. Gather the coagulum in a tared filter, wash with water, dry at 1100 C., and weigh as Albumen.-(The filtrate from the curd of albumen is saved for determination of the Sugar, according to 187, 1. This filtrate contains a minute proportion of an albumenoid called Lacto-protein, which is coagulated by mercuric nitrate -not by nitric acid.) 1 O0 A LB UJILLYOIDS. 168. Quantitative Analysis of Milk. (1) Determine the Total Solids, as directed in 64, b. (.2) Determine the Fats, as directed in 64, b (or a). (3) Determine the Casein and Albumen, as directed in 167. (4) Determine the Sugar, from the filtrate of 167, according to 187, 1. (5) Determine the Salts (soluble and insoluble in water). Evaporate 20 grams in a tared dish, with a tared small glass rod, ignite to whiteness (by triturating); weigh, then extract with water and dry and weigh the residue. 169. Commercial Examinations of Milk usually require, more especially, the following operations: (1) Find the volulne per cenit. of cream. (Or'use a lactoscope-64, c.) (2) Take the speciflc gravity, and consider the relation between this and the amount of cream. Skimmed mi-ilk has a specific gravity about 0.004 greater than entire milk (from CHANDLER'S averages.) (3) For more exact data, find the solidus minus feats, as directed in (1) and (2) of 168. The " solids not fat " is nearly the samle proportion of the milk of' different cows-also, of the whole milk, the skim milk, and the cream, alike (WANKLYN). Hence, variation in this quantity indicates sophistication. (4) Examine with the microscope (presence of colostrum globules usually coinciding with excess of albumen), and test for impurities in general. 170. GELATIN. (Isinglass, Glue, "Gelatin.") An infusible, non-0volatile, amorphous, horny solid; colorless to yellowish, translucent, brittl, odorless, and tasteless.- Characterized as a neutral and indifferent substance, evolving ammonia freely when heated dry with soda-lime or when boiled with potassa solution and permanganate (see Albumenoids, 162, a), and existing in a soluble and an insoluble condition.-Its soluble forlm c7issolbe.S very slowly and slightly in cold water, gradually C-,A R I rJ O l-D A'ES. 161 and completely in boiling water, the solution if not very dilute congealing into a tremulous jelly-like mass when cold (distinction froni Albumenoids which are coagulated by boiling).Gelatin solution is coagdulatedl by alcohol, by mercuric chloride, by chlorine gas, and especially by tannic acid (formation of leather) (the last, a sepctrationl from Gum arabic and Dextrin). In distinction, and separation from Albzumenezoidcs, it is not precipitated by nitric, hydrochloric, or sulphuric acids, or by salts of silver, copper, lead, iron, or aluminum. In not being precipitated by basic acetate of lead, it is separated from Dextrin, soluble starch, starch-paste, and Gums.-Gelatin solution dissolves the recent cupric hydrate, as formed in cupric sulphate solution by excess of potassa, turning the color to dark-violet, which on warming becomes red, without precipitation of cuprous hydrate. It promptly reduces permanganate solution. 100 parts of gelatin, as dried at 130~ C., by precipitation wNith tannic acid, yield about 135 parts of leather precipitate. 171. LEATHER yields its tcannic acid to boiling dilute alcohol;,the gelatin remaining coagulated. The dried and finelyrasped leather is first freed fiom oils and resins by digestion with ether free from alcohol, along Nwith water. Untanned gelatin may be detected in leather, by the translucence of thin shavings (of the central portion), and by yielding a solution of gelatin when lona macerated with water at about 90~ C. CARBO-IDIDRATES. 172. GUMS. Mostly CH O0 (as an anhydride) in combination with alkaline-earthy bases or with water. CJlarcacte2rized1 as infusible and non-volatile, amorphous substances, destitute of nitro(gen, rmore or less perfectly soluble in water, insoluble il 1 i} CR4 WBO IIYlrDX cRA o YDR S. absolute alcohol, ether, benzole, etc.; precipitated by subacetate of lead; and not readily transformed to glucose by boiling with dilute acids (a distinction from Dextrin and from Starch). 173. GUM ARABIC. Gum Acacia. Arabin, or Arabates of calcium, magnesium, potassium, etc. —Soluble (by digestion) in 2 parts of water, forming a syrupy liquid of spec. gray. 1.13, which mixes clear with 24- times its volume of 35 per cent. alcohol. Soluble in 20 to 25 parts of 45 per cent. alcohol. If acidulated (with mineral or acetic acids), arabic acid being liberated, it is much less soluble ill dilute alcohol, i.e. requires for solution alcohol more dilute. Gum arabic is characterized by a white precipitate by subacetate of lead or ammoniacal acetate of lead, in very dilute solutions; by giving (with oxalate) the reactions of calciumn (distinction from Dextrin and Starch); by forming an almost insoluble jelly when in saturated solution it is treated with about ~i volume of concentrated solution of ferric chloride, and by preventing the precipitation of iron salts by alkalies when in dilute solution (two points of distinction from Dextrin). As a red2tcihng agent, fresh solution of gum arabic, with potassio cuprie solution, precipitates the cuprous hydrate after heating to 100~ C. (Dextrin effecting this reduction at a gentle heat). Stale solution of gum arabic generally contains glucose. Gum arabic gives. precipitate with tannic acid (septarcation from Gelatin anc' Ovalbumen); or with mineral acids (separation from Albumenoids); and no reaction with iodine (distinction from Starch). Sulphuric acid, added to its one-half volume of concentrated acacia gum solution,. turns it brown to black. Boiling with dilute sulphuric acid slowly transforms gum acacia (in part) to glucose. Ordinary gum arabic, at 900 to 1000 C., loses 10 to 15 per cent. of moisture; above 1000 C., it is so altered as to be imperfectly soluble. 174. Gumi TRAGACANTII is only in small part directly soluble in water, in which it swells to a jelly; the greater part dissolving DEXTRI:: S TAlR CHL. l3 by long boiling. The solution so formed consists chiefly of Arabin, with a very little Glucose, and gives reactions fbr these substances, according to their proportion. Boiling with dilute sulphuric or hydrochloric acid dissolves the gum more rapidly than with water, producing a little larger proportion of glucose. -The residue not soluble in pure. water contains starch, and is colored blue by iodine. 175. DEXTRIN. British Gum. C6H 005.-A yellow-white to colorless amorphous solid; tasteless and odorless. It is soluble in about one part'of water, to a syrupy semi-liquid, which is miscible with 1~ volumes of 60 per cqnt. alcohol or. with 3 volumes of 50 per cent. alcohol. /It is inisolible in 90 per cent. alcohol, sufficient of which precipitates it from solutions not too dilute; and insoluble in ether, chloroform, bisulphide of carbon, etc.-Commercial dextrin almost always contains glucose; frequently contains " soluble starch " (15 per cent. of which is held not objectionable); and is sometimes brown from presence of caramel. Concentrated sulphuric acid dissolves dry dextrin, without color in the cold but with blackening when warmed.-Sub-acetate -or amlmoniacal acetate of lead precipitates dextrin from very dilute solutions (in cold'and dilute solution, a distinction from Glucose).-Pure dextrin (free from glucose) reduces potassio cupric sulphate at 80~ to 90~ C.. It does not reduce boiling solution of c(upric acetate (distinction from Glucose).-Pure dextrin is not colored by iodine. (distinction from Starch and " soluble starch"); nor precipitated by tannic acid (sepcarationz from Starch and soluble starch, Gelatin, and Ovalbumen); nor by mineral acids (separation from Albumenoids); nor by baryta water (separation from Soluble Starch). Dextrin is dried (over a glycerin-bath) at 110~ C. Its precipitate by subacetate of lead is Pb C o, 00. 176. STARCH. Chiefly C(H 0O,; being an organized body, 164 CAir BOI OY.DRATES. of many varieties of structure, and containing cellulose in the envelopes of the granules.-Varieties of starch are identified by their form under the microscope (a). Starch in general is characterized by its relations to solvents (b); its color with iodine (c); its precipitates with tannic acid, subacetate of lead, and baryta (d); and its easy transformation to "soluble starch," dextrin, and then glucose (e). —Starch-paste and "soluble starch," both, are clistingishecd acd inZ plart sepcarateCd from Albumenoids by non-precipitation with heat, or with mineral acids (e); from Gelatin by precipitation with subacetate of lead (d); fiom Gums by precipitation with tannic acid, and from Dextrin by precipitation with tannic acid or with baryta water (cl). The complete sepctration of starch from Albumen, Gelatin, or Gum is effected by first changing it to glucose (e) and then washing the latter away (from the coaguluml) with strong alcohol.-Starch is separated from Grains or other parts of Plants by water-washing (f), and cetermined directly or as glucose (g). a. The starch grcanules are from 3-o-1 to 6 — inch in diameter, flattened and ovate, with concentric rings (the borders of overlapping layers), and mostly with a small eccentric nucleuas. They are characteristic of each variety. b. Natural starch is insoluble in water, alcohol, ether, etc. Water at 60~ to 750 C. (140~ to 167~ F.) bursts the granules of natural starch; a small part of which is apparently dissolved, the larger part remaining suspended in minute particles forming a gelatinous semi-solution, while a small portion, consisting of the envelopes, readily subsides, the whole being known as Starchp2cste. Boiling water slowly changes starch-paste to "soluble starch" and to Dextrin.-Caustic potassa solution of o or 3 per cent. causes starch to swell to starch-paste; finally forming some "4 soluble starch."-W hen starch is triturated with two-thirds its weight of concentrated sulphuric acid, in the cold, and left for an hour, then washed on a filter with alcohol till free from acid, it is transformed into 1" Solutble Starch." This is a modification of starch, soluble in cold or hot water STA1RCE. 165 to a syrupy liquid not quite so clear as dextrin; colored blue to violet with iodine (distinction from Dextrin); precipitated by alcohol when the latter is as much as 50 per cent. (dextrin requires stronger alcohol for precipitation); precipitated by tannic acid and by baryta water (two wate r (two ways of separating from dextrin); precipitated by subacetate of lead (coinciding with dextrin). Concerning solution of starch by its transformation into Dextrin and Glucose, see e. c. Free iodine-in solution with water or alcohol or water with iodide, or in'vapor —colors starch blue to violet, forming the " iodide of starch " (a product of adhesion). ~ The color is destroyed by heating (returning when cold), by washing with alcohol, and by chlorine, potassa, hydrosulphuric acid, or other agents which bring the iodine into chemical combination. d. Tannic acid precipitates starch-paste; the precipitate being soluble in excess of the starch, and soluble by heat-sepa-'rating again when cold. Baryta water, and solution of subacetate of lead or ammoniacal solution of acetate of lead, precipitate starch-paste (as well as soluble starch). e.:Starch is chanyed to Glucose (through soluble starch and dextriln) very quickly by boiling dilute mineral acids (two to three per cent.); very slowly by boiling with water, and quite effectually by the conditions of the alcoholic and " saccharine" fermentations. f. Ceereal gcrains, or other parts of plants, are finely pulverized, and then washed on a hair sielve with cold water, and the washings allowed to subside (as in manufacture). The starcli residue may be washed again through a bag of fine linen. The residue is then washed on a filter with 45 per cent. alcohol containing 0.1 per cent. potassa, then with 60 per cent. alcohol, then with ether; and dried, first below 600 C., lastly at 1000 to 110~ C., when it may be weighed, as starch. g. Starch may be determined as Glucose (187, l); after boilinTg with dilute sulphuric acid (e) and neutralizing. CI-O1: Ct H, 0 1 80: 162, 166 CA RB OIlYDRA TES. 177. PECTOUS SUBSTANCES. Vegetable products corresponding in properties to the gelatinoilds of the animal kingdom. 178. PECTOSE. Insoluble in water, alcohol, or ether. Dissolved as Pectin, etc., by long boiling with water, more readily with vegetable acids. Hot dilute mineral acids dissolve pectose as Pectin, which by longer treatment becomes Metapectin. Alkalies, by hot aqueous digestion, form soluble salts of Metapectic acid. 179. PECTIN. Neutral; soluble in cold or hot water; gelatinized by dilute alcohol and precipitated by strong alcohol; changed by hot mineral acids to Metapectic acid; changed by cold dilute alkalies into soluble salts of Pectic acid, by hot and strong alkalies into soluble salts of Metapectic acid. 180. PECTIC ACID. In its moist state, gelatinous. Neutral in reaction. Insoluble in cold and scarcely soluble in hot water; by boiling water slowly changed to soluble Parapectic acid, afterward to Metapectic acid. Pectic acid jelly is hardened and parapectic acid solution is precipitated by alcohol and by solution of sugar. Boiling with dilute acids readily converts pectic acid to Metapectic acid. Alkalies, on contact with pectic acid, fbrm pectates soluble in water but insoluble in alcohol. The pectates of non-alkaline metals are insoluble in water. Boiling with aqueous alkalies converts pectic acid into soluble salts of Metapectic acid. 181. PARAPECTIN is neutral, soluble in water, insoluble in alcohol, by Nwhich its aqueous solution is gelatinized. Boiling dilute acids convert parapectin into Metapectin. Aqueous alkalies, on contact with parapectin, form soluble salts of Pectic acid. 182. PARAPECTIC ACID is soluble in water (with acid reaction), the solution changing into one of Metapectic acid. Parapectic acid is precipitated from water solution by strong alcohol. It fornis soluble salts with the alkalies; insoluble salts with the other mnetallic bases. CELL UL OSE. 167 183. METAPECTIN iS soluble in water (with acid reaction), inlsoluble in alcohol. Alkalies form with it the soluble salts of Pectic acid. 184. M/IETAPECTIC ACID is producible from all pectous substances, but produces none of them. It is soluble in water (with acid reaction); soluble in alcohol (separation from all other pectous substances); and forms soluble normal salts with all the bases (the non-alkaline salts of other pectous acids being insoluble.) Solution of subacetate of lead precipitates all the pectous substances (including metapectic acid). I-lot potassio cupric solution is reduced by all the pectous substances. They are but slightly or not at all changed to (lucose, by boiling dilute acids. 185. CELLULJOSfE. (C 0ID,)O. Chsaractecrized by its physical properties and relations to solvents (ca); by its transformation into parchment-paper (b), and into dextrin and glucose (c), and by its formlation of gun-cotton (d). It is selcaracted from Starch by its solubility in arnmonio cupric solution (ca), and by its insolubility in hot dilute acids. a. Pure cellulose is a white, translucent solid; of specific gravity about 1.5; insoluble in water, alcohol, ether, oils, and other neutral solvents. it is slowly disintegrated and partly dissolved with decomposition by strong aqueous alkalies. Hot dilute mineral acids scarcely affect it; moderately dilute nitric acid changing it to Xyloidin.-Finely divided cellulose slowly dissolves in a solution of oxide of copper in strong ammonia; being precipitated therefrom unchanged by hydrochloric acid.Fibres of cellulose, superficially softened by sulphuric acid, or by potassa solution, are colored violet to blue by iodine solution, and are by this means rendered distinctly visible under the microscope. Also, by dipping in a I per cent. solution of potassium iodide and drying, then immersing in strong sulphuric acid and washing with water, cellulose is converted into a blue substance, showing red and blue globules under the microscope (TEnRRELL). 168 C'uiRB OI YDRA TA'ES. b. Sulphuric acid of about 1.5 or 1.6 spec. gray., acting for a very short time on cellulose (unsized paper), changes its state of aggregation so as to form parchment-paper. c. Concentrated sulphuric acid, in the cold, slowly dissolves (thoroughly dry) cellulose to a colorless syrup, which closely resembles dextrin. It is, however, colored blue, or after standing some days in the acid, violet to brown, by iodine. The name anyloicl has been applied to this substance. If it is now, after several days' contact of the acid, diluted with 30 or 40' parts of water and boiled (until a portion is not precipitated by strong alcohol), it is wholly converted into glucose. (c. Nitric acid of spec. gray. 1.5, or a mixture of nitrate of potassa 2 parts and concentrated sulphuric acid 3 parts, at a temiperature below 500 C. (1220 F.), converts clean, dry cotton wool (finely divided cellulose), by 24 hours' contact, into nitrocellulose. This is washed first with cold water, then with hot water, lastly with alcohol and dried at ordinary temperature. 186. NITROCELLULOSE, Pyroxylon, or Gun Cotton is the substitution of (NO,)7_, for Hr_7 in C18I30015-, the lower substitutions being most soluble in ether, the higher substitutions being most explosive. It is more readily soluble in alcoholic than in pure ether-formation of Collodion. It is not attacked by dilute acids or alkalies: strong sulphuric acid dissolves it slowly, strong alkalies dissolve it with decomilposition.-The residue from collodion is unchanged pyroxylon, in a firm and elastic mass, capable of being maoulded at about 140~ C. 187. GLUCOSE. C HOH, 0.O. Grape sugar. Starch sugar. Dextrose.- Chcr-acterized by its physical properties and solubilities (a); its rotation of polarized light (b); its reactions with potassa (c) and, as a reducing agent, with potassio cupric solutions (d), cupric acetate (e), ferricyanide of potassium (f), ammonio silver nitrate (g), bismuthic subnitrate (h), and molyb. date of ammonimn (i), It precipitates ammoniacal acetate of lead (j), and reacts with stainnic chloride and cobaltous hydrate GL UTCOSE. 109 (k).-From Sucrose, it is distizguzishecd by a stronger reducing power (cI, e, f, g, i), by not blackening with concentrated sulphuric acid (IS9, c), but turning brown with potassa solution (c). — i'om Lactose, it is distinguished by stronger reducing power (e, i), less soluble precipitate with ammoniacal acetate of lead (j), and by not blackening with concentrated sulphuric acid.Erom ]'iuctose, it is selparated by crystallization, and clistingcislhed by contrary rotation (b). —It is sep2arated from Dextrin, Soluble Starch, Gums, the Pectous substances save metapectic acid, Gelatin, and Albumenoils, by solution in 90 per cent. alcohol (a) ); from Fats, etc., by insolubility in ether.-It is c7eterminecl by the volumetric solution of potassio cupric salt (1), or by the polariscope (b), or by fermentation (in). ac. Glucose crystc6llizes, with some difficulty, in warty or cauliflower-like masses, hydrated; but from strong alcohol, in anhydrous needles. At 60~ C., the hydrate becomes an anhydrous, white powder; at 1000 C., the hydrate melts to a transparent mass; but the anhydrous glucose melts at 130~ C. For weighing, it should be well dried at 600 C., then at 1100 C. (without melting).-Glucose is soluble in a little more than one part of cold water; a saturated solution having a spec. gray. 1.206 and containing 45 per cent. of anhydrous glucose. Dilute alcohol dissolves it freely; 100 parts of 90 per cent. alcohol dissolve 2 parts in the cold, 20 parts with boiling; in cold, absolute alcohol it is scarcely at all soluble. Insoluble in ether, chloroform, oils.; soluble in 60 parts hot amylic,alcohol; soluble in methylic alcohol. b. Anhydrous glucose has a specific rotatory power of 55~ (Pasteur) to the right. c. Potassa, or milk of lime, when warmed in solution of glucose, causesa?-reddish-yellow to brown color with deposition of a humus-li-kie substance (distinction from Sucrose). (d. The test for reduction of c~~ric hyc&ate to cuprous hydrate-in presence of alkali may be made by adding a drop or two of cupric sulphate solution and then an excess of potassa, or 170 CARB 0.11 YDRAE T~S. by use of enough of the standard solution specified in k to tinge the test-liquid bluish. At a gentle heat (short of boiling) glucose throws down the brownish-yellow precipitate of cuprous hydrate, changed by boiling to a brownish-red precipitate of cuprous oxide. Without heat, the reduction occurs after standing some time. (Compare Sucrose, b.) e. Solution of cupric acetate is reduced by glucose on boiling (distinction from Sucrose and from Lactose-the latter effecting a slight reduction after long boiling). f. Ferricyanide. of potassium (1 part) in solution with potassa (a part), at 80~ to 1000 C., is reduced by glucose to ferrocyanide. The reduction is shown by loss of color, and by a blue precipitate with ferric salt. (Distinction from Sucrose and fiom Dextrin.) g. Boiling solution of glucose separates silver (black) from nitrate of silver; more readily blackens the recent oxide of silver, and gives a dirty gray precipitate in solution of ammonio nitrate of silver (the latter a rcallns of distinction from Sucrose). it. Basic bismuthic nitrate, with carbonate of sodium, is reduced by boiling solution of glucoses with precipitation of bismuthous oxide as a dark gray sediment. i. Solution of molybdate of ammonium, at boiling heat, is reduced by glucose, with formation of the blue molybdic molybdate (distinction from Sucrose, Lactose, and Dextrin). j. Anmmoniacal acetate of lead solution is precipitated by ajdition of concentrated solutions of glucose, the precipitate dissolving in excess of glucose solution, but appearing again on boiling in solutions not too dilute and remaining when cold. k. Stannic chloride blackens when warmed with glucose.Nitrate of cobalt in concentrated solution of glucose is not colored by addition of solid potassa and boiling (with pure Sucrose a violet-blue precipitate is obtained). Quantitative. —. Glucose is determined in its reduction of'copper by use of a stancdardc solq&tionz made as follows: 34.64 granms pure crystallized cupric sulphate dissolved in 200 c.c. G-L UCOSE: LA TOSE. 1 71 water, with 150 grams l+u6r-ptassit in about 500 c.c. of a 10 per cent. solution of soda (sp. gr. 1.14), the mixture diluted to 1 litre. 1 c.c. is reduced'by 0.005 gram of (anhydrous) glucose, or by 0.0067 gram of lactose.* The solution must not suffer change by boiling. The addition of about 100 c.c. of pure glycerin (in the litre) prevents decomposition. The solution of sugar is diluted to such a number of times its own volume that it shall not be far from I per cent. glucose. Then, 10 c.c. of the blue solution are taken in an evaporating-dish, 40 or 50 c.c. of water added, and, while boiling, the graded sugar solution is added, until no blue color remains (after the precipitate has subsided or been filtered out). The quantity of sugar solution used contains 0.05 grams glucose, or 0.067 grams lactose. m. Pure sugar may be determined by fermentation, in a Will's Fresenius' carbonic acid apparatus, as follows: In-the first flask, of about 60 c.c. capacity, place 33.3 grams of the solution to be determined, and which is made of 5 to 10 per cent. strength of sugar. Add 0.3 gram tartaric acid and a small pinch of good pressed yeast, close the first flask (so that gas must pass through sulphuric acid in the second flask), and weigh the apparatus. Set aside at 30~ to 350 C. (86~ to 950 F.) for three days; and weigh again. The weight of carbonic anhydride lost, multiplied with 2.0454, gives the amount of anhydrous glucose, or of crystallized lactose, and, if multiplied by 1.94327 the quantity of sucrose. The results are lnot close, 188. LACTOSE. Co111,O6 (crystallized). Milk Sugar.C]haracterized by its physical properties (a); its reactionsas a reducing agent (b), and with acids and alkalies (c); with ammoniacal acetate of lead and with lime (d); and by its fermenta* That is, 180 parts of glucose (C6 H1206 ), or 240 parts of lactose (4 of C6 Il206 ), suffice to consume 40 parts of oxygen (2X0), reducing 1247 parts (5 Cu S0 [12 0]-) of- copper salt. And 180: 1247:: 5: 34.64. 1'72o ~4CA 1B 0H YDRA TES. tions.-It is dististiihecl from Glucose by a somewhat weaker reducing power (b), a more sparing solubility in cold water or dilute alcohol (a), and by blackening with sulphuric acid (c); from Sucrose by greater reducing power (b) and insolubility in strong, alcohol., It is cdetermzizec volumetrically by the potassiocupric solution (see Glucose, 1). ct. Lactose crystallizes in hemihedral trimetric crystals, hard and colorless, becoming anhydrous (C,122,,O,,) at 1500 C., and turning brown without melting at i60~ C.-It is solbble in 6 parts of water at ordinary temperature or 21 parts hot water, the cold saturated solution having a maximum spec. grav. 1.060, and is insoluble in cold absolute alcohol and in ether. b. The potassio. cupric solution is reduced by lactose very nearly as readily as by Glucose (187, dc and 1) (distinction firom Sucrose); one-third greater quantity being required, however, to produce the same effect.-Solution of cupric acetate is only reduced very slightly and slowly by boiling with lactose (distinction from Glucose). —Molybdate of ammonium solution is scarcely changed in a perceptible degree by boiling with lactose (distinction from Glucose).-Ammoniacal nitrate of silver solution is reduced by boiling with lactose (distinction from Sucrose). c. Concentrated sulphuric acid blackens lactose, rapidly when warmed (distinction from Glucose).-Potassa slowly turns lactose solution brown after heating to boiling point (distinction from Glucose). d. Ammoniacal acetate of lead solution gives but a slight precipitate, soluble in water and not reprecipitated on boiling. With milk of lime, not in excess, lactose forms a compound soluble in water, insoluble in alcohol. 189. SUCROSE. C01:H22011. Cane Sugar. Saccharose.Characterized by its physical properties (ca); its reactions as a reducing agent (b); its reactions with alkalies and acids (c), and with ammoniacal acetate of lead (d).'roiiom Glucose it is clistinguyishecd as a less powerful reducing agent (b), by blackening with sulphuric acid or turning brown with potassa solution (c), SUCROSE. 173 and by its reaction with cobalt (e)<. It is distinguished fiorn Lactose by weaker reducing power (b). It is approximately sejparated from Lactose by solution in cold water, and fully separated from Dextrin, Gums, Gelatin,. and Albumenoids by solution in 90 per cent. alcohol. It is separated from Fats, Resins, etc., by not dissolving in (nearly absolute) ether. It is c7eterminezcd by volumetric solution of potassio copper salt, after being changed to glucose (c, and:187, 1), by the specific gravity of its pure water solutions, by its specific rotatory power as measured in the polariscope, and by fermentation as directed for Glucose, 187, mn. c. Sucrose crystallizes readily in monoclinic (rhomboidal) prisms, generally with hemihedral faces, and anhydrous. At 160~ C. (3~200 F.) it melts to a clear liquid which solidifies to " barley sugar "; at about 210~ C. (4100 F.) Cctramel and other products are formed.-Sucrose is solzuble in about I part of water; scarcely soluble in cold absolute alcohol, insoluble in ether, chloroform, benzole, etc.-Sucrose has a specific rotatory power of 73.S~ to the right. b. Potassio cupric solution is at first not at all reduced by sucrose on warming, or even on digestion over the water-bath, but after boiling 5 or 10 minutes, a slight precipitate of cuprous hydrate appears, (lii; tinction from Glucose, Lactose, and Dextrin). -Solution of acemtte of copper is not reduced by long boiling (distinction from Glucose).-Ferricyanide of potassium is not reduced to fbrrocyanide by hot solution of sucrose (distinction from Glucose).-Stannic chloride is reduced on warming, and chromate with excess of potassa on boiling, with sucrose, (reactions coinciding with those of Glucose and Lactose). —Ammoniacal nitrate of silver solution is not reducedcl, though turned yellowish, on warming with sucrose (a distinction from Glucose). RIecent oxide of silver with excess of potassa is blackened on boiling with sucrose.-Molybdate of ammonium (neutral solution) is unchanged by sucrose (distinction from Glucose). c. Sucrose is not readily colored by warming with solution 174 CARB OHYDRA TES. of potassa (distinction from Glucose). Lime forms a soluble compound with sucrose.-Concentrated sulphuric acid blackens sucrose on warming, with separation of carbon and evolution of sulphurous and formic acids (distinction firom Glucose).-Dilute minreal acids (2 to 3 per cent.), boiled 10 to 15 minutes with sucrose, transform it into glucose. The same change is very slowly effected by long boiling in water, and with moderate rapidity by boiling with dilute vegetable acids. Also by the conditions of alcoholic fermentation. sd. Ammoniacal solution of acetate of lead gives a white precipitate (PbC~H,1180,), scarcely soluble in cold but readily soluble in hot water. e. The blue to violet and rose-red precipitate made by addilng potassa to nitrate of cobalt solution and boiling is scarcely altered by presence of sucrose, or held a little more in the violet. (In presence of Glucose, the mixture after boiling is colorless or brownish, but not violet or blue.) CARAMEL. A mixture of three compounds: CIaramnelctae-brittle at ordinary temperatures, soft at 1000 C., odorless and bitter; deliquescent and very soluble in water, sparingly soluble in alcohol, insoluble in ether. Caranmelene brittle, freely soluble in water, not deliquescent, sparingly soluble in alcohol, insolublin ether. C(aratmelin-black, shining, and infusible; having three modifications with different and varying solubilities. Caramel is precipitated by subacetate of lead solution; and reduces potassio cupric solution. As generally prepared, caramel has a characteristic, "burned-sugar " odor. 190. MANNITE. 06111406. Crystallizes readily from solution in thin, four-sided prisms; melts at 160~ C., and at 200~ C. (392~ F.) distils with little decomposition. It dissolves in 6 or S parts of water of ordinary temperature, in 80 parts of 60 per cent. alcohol or 1400 parts of absolute alcohol or smaller quantities of boiling alcohol, but is insoluble in ether. —It is not black ALCOHOLS. 175 ened by concentrated sulphuric acid,, or turned brown by boiling with potassa, and it does not reduce the potassio cupric:sulphate solution. It is not subject to the alcoholic fermentation. ALCOHOLS AND THEIR PRODUCTS. 191. METHYLIC ALCOHOL. CH40. Recognizedl by its sensible and physical properties (c); its reaction with potassa and, as a commercial article, with sulphuric acid (b); by solution of recent mercuric oxide (c); by its reducing power (d), and its formation of formic acid (e). It is sepacrated by fractional distillation (f). It is approximately deterzined as methyl oxalate (g) or as formic acid (e, and Formic acid j or k). a. Pure methylic alcohol is a colorless liquid, of spec. gray. 0.800, boiling at 66~ C. (151~ F.), and of characteristic taste and odor. The commercial article is seldom free fiom empyreuma. It is miscible in all proportions of water, alcohol, and ether, and dissolves resins and nearly all substances soluble in ethylic alcohol. b. The addition of potassa, with boiling by the heat of the water-bath, causes a brown color in a short time (Ethylic alcohol only after a long time).-Ordinary methylic alcohol giyes. a red to red-brown color with concentrated sulphuric acid. c. Add (to the distillate f) 2 or 3 drops of very dilute solution of mercuric chloride, then solution of potassa in excess, agitate and warm. If methylic alcohol is present, the mercuric oxide will be dissolved. cl. Methylic alcohol readily decolorizes permanganate of potassium solution; but does not reduce silver nitrate, or potassio cupric solution. e. Oxidation to fornmic acid is effected by distillation of 2 176 ALCOHOLS. c.c. of the liquid examined, in a retort of 60 c.c. capacity, with 2 grams of powdered bichromate, 15 c.c. of water, and 25 drops of sulphuric acid-digesting fifteen minutes and then distilling 15 c.c. f. In the cistillation of methylic alcohol, add a little animal charcoal and a little solution of sodic carbonate, and receive the distillate at 660 to 76~ C. (1510 to 169~ F.) Quantitative.-g. Place in a retort 55 grams crystallized oxalic acid and the mixture of 35 grams of concentrated sulphuric acid and 25 grams of distillate f, digest for ten hours, and distil from an oil-bath at 1600 to 180~ C., as long as anything passes over. The distillate consists of oxalic ethers; methyl oxalate being freely soluble in water, while ethyl oxalate is nearly insoluble. The distillate is now washed with 25 times its volume of water; the clear solution decanted, digested, in a close bottle, with excess of potassa, the mixture acidulated with acetic acid and precipitated with calcium chloride (adding potassic acetate). Gather the oxalate of calcium, wash, dry, and ignite to carbonate (adding ammonium carbonate and igniting slightly again, if necessary), CaCOQ; 2GO11;0:; 0.64. 192. ETHtIIYIC ALCOOIHOL. C2EO. Ch6/acicberlizecd by its physical and sensible properties (a); by the extent of its reducing power (b); by its formation of iodoform (c); of various compound ethers (r), and of acetic acid (e). —Seplaracted by fractional distillation, solubility in water, and insolubility in fixed oils. Separated from methylic alcohol as an oxalic ether (191, g), fromn amylie alcohol by solution in water or by fractional distillation. —Determirnecd by the specific gravity or by the boiling point of its mixtures with water. ca. A transparent, limpid liquid, of spec. gray. 0.794, freezing at -95~ C. and boiling at 78~ C. (173~ F.), of an agreeable and pungent odor and a sharp and burning taste. It is miscible with water, ether, chloroform, benzole, petroleuml naphtha, volatile oils and castor oil, and dissolves resins and camphors. ETJIYLJC AL COHOL.' 1 b. Alcohol-as a hot liquid.cl or as vapor-slowly reduces chromiic acid, or a mixture of potassic bichromnate and sulphuric acid-the alcohol being first oxidized to acetic acid. (This is in common with aldehyde, acetic acid, formic acid, and many volatile organic bodies.) Permanganate of potassium is but slowly reduced by ethylic alcohol-so that the red tinge of a slight addition of a -rt solution is scarcely at all afficted for several minutes. (Methylic alcohol, Formic acid, Aldehyde, and many other volatile organic bocies, more readily reduce the permanganate. ) c. The'production of iodoform from alcohol is a result (in part) of the reducing power of the latter upon alkaline iodate: 6KEO+6I=C=KI+KIO,+31E1O KI3+ C2- 60 + 2I = CI+KCHO2 + 2O Take 3 to 5 c.c. of the distillate to be tested, 5 to 6 drops of a 10 per cent. potassa solution; warm to 100~ or 120~ C. (212~ to 248~ F.), and add-of a solution of potassic iodide in five parts of water, saturated with iodine-until the liquid is brownishyellow. If, on agitation, the color does not disappear, add one or two drops of the potassa solution. If alcohol is present, the iodoform appears, sooner or later, in yellow scaly particles.'With a power of 200 to 400 diameters, these are seen as hexagonal stars and rosettes. Ilodoform is formed also by Aceton, Aldehyde, Acetic ether, JButyric alcohol, Amylene. Not formed by Ether, Alnylic Alcohol,. Chloroform, Chloral, Chloral ITydrate, and, according to LIEBEN, not formed by Methylic alcohol. d. See under Acetic acid, 40, b, and Butyric acid, 41,'b. (One c.c. of the distillate to be tested is treated with 0.3 to 0.5 gram of dry potassic acetate and 2 or 3 c.c. of sulphuric acid.) e. Acetic acid is formed from alcohol by digestion with a mixture of bichromate of potassium and dilute sulphuric acid, or of permanganate of potassium and dilute sulphuric acid. See 40. 193. ALJD[EITYDE. C21i4O. Acetic Aldehyde.-A trans 178S 1A L COIOLI2C' PR O) UCTS. parent and colorless liquid, of spec. gray. 0.800 at 0~ C., dcistilling at about 21~ C. (70~ F.), neutral in reaction, of a pungent anid suffocating odor, slightly resembling that of apples. The vapor irritates the eyes.-It is miscible in all proportions with water, alcohol, and ether, but not with aqueous chloride of calcium (separation from Alcohol).; It dissolves sulphur, phosphorus, and iodine.-It promptly reduces ammonio nitrate of silver, forming a specular coating on the glass (distinction from Acetic acid, Alcohol, Ether). It burns readily, with a blue flame. It is blackened by sulphuric acid.-Potassa solution, warmed with aldehyde, colors it brown, with deposition of " aldehyde resin " and formation of acetate and formate (a characteristic test). Ammonia (gas) with aldehyde forms aldehyldate of ammonium, a compound of an ammoniacal, terebinthinate odor, crystallizing (firom ether or alcoholic ether) in transparent acute rhombohedrons. melting between 70~ and 80~ C., and distilling at 100~ C. It dissolves in water, sparingly in alcohol and ether. With other bases aldehyde acts as a-monobasic acid, exchanging one atom of its hydrogen. 194. SULPHETHYLATES. RHCH215S04. Ethyl.sulphates. -Sulphethylic acid is a limpid, oily, acid liquicd, of spec. grav. 1.315, decomposed by heat, evolving ether at 130~ to 140~ C. (266~ to 2840 F.) —t is soluble in water and alcohol, not in ether.-Its metallic salts are all soluble in water, and are mostly soluble in aqueous but not in absolute alcohol, the ammonium salt only is soluble in ether. The sulphethylates are gradually decomposed in boiling water. Barium sulphethylate crystallizes in permanent mnonoclinic prisms, with 2H20 which is expelled in a vacuuml, the anhydrous salt bearing 100~ C. without change. It dissolves in about one part of water, and in a larger quantity of aqueous alcohol. The socdium salt crystallizes in slightly efflorescent hexagonal plates, with H,20, soluble in less than one part of water, melting at 86~ C. When anhydrous, it bears 1000 C. without change. ETHER. 179 195. E'THER. (C,25)20. Recognized by its sensible and physical properties (c). Separatedc by distillation, or by solution (b). a. Spec. yrav., at 15~ C., 0.713; at 17.50 C., 0.7185. Boiling point, 350 C. (950 F.) Ether of spec. grav. 0.72S, and boiling at blood heat, has from 5 to 6 per cent. of about 90 per cent. alcohol; that of spec. grav. 0.750 has about 25 per cent. of 88 per cent. alcohol.-At 17.5~ C. (63.5~ F.), one part of ether dissolves in 12 parts of water, and 35 parts of ether dissolve one part of water. Alcoholic ether is inmre soluble in water: 6Ether" of sp. gr. 0.719 to 0.721 dissolves in 12.0 parts water. " " " 0.724 " 0.726 " " 10.0 " "''" " "' 0.729 6' 0.731 " " 7.7 " "' " "C 0.733 " 0.735 " " 6.2 " " "' " " " 0.738 " 0.741 " " 5.0 " " " " " 0.743 " 0.746 " " 4.3 " "'" " " 0.748 " 0.750 " " 3.8 " " Salts not soluble in ether (as dry potassic carbonate) separate it from water almost wholly. Ether is miscible in all proportions with alcohol, chloroform, benzole, petroleum. naphtha, fixed and volatile oils, and dissolves resins, sulphur, phosphorus, iodine, and ferric, mercuric, and auric chlorides, Tannic acid does not dissolve or deliquesce in absolute ether, but deliquesces in the "stronger ether" of spec. grayv. 0.728. Ether is less soluble in glycerin than in water. It mixes with concentrated sulphuric acid, the liquid turning brown when warmed. —In the air, ether very slowly oxidizes to acetic acid. Its combustibility renders it necessary to use strict precautions in the manipulation of its vapor. b. Ether is approximately separated from alcohol by means of glycerin (or water). A test-tube of over 20 c.c. capacity is graduated from the point of 10 c.c. contents (marked 0) to the point of 20 c.c. contents (marked 10). Ten c.c. of glycerin or I80 ALCOHOLIC PROD UCThS'. water is taken in the tube, then 10 c.c. of the ether is added, the contents shaken together, the ether allowed to separate, and the increase in the lower layer is read off. 196. NITROUS ETHER. CH5NO2. Nitrite of ethyl.Cctaracterized by its sensible and physical properties (ct) and by reactions of nitrites. —Estimated, in its alcoholic mixtures, by their boiling point (b), and by volumetric trial with permanganate (). a. Nitrite of ethyl is a yellowish liquid, of spec. grav. 0.947, boiling at 16.6~ (62~ F.), and of an agreeable odor of apples. It is soluble in 48 parts of water, in all proportions of alcohol, and freely soluble in dilute alcohol. It gradually decomposes; more quickly in contact with water. b. "Spirit of nitrous ether," of 5 per cent. nitrite of ethyl, boils at 63~ C. (145~ F.): the test-tube containing it being immersed in water of that temperature, and a few fragments of broken glass added. Quantitative..-c. 10 grams of the spirit of nitrous ether are macerated, with 1.2 to 1.5 grams of fused potassa, in a stoppered flask, for 12 hours, occasionally agitating. Then pour the mixture into a beaker, dilute with an equal bulk of water, and leave at a warm temperature till the odor of alcohol disappears. Acidulate slightly with sulphuric acid, and add, from a burette, a solution of potassium permanganate of known strength, until the color ceases to be discharged. The number of grams of permanganate expended, multiplied by 1.18, equals the number of grams of ethyl'nitrite in the 10 grams of material takef. 197. CHLOROFORM. CHO,. Idcentified by its sensible and physical properties (a); its liberation of chlorine when decomposed (b), and its production of isonitril (e). It acts as a reducing agent (d). It is sepacrateci by washing with concentrated sulphuric acid and with water, and rectification from alkaline carbonate, lime, calcium chloride, animal charcoal (e). It may CIIHL OR OF OR J. 1i81 be estimaltel from the chloride it gives after digestion with alcoholic fixed alkalies; Ca. Chloroformll is a colorless liquid;,: oec. grav. 1.497 (at 15~ C.), boiling at 61i C. (1420 F.). It. is:Jieutral ill reaction, and has an agreeable sweet ethereal odoi' and burning sweet taste. It is not readily combustible, but burns with paper, with a green-bordered flame. By standing, especially in the light and if free from alcohol, it becomes acid and gives reactions for chlorine and hydrochloric acid.-Chloroform is not miscible in water except in traces, bUt;is soluble in all proportions of' alcohol, ether, benzole, petroeum naphtha, bisulphide of carbon, fixed and volatile oils-noic concentrated sulphuric acid. It dissolves sulphur, phoshoi; iodine, iodoform, resins, caoutchouc, and gutta perla.'I b. Chloroform is 4ec mposed, with production of chlorine and hydrochloric acid, when it is passed in vapor through a redhot tube; or, with production of chloride and. formate, when digested with alcoholic solution of potassa (slowly by aqueous potassa). (Alcoholic amnmonia produces ammonium cyanide and chloride-the better with help of potassa.) CIH C13+4KH O 3K C1+- C-KH, 02+2,2O CH C1,-+5N H, =3NH4,C1+N H C N Also, with production of hydrochloric acid, by nascent hydrogen, as evolved by zinc with. sulphuric acid diluted with alcohol.The free chlorine is made evident by potassic iodide (and starch), and the hydrochloric acid by silver salt. (Neither pure nor alcoholic chloroform affects silver nitrate.) c. Chloroform, even in solution with 5,000 parts of alcohol, when treated with anilin (or other monaminhe) and then with alcoholic soda, forms an isonitril, recognized by its characteristic odor (HIFFMANnX). This test distinguishes chloroform from Chlorcethylidene (C,2HC1l,). Iodoform, Bromoform, Chloral, etc., react in the test, the same as chloroform. 18~2 Aig:lC:~IOOrLIC PROD UCTS. d. Chloroform roadily reduces the hot potassio cupric solution (distinction froAi r chlorcethylidene and from alcohol). e. Chloroform( Vi be separated from slight mixtures of Ether, Alcohol, Wxva!te.i et, as fbllows: To 10 parts of the impure chloroform, add 2:. p'arti f concentrated sulphuric acid, and shake together occasionally forb, 24- -hours. Remove the upper' layer, add to it I part of'(crystallized) carbonate of sodium previously dissolved in 1 part of water, -gitate and digest (cold) for half an hour, then remove th'e lower layer ankd distil it from A- part of freshly-burned lime.-Distillatio'from dry calcium chloride separates chloroform from aicoh1-To separate from Ethereal Oil (ethyl and ethylene- suphates), distil from animal charcoal. 198. CHLORAL HYDRATE, C2130O.II2O. Char'acterized by its sensible and physical properties (a), and its formation of chloroform (b), and of chloralide (c). It has, with alkalies, considerable reducing power (d). Separated from chloral alcoholate by its slight solubility in cold chloroform and its greater solubility in cold water.-E'stimated from the amount of chloroform it produces (e). a. A friable solid, crystallizing from solvents in transparent -rhomboidal crystals, or congealing in a white crystalline mass, melting at about 60~ C. (140~ F.) and boiling at 950 C. (203~ F.) — (the Alcoholate boils at 1160 C.). It slowly sublimes, in the bottle, at ordinary temperatures. It is neutral in reaction, and of an aromatic, penetrating, and slightly acrid odor, and bitter, caustic taste. Melted in a spoon, over the flame, it does not take fire (distinction from the alcoholate).-It is slightly deliquescent, readily soluble in 1 parts of water (the alcoholate dissolves sparingly in cold water); soluble in alcohol, ether, benzole, petroleum naphtha, bisulphide of carbon; slightly soluble in cold chloroform (the alcoholate freely soluble). It forms liquid mixtures with camphor, and with phenicacid, and a crystalline mixture with glycerin. CHLOR-AL HID)LI TB. 183 b. Fixed and volatile alkalies, and their carbonates, in solution, decompose chloral hydrate-the chloroform subsiding from the milky mixture. c2i ci o.o2 + KiHO = l CHC13+KCH02+ 20 (100 parts chloral hydrate producing 72.2 parts of chloroform.) (Trichloracetic acid, also decomposed by alkalies into chloroform and formate, has an acid reaction, and boils at 195~ C.) c. Concentrated sulphuric acid separates, from about an equal weight of chloral hydrate, anhydrous chloral-the latter rising to the surface, as a pungent and irritating oily liquid, of spec. grav. 1.5. —Chloralide is formedwhen chloral hydrate (concentrated, if necessary, by distillation froni chloride of calcium) is heated with about six times its volume of concentrated sulphuric acid, at 125~ C., for some time. When cool, the mixture is diluted with six measures of water, and, if carbonized at all, extracted with ether. On evaporating the ether the chloralide (C05H,ClO,) crystallizes in stellate groups of prisms (or in needles) which melt at 116~ C. and burn at 200~ C. with a green-edged flame.-In certain conditions, sulphuric acid changes chloral into metachloral (insoluble in water, alcohol, or ether). d. Chloral hydrate, in the act of decomposition by ammonia, promptly reduces nitrate of silver as a specular coating.Aqueous solution of pure chloral hydrate does not within a few minutes perceptibly decolorize the permanganate of potassium solution, and does not at all affect argentic nitrate.-The potassio cupric solution is reduced by chloral according to 197, cd. Quantitative.-e. Take 10 grams of the chloral hydrate, dissolve in the least quantity of water, and add, in a graduated tube holding 20 c.c., ammonia enough to be a slight excess for the absolute chloral hydrate taken, according to the equation in b (5 c.c. of water of ammonia of spec. grav. 0.90). Stopper tightly in the tube, which should be nearly filled by the liquid, and leave until the subsident layer no longer increases-four to twelve 184 A L CO1OLIC PROD UCTS. hours. The c.c. of chloroform are multiplied by 1.5 for grams. Closer results are obtained by taking 50 grams chloral hydrate. 199. IODOFORM. CH I.. A sulphur-yellow solid, crystallizing in hexagonal plates, stars, and rosettes; melting, at 1150 to 120~ C., with partial vaporization and partial decomposition into carbon, hydriodic acid, and iodine. It has a safli'on-like odor, reminding of chloroform and of iodine, and a taste like the same substances, becoming unpleasantly strong of iodine.-It is soluble in 13,000 paswts of water (to which it imparts a slight odor and taste), in 80 parts of cold or 12 parts of boiling alcohol of 80 per cent., in 20 parts of ether, and soluble in chloroform, bisulphide of carbon, fixed and volatile oils. The alcoholic solution is straw-yellow; the ether solution, gold-yellow; both solutions are neutral, and have a sweet-ethereal, burning taste and iodine-like after-taste.-It is difficultly and imperfectly decomposed by boiling aqueous potassa, but (WITTSTEIN) alcoholic potassa decomposes it, forming iodide and formate (see chloroform, b). 200. CROTON-CHLORAL HYDRATE. C4HC1i0. The trichlorinated aldehyde of crotonic acid.-Thin, dazzling-white plates, melting at 78~ C., volatile in steam at 100~ C., boiling at 163~. It has a sweetish, melon-like taste, and its vapor irritates the eyes. It is sparingly soluble in cold, freely in hot water, and soluble in alcohol and in glycerin. Potassa decomposes it with formation of potassic chloride and formate and dichlorallylene (C32C12,). 201. AMYLIC ALCOHOL. C,1120. Ucarccterized by its sensible and physical properties (a); by its production of red sulphamylic acid (b); by its formation of odorous ethers (c).-It is sep9rcuted from alcohol by fractional evaporation or distillation, or by adding water and extracting with ether (d); from water, in the slight proportions miscible, by adding petroleum naphtha or benzole, or by adding common salt (e). AXIYLIC ALCOHOL. 185 a. A colorless and transparent liquid, of spec. grav. 0.816, boiling at 132-3~ C. (270~ F.), and having a sharp taste and a characteristic, pungent odor. its vapor excites coughing, a few moments after it is inhaled.-It is soluble in about 40 parts of water, less soluble in solutimt of common salt, soluble in all proportions of alcohol, ether, chloroform, benzole, petroleum naphtha, fixed and volatile oils. It makes a slowly evanescent oil-spot upon paper.-It burns with a smoky flame. b. When two parts of amylic alcohol are digested warm with three parts of concentrated sulphuric acid, sulphamnylic acid, or amyl sulphuric acid is formled-having a red color anid dissolving freely in water. c. Distilled or digested hot with concentrated sulphuric acid and potassic acetate, the odor of " pear-oil " is developed -from formation of amyl acetate.-Distilled or digested with sulphuric acid ancl a little water and bichromate of potassium, the apple-odor of valeric aldehyde is first generated, and theni the peculiar odor of valeric acid (42). d. It is separated from (aq-ueous) ethylie alcohol, by adding an equal volume of pure ether, andcl then to the whole an equal volume (or enough) water to cause the ether to separate. The latter will contain most of the amylic alcohol. Benzole or petroleumn naphtha may be used instead of ether. e. If from 100 c.c. of' commercial "'fusel-oil" are slowly distilled 5 c.c., and this be agitated with a saturated solution of common salt, the separation of an oil-layer of 2.5 c.c. or over indicates that there is less than 15 per cent. of " proof spirit" in the fasel-oil taken. 202. " FUSEL-OIL 9contains, besides amylic alcohol, small proportions of Butyric, Valerie, and volatile Fatty Acids, andl of propylic and. butyric alcohols.-In examination of spirits for fusel-oil, add 2 or 3 c.c. of' potassa solution, to about 30 c.c. of' the material, and evaporate by a gentle heat to dryness. Add 5 or 6.ce. of sulphuric acid and nearly as much water: I 86 ALCOHOLICr PROD UCTS. when, if the acids in question are present, their odor will be apparent.* 203. NITRITE OF AMYL. C5H1lNO2. A light-yellowish liquid, darkening when heated, of spec. grayv. 0.877, boiling at about 960 C. Its vapor has a reddish-yellow color. Its odor resembles that of ethyl nitrite.-Sulphuric acid (concentrated) decomposes it with explosive violence, sometimes with combustion. Alcoholic potassa decomposes it quickly, fbrming potassic nitrite: aqueous potassa decomposes it slowly. * Farther, see Prescott's ExamJnation of Alcoholic Iiquors, New York, 1875. INDEX. ABSINTHIN, 151, 156. Balsam of Copaiba, 96. Acacia, 162. Peru, 102, 103. Acetic Acid, 13, 58. Tolu, 103. Acetic Ether, formation of, 59. Baranilin, 120. Acids, 13. Bases, Volatile, 120. Separated as lead salts, 59. Beech-nut Oil, 73, 76, 81 Aconitia, 125, 128, 135, 137 to 140, 142 Benzene, 119. to 144, 148, 150. Benzoin, 94, 103. Aconitic Acid, 13, 21. Benzole 13, 118. Acrolein, formation of, 86. Benzoyi Hydride-see Bitter AlAcrylic Acid, formation of, 86. mond Oil. Agaric Resin, separated from Gam- Berberina, 125, 128, 135 to 138, 140, boge, 98. 142, 143, 145, 147, 149, 151. Separated by Chloroform, 10-4. Bergamot Oil, 107 to 110, 112, 114. Albumen, 158. Bitter Almond Oil, 107 to 111. Albumenoids, 13, 157. Artificial-see Nitrobenzole. Alcohol, 13, 176. Formation of, 62. Alcohols, 175. Boheic Acid, 13, 36. Aldehyd, 13, 177. Bone Oil, 76, 81. Aldehyds, as Volatile Oils, 104. British Gum —see Dextrin. Alkaloids, Fixed, 13. Bromated Camphor, 116. Volatile, 13, 120. Brucia, 125, 128, 135, 137 to 140, 142, Allspice Oil-See Pimento Oil. 143, 145 to 150. Almond Oil, 73, 76 78, 81. Butter, 74, 81. Almonds, Oil of Bitter-See Bitter Butyric Acid, 13, 60, 61. Almond Oil. Ether, Formation of, 62. Aloes Resins, 93, 103. Butyrin in Butter, 81. Separation of Gamboge from, 98. Aloin, 151, 156. CACAO Butter, 74. Amber, 93, 103. Cacodyl, Formation of, 59. Amber Oil, 107, 108, 109, 111, 114. Caffeina, 125, 127, 128, 135 to 140, 142 Ammonia, 124. to 145, 148 to 150. Ammoniac, 93, 103. Caffetannic Acid, 13, 28, 35. Amygdaliu, 144, 152. Cajeput Oil, 107 to 110, 112, 114. Amylic Alcohol, 13, 184. Calamus Oil, 107 to 110. Amyl, Nitrite of, 186. Calvert's Tests for Fixed Oils, 78. Amyloid, 168. Camphor Oil, 107. Anilin, 120140, 142, 146, 148. Camphors, 13, 116. Compounds, 13 14. Canaiiba Wax, 95 103. Anise Oil, 107 to 111, 114. Cane Sugar —see Sucrose. Anthracene, 13, 117. Cannabin, 98. Arabic Acid, 162. Caoutchouc, 95, 103. Arabin, 162. Capric Acid, 67, 68. Asparagin, 152, 156. Caproic Acid, 67, 68. Assafetida, 94, 103. Caprylic Acid, 67. Atropia, 125, 128, 135, 137 to 149, 142 Caramel, 173, 174. to 144, 147, 148. 150. Caramelane, 174. Auric Chloride, as Reagent for Al- Caramelene, 174. kaloids, 150. Caramelin, 174. Caraway, Oil of, 107 to 110, 112. BALM Oil, 107, 112. Carbazotic Acid-see Nitrolphenic Balsams, 93. Acid. 187 18 $8 IINDE'X. Carbohydrates, 13, 161. Colombo Bitter-see Colombin. Carbolic Acid-see Phenic Acid. Colopholic Acid, 96. Carbon, uncombined, 11. Colophony, 95, 103. Compounds of, 111. Separation from Lac, 101. Cardamon Oil, 107, 108. Color Resins, 93. Carminic Acid, 13, 40. Columbic Acid, 13, 39. Carmine-see Carminic Acid. Columbo Root, separation of Acid Cascarilla Oil, 107, 109 112. from, 39. Casein, 159. Colza Oil, 73. Castor Oil, 73, 70, 78, 80, 81. Conia, 123, 128, 135to138, 140, 142 to Catechu, 34. 145, 149. Catechuic Acid, 13, 28, 34. Convolvulic Acid, 100. Catechutannic Acid, 13, 28, 33. Convolvulin, 100,103. Cathartic Acid, 153, 156. Separation from Gamboge, 98. Cathartin-see Cathartic Acid. Convolvulinol, 100. Cellulose, 13, 167. Convolvulinolic Acid, 100. Cephaelic Acid, 28. Copaiba Oil, 107, 108 110, 113, 114. Ceroso-ceric oxide, as Reagent, 146. Copaiba Resins and Balsam, 96. Cerotic Acid, 13, 70. Copaivic Acid, 96. Chamomile Oil, 107, 108, 109. Copal, 96, 103. Chloral Hydrate, 13, 1 82. Coriander Oil, 107, 113. with Oil of Peppermint, 115. Cotton-seed Oil, 73, 76, 81. Chloralide, 182. Creosol, 68. Chlorine, as Reagent for Alkaloids, Creosote, 13, 116. 148. Cresylic Acid, separation of Phenic Chloroform, 13, 180. from, 48, 50. Chrysammic Acid, 152. Croton Chloral Hydrate, 184. Chrysophanic Acid, 13, 41. Oil, 73, 77. Chrysophane - see Chrysophanic Cubebin, 135 to 138, 145, 154, 156. Acid. Cubeb Oil, 107 to 110. Cinchona Bark, separation of Acids Cumidin, 120. from, 37, 39. Cummin Oil, 107, 108. Cinchonia, 125, 128 136 to 140, 142, Curarin, 136, 137, 1429, 145, 146, 147. 143, 145, 149, [50. Cymidin, 120. Cinchonidia, 125, 128, 149, 150. Cytisin, 142. Cinchotannic Acid-see Quinotannic Acid. DAMMARA (Dammaran, etc.), 96, 103. Cinnamate of Cinnyl, 102. Daphnin, 125, 128, 148. Cinnamon Oil, 107 to 110, 112, 114. Daturia —see Atropia. Citric Acid, 13, 18. Delphina, 125, 128, 135 to 138, 141 to Citric Acic, distinguished from Tar- 145, 149, 150.: taric, 15. Dextrin, 13, 162. Cloves, Oil of, 107 to 111. Dextrose-see Glucose. Cochileal, separation of Carminic Dextrotartaric Acid, 13. Acid from, 26. Dialysis of Alkaloids, 131, 134. Cocoa-nut (Coco-nut) Oil, 80. Digitaleic Acid-see Digitalic Acid. Codeina, 125, 127, 128, 136 to 138, 140 Digitalic Acid, 13, 26. to 143, 145, 147 to 150. Digitalin, 125, 27, 128, 135 to 139, 141, Cod-liver Oil, 73, 77, 78, 80, 81. 143 to 145, 149, 150. Coffee, separation of Caffetannic Digitoleic Acid-see Digitalic Acid. Acid from, 35. Dill Oil, 107, 111. Cohesion-figures of Oils, 74, 105. Distillation, Fractional, 66. Colchicia (Colchicin), 125, 127, 128, Dragendorff's Method with Alka135 to 140, 142 to 150. loids, 131, 134, 136. Colocynth, separation from Gam- Dragon's Blood, 97, 103. boge, 98. Colocynthin, 136, 137, 145. ELAIDIN, formation of, 75 Colombic Acid-see Columbic Acid. Elsoptenes, 104. Colombin, 145, 151, 156. Elaterin, 136, 145, 154, 156., AYDE)& 189 Emetia, 125, 128, 135 to 138, 141, 142, Graham and Hofmlann's Method, 131, 145, 149, 150. 134. Emulsions, formation of, 74. Grape-seed Oil, 72. Ergotina, 125, 128, 141, 145. Grape Sugar, 168. Erucic Acid, 13, 70. Guaiacol, 116. Essence of MiIirbane-see Nitroben- Guaiac Resin, Separation from Gamzole. boge, 98, 103. Ether, 13, 179. Guaiacum, 98, 103. Ethers, Compound, 13. Guaiaretin, formation of, 98. Ethylic Alcohol, 176. Gum, 13, 161. Ethyl Sulphates, 177. Arabic, 161. Eucalyptus Oil, 107, 109, 113. Tragacauth, 162. Gum-resins, 93. FATTY Acids, 13. Gun Cotton'-see Nitrocellose. Separation from Neutral Fats, 71. HIAGER'S Method with Volatile Oils, Non-volatile, 68. 111. Volatile, 67. Hazel-nut Oil, 73. Fats, 72. Hemp Resin 98, 103. Fennel Oil, 107, 108, 109, 112. Hemp-seed 6il, 72, 77, 80, 81. Ferric Chloride, as Reagent for Al- Hesperidin, 145. kaloids, 148. Hippuric Acid, distinguished from Fixed Oils 72. Benzoic, 43. Formic Acid, 13, 55, 60, 75. Hop Oil, 107, 109. Ether, formation of, 56. Hydrastia, 125, 128, 138, 145, 146, 148. Fractional Crystallization, 68. Hyoscyamia, 125, 128, 135 to 138, 142, Fusion, 71. 144, 145, 148 to 150. Saturation and Distillation, 66. Frankincense, 102. IGASURIA, 125 128, 138, 145, 147, 148. Fraxin, 154, 156. Incense-see Olibanum. Frohde's Reagent, 144. Indian Hemp-see Hemp Resin. Fuchsin, 120. India Rubber-see Caoutchouc. Fusel-Oil, 185. Indigo Blue, 99, 103. Fustic, separation of Morintannic Iodine Solution, as Reagent, 139, 144. Acid from, 35. Iodoform, 13, 1717, 184. GALANGAL Oil, 107. JALAP Resins, 99. Galbanum Oil, 107. Jalapic Acid, 100. Gallic Acid, 13, 30. Jalapin, 99, 103. Gallotannic Acid, 28. Separation from Gamboge, 98. Gamboge, 97. Jalapinol, 100. Resin of, 97, 103. Jalapinolic Acid, 100. Gambogic Acid, 13, 41, 97. Jasmin Oil, 107. Gasolene, 119. Juniper Oils, 107, 108, 109, 113, 114. Gelatin, 13, 160. Gentianic Acid, 13, 39. KINIC Acid-see Quixic Acid. Gentianin-see Gentianic Acid. Kinotannic Acid, 33. Gentian Root, separation of Gen- Kinovic Acid-see Quinovic Acid. tianic Acid from, 40. Kinovin-see Quinovic Acid. Gentisic Acid-see Gentianic Acid. Kuphanilin, 120. Gentisin-see Geiltianic Acid. Geranium Oil, 107, 113. LAC (resin), 100, 103. Glucose 168. Lactic Acid, 13, 53. Glucosides (with Alkaloids), 125. Lactoscope, Vogel's, 84. Glue-see Gelatin. Lactose, 171. Glyceric Acid, resemblance to Lac- Lactucin, 154, 156. tic, 53. Lard, 74. Glycerin, 13, 85. In Butter, 83. Determined in Soap, 91. Oil, 73, 76, 78, 80, 81. 190 IN~DEX=. Lauric Acid, 13, 70. Nitrobenzole, 13, 112, 119. Lavender Oil, 107 108, 110, 113, 114. Nitrocellulose, 168. Lead Salts of Acids separated, 59. Nitrogenous Neutral Bodies, 157. Leather, 161. Nitrophenic acid, 13, 49, 51. Lemon Oil, 107 to 110, 113, 114. Nitrous Ether, 180. Limonin, 145. Non-drying Oils, 73, 75. Linoleic Acid, 13, 69. Non-volatile Alkaloids, 125. Liquid Non-volatile Acid, 53. Fat Acids, 68. Volatile Acids, 55. Nutmeg Oil, 107, 111, 114. Liquids, Preliminary Examination of, 12. OENANTHYC Acid, 67, 68. Oenanthylic Acid-see Oenanthyc. MACE, 107, 109, 113. Oils, Fixefl, 13, 72. Magenta, 121. Volatile, 13, 104. Maisch's tests for Volatile Oils, 110. Oleic Acid, 13, 69. Marjoram Oil, 107, 109, 113. Oleo-resins, 93. Malic Acid, 13, 22. Olibanum (resin), 102. Mannite, 174. Olive Oil, 73, 76, 77, 80, 81. Mastic, 101, 103. Ononin, 145. Masticin, 101. Opiania, 126, 127, 129, 148. Mayer's tests with Volatile Alka- Opianyl-see 5Meconin. loids, 124. Opium, Separation of Meconic Acid Meconic Acid, 13, 24. from, 24, 25. Meconin, 145. Orange Flower Oil, 107, 109, 113. Metachloral, 183. Peel Oil, 107, 109, 110, 113, 114. Metapectic Acid, 167. Organic Compounds, determined as Metapectin, 167. such, 11, 12. Metatungstic Acid, as Reagent, 141. Origanum Oil, 107. Methylic Alcohol, 13, 174. Otto-Stas' Method with Alkaloids, Milk Albumen, 159. 130. 131. Commercial Examination of, 160. Ovalbumen, 158. Determination of Fats in, 84. Casein in, 159. PALMITIC Acid, 13, 70. Quantitative Analysis of, 160. Papaverina, 126, 127, 129, 135 to 138, Sugar-see Lactose. 141 to 145, 149, 150. Mirbane, Essence of-see Nitroben- Paracumaric Acid, formation of, 93. zole. Parapectic Acid, 166. Molybdate, as Reagent, 141. Parapectin, 166. Monophenylamin-see Anilin. Parmelia Parietina, Chrysophanic Morintannic Acid, 13, 28, 35.. Acid from, 41. Morphia, 126 to 128, 136 to 139, 141 to Parsley Oil, 107, 109, 113. 145, 147 to 150. Patchouli Oil, 110. Mustard Oils, 73. Paytina, 126, 129, 138. Myristic Acid, 13, 70. Pectic Acid, 166. Alcohol, 95. Pectin, 13, 166. Myrrh Oil, 107. Pectose, 166. Resin, 101, 103. Pectous Substances, 166. Separation of, from Gamboge,98. Pelargonic Acid, 67 68. Peppermint Oil, 167, 109, 11, 112, NARCEINA, 126 to 128, 133 to 138, 141 114, 115. to 150. Pepper Oil, 107, 114. Narcotina 126 to 128, 135 to 138, 140 Peru Balsam, 102, 103. to 145, 147 to 149. Petroleum Naphtha, 13, 119. Nicotia, 123, 124, 128, 135 to 138, Phenic Acid 48. 141 to 145, 148, 149. Phenol-see Phenic Acid. Nitric Acid, as Reagent for Alka- Phenylamin-see Anilin. loids 147. Phenylic Alcohol-see Phenic Acid. Nitrite of Amyl, 186. Phenyl Sulphuric Acid-seo SulphoEthyl, 180. phenic. Phloridzin, 145, 155, 156. Rosin Oil, 96. Phosphomolybdic Acid, as Reagen., Rue Oil, 108, 109, 111, 113. 139, 140. Physostigmia, 126, 129, 135, 136, 138, SABADILLIA, 126 129, 142, 148. 141 to 145, 148, 150. Sabadilla Seeds, Veratric Acid from, Picramic Acid, 52. 47. Picric Acid, as Reagent, 139. Saccharose-see Sucrose. See Nitrophenic Acid. Salicin, 126, 129, 136, 137, 138, 145. Picrotoxin, 126, 127, 129, 136 to 13S, Salicylic Acid, 13, 47. 146. Sandarac, 102, 104. Pimaric Acid-see Colopholic Acid. Sanguinarin, 142. Pimento Oil, 107. Santalic Acid, 13, 42. Pinic Acid, in Colophony, 96. Santalin-see Santalic Acid. Piperidir, 141. Santonin, 137. Piperin, 126, 129, 134, 136, 137, 138, Saponification, Means of, 75. 141 to 145, 147. Saponin, 126, 129, 138. Platinic Chloride, as Reagent for Sarcolactates, 54. Alkaloids, 148. Sarsaparillin, 146, 156. Podophyllum Resin, 102, 103. Sassafras Oil, 108, 109, 110. PopDy-seed Oil, 72, 77, 78, 80. Saturation, Fractional, 6(. Populin, 137, 145, 155 156. Savine Oil, 108, 109, 114. Potassio Mercuric iodide, as Re- Scammonin-see Jalapin. agent, 139. Scammony, 102. Cadmic Iodide, as Reagent, 141. Seal Oil, 80. Propylamin-see Trimethylamia. Secalin-see Trimethylamia. Pseudomorphia, 126, 127, 129, 138, Senagin, 146. 142, 145, 148. Senna Resin, Separation from GamPyrogallic Acid, 13, 32. boge, 98, 104. Pyrogalline-Pyrogallol-see Pyro- Separation of Acids, as Lead Salts, gallic Acid. 59. Pyroxyllon-see Nitrocellulose. Alkaloids from other matters, 130. each other, 156. QUASSIN, 155, 156. Glucosides, 156. Quercitannic Acid, 27, 28. Fixed Oils, 85. Quinia, 126, 129, 135 to 138, 140 to Non-volatile Fat Acids, 71. 142, 144, 145, 148, 149, 150. Resins, 103. Quinic Acid, 13, 36. Solids from Liquids, 12. Quinidia, 126, 129, 135, 136, 138, 140, Volatile Fat Acids, 66, 68. 141, 142, 145, 149, 151. Volatile Oils, 105. Quinone, Formation of, 37. Seralbumen, 158. Quinotannic Acid, 13, 28, 33. Sesame Oil, 73, 76, 80, 81. Quinovic Acid, 13, 38. Shell Lac, 101. Quinovin-see Quinovic Acid. Soaps, 13, 87. Solania, 126, 127, 129, 136, 138, 141 to RACEmIC Acid, 13, 18. 145, 147, 148, 151. Rape-seed Oil, 73, 76, 78, 80, 81. Solids, Preliminary Examination Resinified Oils, 105, 115. of 11. Resins, 13, 92. Solid Volatile Acids, 42. Determined in Soaps, 90. Non-volatile Acids, 14. Roeadia, 126, 129, 138. Soluble Starch, 164. Rhubarb, Chrysophanic Acid from, Smilacin, 146. 41. Spermaceti, 74. Ricinoleic Acid, 13, 69. Spearmint Oil, 108, 110. Rodgers and Girdwood's Method, Spirit of Nitrous Ether, 180. 130, 132. Starch, 13, 164. Rosanilin, 121. Starch Sugar-see Glucose. Rosemary Oil, 107, 109, 111, 113, 11 Stas and Otto's lMethod with Alka. Rose Oil, 107, 109, 111, 113, 114. loids, 130. Rosewood Oil, 107. Stearic Acid, 13, 70. 1 92s I-VI),X. Stearoptenes, 104. Toluidin, 120, 121. Storax Resin, 102. Tolu Resin, Separation from GamStrychnia, 126, 127, 129, 135, 137, 138, boge, 98. 140 to 144, 146, 151. Tragacanth, 162. Test, 146, 149. Trimethylamia, 123, 124. Styracin, 102, 103. Trinitrophenic Acid - see NitroSuccinic Acid, 45. phoenic. Sugars, 13, 168. Trommer's Sugar Test, 169. Sulphuric Acid, as Reagent, 144, 155, 156. USLAR and Erdmann's Method, 130, See, also, under Glucosides. 133. Sunflower Oil, 73, 77. Sweet Spirits of Nitre-see Spirits VALERIANIC Acid-see Valeric. Nitrous Ether. Valerian Oil, 108, 109, 111, 112, 115. Sylvic Acid, in Colophony, 96. Valeric Acid, 13, 60, 63. Syringin, 136, 16. Vanillin, 156. Veratria, 127, 129, 135 to 139, 140 to TALLOW, 74. 144, 146, 148, 151. in Butter, 82, 83. Veratric Acid, 13, 47. Tannic Acid, 13, 18, 146. Vogel's Lactoscope, 84. distinguished from Gallic, 31. Volatile Bases, 120, as Reagent, 139, 143. Fat Acids, 67. Tannic Acids, 26. Tanoxylic Acid, 27. WALL Lichen-see Parmelia p. Tansy Oil, 108, 109, 114. Walnut Oil, 72, 77. Taraxacin, 156. Wax, Bees', 74. Tartaric Acid, 13, 14. Whale Oil, 73, 78. Tea, Black, Separation of Boheic Wintergreen Oil, 108, 110. Acid from, 36. Wormseed Oil, 108 to 111, 114. Thebaina, 126, 127, 129, 135 to 138, Wormwood Oil, 108, 109, 111, 114. 142, 143, 146, 149, 151. Theobromina, 127, 129, 136 to 139, XILIDIN, 120. 141, 142, 146, 148, 149, 151. Thyme Oil, 108, 1, 114. YARROW Oil, 108. Tolu Balsam, 103. Ylang Ylang (Oil), 108, 114. SCIENTIFIC BOOKS PUBLISHED BY D.o VWAN' iSOSTANDT, 23 AURRAY STREET & 27 WARREN STREET, NEW YORK. iWeisbach's Mechanics. New an-d Revised Ed ition. 8vo. Cloth. $10.00. A IANUAL OF THE MECHANICS OF ENGINEERING, ancl of the Construction of Mfachines. ByS JULIrUS WVEISBACI, PI. ]D. Translated from the fourtl augmented and improved German edition, by ECKLEY B. Coxe, A.M., Mining Engineer. Vol. I.-Theoretical Mechanics. l,100 pages, and, 902 wood-cut illustrations. ABSTRACT OF CONTENTS.-Introcluction to the Calculus-The General Principles of [Mechanics-Phoronomics, or the Purely Mathematical Theory of Motion-M-echanics, or the General Physical Theory of Motion-Statics of Rigid Bodies-The Application of Statics to Elasticity and Strength-Dynamics of Rigid Bodies-Statics of Fluids-Dynamics of Fluids-The Theory of Oscillation, etc. "The present edition is an entirely new work, greatly extended and very much improved. It forms a text-book which maust find its way into the hands, fiot only of every student, but of every engineer who desires to refresh his memory or acquire clear ideas onil doubtful points." —Manufacturer and Builder. "We hope the dlay is not far distant when a thorough course of study and education as such shall be demanded of the practising engineer, and with this view we are glad to welcome this translation to our tongue and shores of one of thp'.l most able o(f the cdor-catr"os of EuorolS',.7chne iegst. 2 A(;2NlVXTIFrI 3P0 0K1 Ai7'iBTiSIED BYl Francis' Lowell Hydraulics. hThr4 E dition. 4lto. Cloth. 15.00. LOWELL IHYDRAULIC E]XPERIaMENTS — being a Selection frolm Experinzents on Hydraulic Miotors, on the Flow of Water over AWeirs, and in Open Canals of Uniform RIectangular Section, made at Lowell, MB5ass. ]By J. B. FmANcis, Civil Engineer. Third edition, revised and enlarged, including many New Experinlents on Gauging WVater in Open Canals, and on the Flow through Submerged Orifices and Diverging Tubes. IWith 23 copperplates, beautifully engraved, and about 100 new pages of text. The work is divided into parts. PART I., on hydraulic motors, includes ninety-two experiments on an improved Fiourneyron Turbine Water-Wheel, of about two hundred horse-power, with rules and tables for the construction of similar motors; thirteen experiments on a model of a centre-vent waterwheel of the most simple design, and thirty-nine experiments on a centre-vent water-wheel of about two hundred and thirty horse-power. PART II. includes seventy-four experiments made for the purpose of determining the form of the formula for computing the fow of water over weirs; nine experiments on the effect of back-water on the flow over weirs; eightyeight experiments made for the purpose of determining the formula for computing the flow over weirs of regular or standard forms, with several tables of comparisons of the new formula with the results obtained by former experimenters; five experiments on the flow over a dam in which the crest was of the same form as that built by the Essex Company across the Merrimack River at Lawrence, lMassachusetts; twenty-one experiments oll the effect of observing the depths of water on a weir at different distances rfom the weir; an extensive series of experiments made for the purposo of determining rules for gauging streams of water in open canals, with tables for facilitating the same; and one hundred and one experiments on the discharge of water through submerged orifices and diverging tubes, the whole being fully illustrated by twenty-three double plates engraved on copper. In 1855 the proprietors of the Locks and Canals on Merrimack River consented to the publication of tlie first edition of this work, which contained a selection of the most important hydraulic experiments made at Lowell up to that time. In this edition the principal hydraulic experiments made there, subsequent to 1855, have besn added, including the important series above mentioned, for determining rules for the gauging the flow of water in open analls, and the interesting series on the flo-w through a's-ibmuerged V7enturi's tubec in wlhich a larger flow was oebtair.cd thall ainy wo find recorded. 9... NO'Z -.A I.. Francis Oil Cast-Iron..... 3vo. Cloth. $2.00. ON THE STRENGTHI OF CAST-IRON PILLARS, wit-h Tables for thle use of Engineers, Architects, and DBuilders. [By Ja.Sis B. Fin-NcIs, Civil Engineer. xiSerril's Iron Truss Bridges. S~coi~tZ E(lttifon 4to. Cloth. $5.00. IRON TRUSS BRIDGES FO R RAILROADS. The iMethod of Calculating Strains in Trusses, with a careful comparison of the most prominent Trusses, in reference to economy il combination, etc., etc. By Brevet Coionel WVILLIA: ]E. E- RI:LL, U.S.A., %Major Corps of Engineers. Nine lithe1ographed plates of illustrations. "The work before us is an attempt to give a basis for sound reform in this feature of railroad engineering, by throwing'additional light upon the nlethod of calculating the maxima strains that can come upon any part of a bridge truss, and upon the manner of proportioning each part, so that it shall be as strong' relatively to its own strains as any other part, and so that the entire bridge may be strong enough to sustain several times as great strains as the greatest that can come upon it in actual use.' " —cien'ific American. "' The anthor has presented his views in a clear and intelligent manner, and the ingenuity displayed in coloring the figures so as to present certain facts to the eye faorms no inappreciable part of the merits of the work. The reduction of the'formulh for obtaining the strength, volume, and weight of a castiron pillar under a strain of compression,' will be very acceptable to those who have occasion hereafter to make investigations involving these conditions. As a whole, the work has been well done."-Railroad Gazelte, Cficaygo.:lumibers Strains in Girders. 18ISo. Cloth. $2.50. A HA DY BOOK FOR THE CIALCOULATION OF STRAIkNS IN GIRDERS and Similar Structures, and their Strength, consisting of Formuhl and Corresponding Diagrams, with niuLrerous details for practical application. [By ~WILLI.a.IuB.Rn, Fully illustrated. 4 S 3CIE,1 L'-IC B 0 OZh5' P U-JLESIiZJD B Y Shreve on Bridges and Roofs. Svo, 87 wood-cut illustrations. Cloth. $5.00. A TIREk.TISE ON THE STRENGTH OF BRIDG-ES AN-D ROOFS —comprising the determination of Algebraic formulas for Strains in Horizontal, Inclined or Rafter, Triangular,:Bow-'string, Lenticular and other Trusses, from fixed and moving loads, with practical applications and examples, for the use of Students and LEngineers. By SxaruEL I. SREvE, A.-Mi., Civil Engineer. "On the whlole, Mir. Shreve has produced a book which is tlhe simplest, clearest, and at the same tihnme, the most systernatic and -with the best 1mathematical reasoning of any wxvork Lpon the samle subject in the language."S_1airocad (Gazette. " From the unusually clear language in whlich iMr. Shreve has given every statemlent, the' student will have but hiniself to blanme if lhe does not become, tllorough- master of the subject."-fLomndob Minbig JoTrnal.c " lIr. Shreve has produced a work that nmust always take ]lidlh rank as a text-book, * and no Bridge Engineer sllould be without it, as a valuable work of reference, and one that will frequently assist him out of difficulties. " — Fraklrn Inst'itato Jjounal. The K ansas City Bridge. 4to. Cloth. $6.03 WaITH AN ACOOTJNT OF THE RIEGIfEN OF THE M] ISSOURBI RIVER, aid a description of the }Methods used for [Founding in that River. 3By 0. CIANNUTE, Chief Engineer, and GEonGE MORISONx, Assistant Engineer. Illustrated with five iEthographic views and tmwelve plates of plans. Illustrctions. VIEWS.-View of the Kansas City tion Works, Pier No. 3. IV. Founda[Bridge, A-ugust 2, 1869. Lowering tion Works, Pier No. 4. V. FoundaCaisson No. 1 into position. Caisson tion'Works, Pier No. 4. VI. Caisson for Pier No. 4 brought into position. No. 5-Sheet Piling at Pier No. 6View of Foundation ]Works, Pier No. Details of Dredges-Pile Shoe —Beton 4. Pior No. 1. Box. VIT. Masonry-Draw ProtecPLATES.-I. M'tap showing location tion-False Works between Piers 3 of Bridge. II. Water Record-Cross ancl 4. VIII. Floating Derricks. Section of River-Profile of Crossing; IX. General Elevation-176 feet span. — Pontooni Protection. III. WTater IX. 248 feet span. XI. Plans of Draw. Deadener —Cisson No. 2 —Founda X II. Strain Diagramrs. P1. VAX 1JY08STBANYD. 5 Clarke's Qiilny Bridge. 4to. Cloth. $7.50. DESCRIPTION OF THE IRON RiAILWTAY Bridge across the Mississippi River at Quincy, Illinois. By THUoBAS CURTIS CL.ARE, Chief Engineer. Illustrated with twenty-one lithographed plans. iflustrcio es. PLATES.-General Plan of i1issis- Curve of Deflections. X. [Foundasippi River at Quincy, showing loca- tions of Pier 2, in Process of Contion of Bridge. IHa. General Sections struction. XI. Foundations of Pier of Mississippi River at Quincy, show- 3, and its Protection. XII. Foundaing location of Bridge. ISb. General tions of Pier 3, in Process of ConstrucSections of 1VMississippi River a- Quin- tion, and Steam Dredge. XIII. Founey, showing location of Bridge. III. dations of Piers 5 to 18, in Process General Sections of Mississippi River of Construction. XIV. False Works, at Quincy, showing location of Bridge. showino Process of Handling and SetIV. Plans of liasonry. V. Diagram ting Stone. XV. False Works for of Spans, showing the Dimensions, Raising Iron Work of Superstructure. Arrangement of Panels, etc. TI. Two XVI. Steam Dredge used in Founcahundred and fifty feet span, and de- tions 9 to 18. XVII. Single Bucket tails. VII. Three hundred and sixty Dredgo used in Foundations of Bay feet Pivot DLraw. VIII. Details of Piers. XVIII. Saws used for Cutthree hundred and sixty feet Draw. ting Piles undcer water. XIX. Sand IX. Ice-Breakers, Foundations of Piers Pump and Concrete Box. XX. MIaand Abutments, Water Table, and sonry Travelling Crane.! Whipple on Bridgoe Euiding Svo, Illustrated. Cloth. $4.00. AIT ELEM]ENTARY AND PRACTICAL TREATISE ON BRIDGE BUiLDI)NG. An enlarged and improved edition of the Author's original work. By S. ATvIPPLE, C. E., Inventor of the Wahipple Bridges, &c. Second Edition. lhe design has been to develop from Fundamental Principles a system easy of comprehension, and such as to enable the attentive reader and student to judge understandingly for himself, as to the relative merits of different plans and combinations, and to adopt for use such as may be most suitable for the cases he may have to deal with. It is hoped the work may prove an appropriate Text-Book upon the subject treated of, for the Elngineering Student, and a useful manual lor the Practicing Engineer and Bridge Builder. 6,SCIEVTII;'IC B OOKS PU29 BLJ;'-fIED B Stoney on Srains. New antc 2Bevaised Edition, with tnumerous illuestrations. Royal 8vo, 664 pp. Cloth. $12.50. THE THEORY OF STRAINS IN GIRDERS and Similar Structures, with Observations on the Application of Theory to Practice, and Tables of Strengthl and other Properties of Materials. By BBINoN B. STONEY, B. A. Roebling's Bridges. Im-perial folio. Cloth. $25.00. LONG AND SHORT SPAN RAILWAY BRIDGES. By JoHx A. ROEBLING, C. E. Illustrated with large copperplate engravings of plans and views. List of Pllates i. Parabolic Truss Railway Bridge. 2, 3, 4, 5, 6. Details of Parabolic Truss, with centre span 500 feet in the clear. 7. Plan and View of a Bridge over the Mississippi River, at St. Louis, for railway and common travel. 8, 9,.10, 11, 12. Details and View of St. Louis Bridge. 13. Railroad Bridge over tihe Ohio. jiedrichs' Theory of Strains. 8vo. Cloth. $5.00. A Compendium for the Calculation and Construction of Bridges, Roofs, and Cranes, with the Application of Trigonometrical Notes. Containing the most comprehensive information in regard to the Resulting Strains for a permanent Load, as also for a combined (Permanent and Rolling) Load. In two sections adapted to the requirements of the present time. [By JouN DIEDRncIIs. Illustrated by numerous plates and diagrams. " The -want of a compact, universal and popular treatise on the Construction of Roofs and Bridges-especially one treating of the influence of a variable load-and the unsatisfactory essays of different authors on the subject, induced me to prepare this work." J). YVJIA- A70OST'_IAND. 7 WVhilden's Strength of Materials1 12mRo. Cloth. $2.00. ON THE STRtENGTH OF MATERIIALS used in Engineering Construction. B3 J. K.. XTHILDEN. Campin on Iron Roofs. Large 8vo. Cloth. 82.00. ON THE CONSTRUCTION OF IRON ROOFS. A Theoretical and1 Practical Treatise. B]y F cics CxnpIu. sWith wood-cuts and plates of Roofs lately executed. 6The mathemnatical formulas are of an elementary kind, and the process admits of an easy extension so as to embrace the prominent varieties of iron truss bridges. The treatise, though of a practical scientific character, may be easily mastered by anlly one familiar with elementary mnechanics and plane t'i"gonometry." tolie s Ra lwaEy Practice. 1 vol. folio. Cloth. $12.00. AMERICAN AND EUROPEAN BAILVAPTY PRACTICE, in the Economical Generation of Steam, including the materials and construction of Coal-burning, Boilers, Combustion, the Variable Blast, Vaporization, Circulation, Super-heating, Supplying and IHeating Feed-water, &c., and the adaptation of Wood andl Coke-burning Engines to Coal-burning; and in Permanent AVay, including Road-bed, Sleepers, Rails, Joint Fastenings, Street Railways, &c., &c. By ALEXAANDE L. HoLLE, B. P. With 77 lithographed plates. "11This is an elaborate treatise by one of our ablest civil engineers, on the construction and use of locomotives, with a few chapters on the building of IaLilroads. * *:' All these subjects are treated by the author, who is; first-class railroad engineer, in both an intelligent and intelligible manner. Tho facts and ideas are well arranged, and presented in a clear and simple sSyle, accompanied by beautiful engravings, and we presume the work will be regardcL ed as indispensable by all who are interested in a knowledge of the construction of railroads ancd rolling stock, or the working of locomotives." —ScfentfsI Aezerican, 8 SC I8JVX`TFI. C B 0 0K)HS P BUBLJ8IIE-D B Y Henrici9s Skeleton Structureso Svo. Cloth. $1.50. SKELETON STRtUCTURES, especially in their Application to the. building of Steel and Iron Bridges. By OLAUJS HENRCI. WVith folding plates and diagrams. By presenting these general examinations on Skeleton Structures, -with particular application for Suspended Bridges, to Engineers, I venture to express the hope that they will receive these theoretical results with some confidence, even although an opportunity is wanting to compare them with practical results. 0. If. Useful Information for Railway Men. Pocket form. Morocco, gilt, $2.00. Compiled by W. G. HImnILTOIT, Engineer. Fifth edition, revised and enlarged. 570 pages.' It embodies many valuable formulse and recipes useful for railway men, and, indeed, for almost every class of persons in the world. The'information' comprises some valuable formule and rules for the construction of boilers and engines, masonry, properties of steel and iron, and the strength of materials generally." —Rauilroad Gczette, CAicago. Brooklyn lWater WVorks. 1 vol. folio. Cloth. $25.00. A DESCRIPTIVE ACCOUNT OF THE CONSTRUCTION OF THE WORKS, and also Reports on the Brooklyn, Hartford, Belleville, and Cambridge Pumping Engines. Prepared anld printed by order of the Board of AWater Commissioners. WVith 59 illustrations. CONTENTs.-Supply Ponds-The Conduit -Ridgewood Engine House and Pump WVell-R-idgewood Engines —Force AMains-Rtidgewoocd ReservoirPipe Distribution-Mount Prospect Rcservoir-M-iount Prospect Engine House and Engine —Drainage Grounds-Sewerage Works —Appendix. Kirkwood on Filtration. 4to. Cloth. $15.00. iEPORT 0OT THE FILTRATION OF RIVE S WATERS, for the Supply of Cities, as practised in ]Europe, made to the Board of WTater Commissioners of the City of St. Louis. By JA.As 1'. KIRiwoo D. Illustrated by 30 double-plate engravings. CoNTENTS.-Report on Filtration-London Aorks, General-Chelsea WrVater Works and Filters-La-mbeth AWater WV'orks and Filters-Southwark and Vauxhall Water W'Torks and Filters-Grand Junction Water Works and Filters-West MIfiddlesex WJater W7forks and Filters-New River Water ~Works and Filters-East London Wyater Works and Filters-Leicester Wtater VWMorks and Filters-York Water WVorks and Filters-Liverpool Water Works and Filters-Edinburgh Water W(orks and Filters-D)ublin Water WTorks and Filters-Perth Water W~orks and Filtering Gallery —Berlin WTater W?~orks and Filters —Iamburg Water W[Torks and Reservoirs-Altona VWater Works and Filters-Tours Water Waorks and lFiltering Canal-Angers Water WV;orks and Filtering GOalleries-Nantes WTater Works and Filters-Lyons Water.W[orks and Filtering Galleries-Toulouse Water ~Works and Filtering Galleries-M;iarseilles *Water Works and Filters-Genoa WVater Wrorks and Filtering Galleries-Leghorn ~Water Works and Cisterns-Wakefield Water 7Works and Filters-Appendix. Tunner on Roll-Turning. 1 vol. 8vo. and 1 vol. plates. $10.00. A TREATISE ON ROLL-TURNING FOR TI:E 3IANUFAC. TURE OF IRON. By PETrnr TUNMER. Translated and adapted. By JoiiN ]B. PEanSE, of the Pennsylvania Steel Works. %With numerous wNool-cuts, Svo., together with a folio atlas of 10 lithographed plates of Rtolls, ]Measurements, &c. " We commend this book as a clear, elaborate, and practical treatise upon the department of iron manufacturing operations to which it is devoted. The writer states in his preface, that for twenty-five years he has felt the necessity of such a work, and has evidently brought to its preparation the fruits of experience, a painstaking regard for accuracy of statement, and a desire to furnish information in a style readily understood. The book should be in the hands of every one interested, either in the general practice of mechanical engineering', or the special branch of manutacturing operations to which the work relates."'-Ame ricc?3 Artiscan. 10 &C J1j\72:'7LijiC B 00.A%'$ OKS'.P B;ISIIE9~. _B Y' G yntn on the Power of eater. 12mo. Cloth. $1.00. A TREATISE ON THE PO~VWER OF WVATER, as applied to drive Flour Mills, and to give motion to Turbines and other Hydrostatic Engines. By JOSnEP GLYNN, F.R. S. Third edition, revised and enlarged, with numerous illustrations. eewson on Embankmnents. 8vo. Cloth. $2.00. PRiINCIPLES AND PRACTICE OF EM2iBAN:KING LANDS from River Floods, as applied to the Levees of the Mississippi. By WILLIA. IHEWSON, Civil Engineer. " This is a valuable treatise on the principles and practice of embanking lands from river floods, as applied to the Levees of the Mississippi, by a highly intelligent and experienced engineer. The author says it is a first attempt to reduce to order and to rule the design, execution, and measurement of the Levees of the Mississippi. It is a most useful and needed contribution to scientific literature.-Pl;aciaelp?&,ia EEvening Jocas. Griiner on Steel. 8vo. Cloth. $3.50. THE MANUFACTURE OF STEEL. By MI. L. GRUNER, translatecl from the French. By Lenox Smith, A. WM., E. M., with an appendix on the Bessemer Process in the United States, by the translator. Illus trated by lithographed drawings and woodl-cuts. "The purpose of the work is to present a careful, elaborate, and at the same time practical examination into the physical properties of steel, as well as a description of the new processes and mechanical appliances for its manufacture. The information which it contains, gathered from many trustworthy sources, will be found of much value to the American steel manufacturer, who may thus acquaint himself with the results of careful and elaborate experiments in other countries, and better prepare himself for successful competition in this important industry with foreign makers. The fact that this volume is from the pen of one of the ablest metallurgists of the present day, oannot fail, we think, to secure for it a favorable consideration.-Iror Age. BauermZan on. Iron 123mo. Cloth. $2.00. TtREATISE, ON THE -METALLURGY OF IRON. Containing outlines of the History of Iron lIManufacture, methods of Assay, and analysis of Iron Ores, processes of muanufacture of Iron and Steel, etc., etc. By II. PUEirMAN. First American edition. Revised and enlarged, with an appendix on the Martin Process for making Steel, from the report of Abram S. Hewitt. Illustrated with numerous wood engravings. "This is an important addition to the stock of technical works published in this country. It embodies the latest facts, discoveries, and processes connectedl with the manufacture of iron and steel, and should be in the hands of every person interested in the subject, as well as in all technical and scientific libraries."-Scientific Americanz. Link and Valve Motions, by NV. S. Auchincloss. 8vo. Cloth. $3.00. APPLICATION OF THE SLIDE VALVE and Link lbotion to Stationary, Portable, Locomotive anctd Marine Engines, with new andc simple methods for proportioning the parts. By WILLIair S. AuCHINCLOSS, Civil and Miechanical Engineer. Designed as a hand-book for M1echanical Engineers, Mlaster Msechanics, Draughtsmen and Students of Steam Engineering. All dimensions of the valve are found with the greatest ease by means of a Printed Scale, and proportions of the link cleterminedl -without the assistance of a model. Illustrated by 37 wood-cuts and 21 lithographic plates, together with a copperplate engraving of thel Travel Scale. All the matters we have mentioned are treated with a clearness and absence of unnecessary verbiage which renders the work a peculiarly valuable one. The Travel Scale only requires to be known to be appreciated. Mr. A. writes so ably on his subject, we wish he had written more. London EnZ gineering. We have never opened a work relating to steam which seemed to us better calculated to give an intelligent mind a clear undcrstanding of the depart, ment it discusses.-Scientzifc American. 12 SCIENT'IFIC 30 0KS PUTBLISI'ED -BY Slide Valve by Eccentrics, by Prof. C, TV. MacCordo 4to. Illustrated. Cloth, $4.00. A PRACTICAL TREATISE ON THIE SLIDE VALVE BY ECCENTRICS, examining by methods, the action of the Eccentric upon the Slide Valve, and explaining the practical processes of laying out the movements, adapting the valve for its various duties in the steam-engine. For the use of Engineers, Draughtsmen, Machinists, and Students of valve motions in general. By C. WV. lMACCORD, A. M., Professor of AMechanical Drawing, Stevens' Institute of Technology, IHoboken, NY J. Stillman's Steam-Engine Indicator. l2mo. Cloth. $1.00. THE STEAM-ENGINE INDICATOIR, and the Improved Manometer Steam and Vacuum Gauges; their utility and application By PAUL STILLMAN. New edition. Bacon's Steam-Engine Indicator. 12mo. Cloth. $1.00. Mor. $1.50. A TlREATISE ON THE RICHARDS STEAM-ENGINE INDICATOR, with directions for its use. By CHARLES T. PORTER. Revised, with notes and large additions as developed by American Practice, with an Appendix containing useful formulse and rules for Engineers. By F. W. BAcoN, Mf. E.,* Member of tho American Society of Civil Engineers. Illustrated. Second Edition In this work, Mr. Porter's book has been taken as the basis, but IMvr. Bacon has adapted it to American Practice, and has conferred a great boon on American Engineers. —Artisan. Bartol on Marine Boilers. 8vo. Cloth. $1.50. TREATiSE ON THE MARINE BOILERS OF THE UNITED STATES. By II. B. BARTOL. Illustrated. J). VAV7 XNOSTRAND. 13 Gillmore's Limes and Cements.:Fourtlh Edizton. Revisedt and Enlacrgd. 8vo. Cloth. $4.00. PRACTICAL TREATISE ON LIMiES, HYDRAULIC CEMIENTS, AND MIORTARS. Papers on Practical Engineering, U. S. Engineer Department, No. 9, containing Reports of numerous experiments conducted in Newr York City, during the years 1858 to 1861, inclusive. 13y Q. A. GILLMORE, Brig-General U. S. Volunteers, and Major TU. S. Corps of Engineers. Wir.L numerous illustrations. " This work contains a record of certain experiments and researches made under the authority of the Engineer Bureau of the War Department from 1858 to 1861, upon the various hydraulic cements of the United States, and the materials for their manufacture. The experiments were carefully made, and are well reported and compiled.' —Jouzrnal Frankili Institute. Gillmore's Coignet Beton. 8vo. Cloth. $2.50. COIGNET B1ETON AND OTHER ARTIFICIAL STONE. By Q. A. GILLAORE. 9 Plates, Views, etc. This work describes with considerable minuteness of detail the several kinds of artificial stone in most general use in Europe and now beginning to be introduced in the United States, discusses their properties, relative merits, and cost, and describes the materials of which they are composed. The subject is one of special and growing interest, and we commend the work, embodying as it does the matured opinions of an experienced engineer and expert, Williamson's Practical Tables. 4to. Flexible Cloth. $2.50. PRACTICAL TABLES IN METEOROLOGY AND HYPSOMETRY, in connection with the use of the Barometer. By Col. R. S, WILIIAMso,-, U. S. A. 14 /,J (1'5_, _ f3 00JC/I'.J- O, 7U.) XJ';JSiL B) Y'" Williatsoan on the Barometer. 4to. Clotllh. $15.00. ON THIE USE OF THE B3ARWOIETER ON SURVTEYS AND RECONNAISSANCES. Part I. nMeteorology in its Connection with ilypsometry. Part II. Barometric Ilypsometry. 13y R. S. WILLIAaLSON, BVt. Lieut.-Col. U. S. A., Maijor Corps of Engineers. W~ith Illustrative Tables and Engravings. lPapcr No. 15, Professional Papers, Corps of Engineers. " SAN FRANCISCO, CAL., Feb. 27, 1867. " Gen. A. A. I IuMPHREYS, Chief of Engineers, U. S. Army: "GENEmAL,-I have the honor to submit to you, in the following pages, the results of my investigations in iaeteorology and hypsometry, made with the view of ascertaining how far the barometer can be used as a reliable instrument for determining altitudes on extended lines of survey and reconnaissances. These investigations have occupied the leisure permitted me from my professional duties during the last ten years, and I hope the results will be deemed of sufficient value to have a place assigned the assigned them among the printed professional papers of the UInited States Corps of Engineers. " Very respectfully, your obedient servant, "R. SS. WILLIAMSON, " Bvt. Lt.-Col. U. S. A., Major Corps of U. S. Engineers." Von Ootta's Ore Deposits. Ovo. Cloth. $4.00. TREATISE ON ORE DEPOSITS. By B3ERNHARD VON COTTA, Professor of Geology in the Royal School of Miines, Freidberg, Saxony. Translated from the second German edition, by Fr7EDERICK PRIE, Jr., Mining Engineer, and revised by the author, with numerous illustrations. " Prof. Von Cotta of the 1Freiberg School of Mines, is the author of the best modern treatise on ore deposits, and we are heartily glad that this admirable work has been translated and published ill this country. The translator, Mlr. Frederick Prime, Jr., a graduate of Freiberg, has had in his work the great advantage of a revision by the author himself, who declares in a prefatory note that this may be considered as a new edition (the third) of his own book. "It is a timely and welcome contribution to the literature of mining in this country, and we are grateful to the translator for his enterprise and good judgment in undertaking its preparation; while we recognize with equal cordiality the liberality of the author in granting both permission and assistance."-ith;tractf ron? Rev.iewo i,, Engzineering/ aad 1W1ni:in JoZu'ralC. Plattner's Blow-Pipe Analysis. Second edition.:Revised. Svo. Cloth. $7.50. PLAr1TNER'S MANUAL OF QUALITATIVE AND QUANqT TITATIVE ANALYSIS W~ITHI TIHE BLOW-PIPE. From the last German edition Revised and enlarged. By Prof. Tn. RICiTER, of the Royal Saxon Mining Academy. Translated by Prof. II. B. CORNwALL, Assistant in the Columbia School of Mines, New York; assisted by JOHIN H. CASWELL. Illustrated with eighty-seven,wood-cuts and one Lithographic Plate. 560 pages. "Plattner's celebrated -work has long been recognized as the only complete book on Blow-Pipe Analysis. The fourth German edition, edited by Prof. hichnter, fully sustains the reputation which the earlier editions acquired during the lifetime of the author, and it is a source of great satisfaction to us to know that Prof. Richter has co-operated with the translator in issuing the American edition of the work, which is in fact a fifth edition of the original work, being far more complete than tho last German edition."-Sillimacn's Journal. There is nothing so complete to be found inl the ]English language. Plattner's book is not a mere pocket edition; it is intended as a comprehensive guide to all that is at present known on the blow-pipe, and as such is really indispensable to teachers and advanced pupils. " Mr. Cornwall's edition is somethling more than a translation, as it contains many corrections, emendations and additions not to be found in the original. It is a decided improvement on the work in its German dress."-Journal of Applied Ceizmistry. Egleston's Mineralogy. 8vo. Illustrated with 34 Lithographic Plates. Cloth. &450. LECTURES ON DESCRIPTIVE MIINERALOGY, Delivere'd at the School of Mlines, Columbia College. BY PorFEsson T. EGLESTON. These lectures are what their title indicates, the lectures on Mineralogy delivered at the School of Mines of Columbia College. They have been printed for the students, in order that more time might be given to the various methods of examining and determining minerals. The second part has only been printed. The first part, comprising crystallography and physical mineralogy, will be printed at some future time. Pylnchon's Chez, nical Physics. New E~ition. Bevisetl ad~ E." Wred. Crowln 8vo. Cloth. Y3.00o INTRTODUOCTION TO CHEM3!ICAL PHYSICS, Designed for the TJse of Academies, Colleges, and High Schools. Illustrated withi LnulmerLous engravings, andl containing copious experiments with directions for preparing tlhem. By TroMris RcUGGLEs PYNCHON, M1v.A., Professor of Chemistry andl the Natural Sciences, Trinity Coilege, Hi-artford. Hitherto, no wrork suitable for general use, treating of all these subjects within the limits of a single volume, couldl be found; consequently the attention they have received ias not been at all proportionate to their importance. It is believed that a book containing so much valuable information within so small a compass, cannot fail to meet with a ready sale among all intelligent persons, while Professional men, Physicians, Medical Students, Photographers, Telegraphers, Engineers, and Artisans generally, will find it specially'valuable, if not nearly indispensable, as a book of reference. "W,7e strongly recommend this able treatise to our readers as the first work ever published on the subject free from perplexing technicalities. In style it is pure, in description graphic, and its typographical appearance i-; artistic. It is altogether a most excellent work."-E-lsctio 3fedical Journa7l. "It treats fully of Photography, Telegraphy, Steam Engines, and the various applicatibns of Electricity. In short, it is a carefully prepared volume, abreast with the latest scientific discoveries and iaventions." —aritford Uourvant. Piymn.pton's Bloxw-Pipe Analysis. 12mo. Cloth. $1 50. TIHE BLOW-PIPE: A Guide to Its Use in the Determination of Salts and Minerals. Compiled from various sources, )by GEORGE W. PLYMIPTON, C.E., A.M., Professor of Physical Science in the Polytechnic Institute, Brooklyn, N. Y. "This manual probably has no superior in the English language as a textbook for beginners, or as a guide to the student working without a teacher. To the latter many illustrations of the utensils and apparatus required in using the blow-pipe, as well as the fully illustrated description of the blowpipe flame, will be especially serviceable.' —~New Yorl Teeacche,. D. VAN XoSTRAND. 17 lUre's Dictionary. Sixth Edition. London, 1872. 3 vols. 8vo. Cloth, $25.00. Half Russia, $o2.50. DICTIONARY OF ARTS, IANUFACTURES, AND MINES. By ANDREmv TUI, MI.D. Sixth edition. Edited by ROBEPnT IUNT, F.R.S., greatly enlarged cand rewritten. Brande and Cox's Dictionary. New Edition. London, 1872. 8 vols. 8vo. Cloth, $20.00. Half Morocco, $27.50. A Dictionary of Science, Literature, and Art. Edited by W. T. B3RANDE and Rev. Gseo. AWV. Cox. New and enlarged edition.'Watt's Dictionary of Chemistry. Suappenenmgtary Folume. 8vo. Cloth. $9.00. This volume brings the Record of Chemical Discovery down to the end of the year 1869, including also several additions to, and corrections of, former results which have appeared in 1870 and 1871.: ** Complete Sets of the WITork, New and Revised edition, including above lsupplement. 6 vols. Svo. Cloth. $62.00. Rammelsberg's Chemical Analysis. Svo. Cloth. $2.25. GUIDE TO A COU1RSE OF QUANTITATIVE CHEMICAL ANALYSIS, ESPECIALLY OF MINERALS AND FU'RNACE PRODUCTS. IllhUst'ated by Examples. B]y C. IF. IMIMELBSDEnRG. Translated by J? TOWLEn, M.D. This work has been translated, and is now published expressly for thloso students in chemistry w-hose timne and other studies in colleges do not permait them to enter upon the snore elaborate and expensive treatises of Fresenils and others. It is the condensed labor of, a -master in chemistry and of a pracical analyst. 18 S',7CIEATl7ICIS6,B 0 S PUBLISEYED B Y Eliot and Storer's Qualitative Chemical Analysis. Nerw E cition, Revisecd. 12mo. Illustrated. Cloth. $1.50. A COMPENDIOUS }MANUAL OF QUALITATIVE CHEAMaICAL ANALYSIS. By CuARnLES WV. ELIOT and F.isn IE. STrolr. Revised witlh the Co6peration of tho Authors, by WVILLIAUiI RIPLEY NTICHOLS, Pl'ofessor of Cllemistry in the Mtassachusetts Instiiute of Technology. "This Mianual has great merits as a practical introduction to the science and the art of which it treats. It contains enough of the theory and practice of qualitative analysis, " in the wet way," to bring out all the reasoning involved in the science, and to present clearly to the student the most approved methods of the art. It is specially adapted for exercises and experiments in the laboratory; and yet its classifications and muanner of treat;ment are so systematic and logical throughout, as to adapt it in a high degree to that higher class of students generally who desire an accurate knowledge of the practical methods of arriving at scientific facts."-LSLtf7lern Oa5serve7'. " We wish every academical class in the land could have the benefit of the fifty exercises of two hours each necessary to master this book. Chemistry would cease to be a mere matter of memory, and become a pleasant experimental and intellectual recreation. ATe heartily commend this little volume to the notice of those teachers who believe in usingr the sciences as means of mental discipline."-College Cozra'dt. Craig's Decimal System. Square 32mo. Limp. 5Oc. WEIGHTS AND MiEASURES. An Account of the Decimal System, with Tables of Conversion for Commercial and Scientific Uses. By B. F. CRAIG, il. D. "The most lucid, accurate, and useful of all the hand-books on this subject that we have yet seen. It gives forty-seven tables of comparison between the [English and French denomninations of length, area, capacity, weight, and tho Centigrade and Fahrenheit thermometers, with clear instructions how to use them; and to this practical portion, which helps to make the transition as easy as possible, is prefixed a scientific explanation of the errors in the metric system, and how they may be corrected in the laboratory."-N'dtM2o0. XD. ATN NVOSTR`?AND. 19 N-ugent on Optics. l2mo. Cloth. $2.00 TREATISE ON OPTICS; or, Light and Sight, theoretically and practically treated; iith the application to Fine Art and Industrial Pursuits. By E. NUGENT. With one hundred and three illustrations. 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It is the best summary of the arguments in favor of the metric weights and measures with which we are acquainted, not only because it contains in small space the leading facts of the case, but because it puts the advocacy or that system on the only tenable grounds, namely, the great convenience of a decimal notation of weight and measure as well as money, the value of international uniformity in the matter, and the fact that this metric system is adopted an& in general use by the majority of civilized nations."- The zaitafobi. The Young MIeohanio. Illustrated. 12mo. Cloth. $1.75. THE YOTUNG. MECHANIC. Contaniing directions for the use of all kinds of tools, and for the construction of steam engines and mechanical models, including the Art of Turning in WVood and Metal. By the author of "The lathe and its Uses," etc. From the English edition, with corrections. 20 SCEIia-, TFIPIC BOOK)S PU1B.LISHi ED'BY Hlarrison s Mechanic's Tool-Book. 12mo. Cloth. $1.jO. MEC}HANIC'S TOOL BOOK, with practical rules and suggestions, for the use of Miachinists, Iron Waorkers, and others. By WV. B. HA-RRIsoN, Associate Editor of the "' American Artisan." Illustrated with 44 engravings. "This work is specially adapted to meet the wants of MIachinists and workers in iron generally. It is made up of the work-day experience of an intelligent and ingenious mechanic, who had the faculty of adapting tools to various purposes. The practicability of his plans and suggestions are made apparent even to the unpractised eye by a series of well-executed wood engravings."Philadelnphicb Inquirer. Pope's -Miodern Practie0 of the Eiectrio Telegraph. Eighth Edition. 8vo. Cloth $2.03. A Hand-book for Electricia-ns and Operators. By FiANK L. POPE. Seventh edition. IReTised and enlarged, and fully illustrated. Etract from Letter of Prof. Tforse. "I have had time only cursorily to examine its contents, but this examination has resulted in great gratification, especially at the fairness and unprejudiced tone of your whole work. " Your illustrated diagrams are admirable and beautifully executed. "I think all your instructions in the use of the telegraph apparatus judicious and correct, and I most cordially wish you success." Ext'ract from Letter of Prof. G. JT.lough, of the Dudley Observatory. "There is no other work of this kind in the English language that contains in so small a compass so much practical information in the application of galvanic electricity to telegraphy. It should be in the hands of every one interested in telegraphy, or the use of Batteries for other purposes." orsels Tele1egraphi Apparatnso Illustrated. 8vo. Cloth. $2. 00. EXAMINATITON OF THE TELEGRAPHIC APPARATUS AND THE PRIOCESSES IN TELEGAPHY. By SA-MUEL F. Bt. MORSE), LL.D., United States Commissioner Paris Universal Exposition, 1867. D. VAY N OSTBRANV-D. 21 Sabine's History of the Telegraph. 12mo. Cloth. $1.25. HISTORY AND PR(OGRESS OF THE ELECTRIC TELEGRAPH, with Descriptions of some of the Apparatus. By ROBERT SXBINE, C. E. Second edition, with additions. CONTENTS.-I. Early Observations of Electrical Phenomena. II. Telegraphs by Frictional Electricity. III. Telegraphs by Voltaic Electricity. IV. Telegraphs by Electro-Magnetism andl Ml1agneto-Electricity. V. Telegraphs now in use. VI. Overhead Lines. VII. Submarine Telegraph Lines. VIII. Undergrounln Telegraphs. IX. Atmospheric Electricity. aiskins' Galvanometer. Pocket form. Illustrated. Morocco tucks. $2.00. THE GALVANOM]ETER, AND ITS USES; a MBanual for Electricians and Students. By C. Hi. HASKINS. "We hope this excellent little work will meet with the sale its merits entitle it to. To every telegrapher who owns, or uses a Galvanometer, or ever expects to, it will be quite indispensable."-'-The Telegrcaher. Culley's 1and-Book of Telegraphy. 8vo. Cloth. $S.00. A HAND-BOOK OF PRACTICAL TELEGRAPHY. By R. S. CULLEY, Engineer to thle Electric and International Telegraph Comnnpany. Fifth edition, revised and enlarged. Foster9s S-nubmarine Blasting. 4to. Cloth. $3.50. SUB-MARINE BLASTING in Boston I{arbor, MassachusettsRemoval of Tower and Corwin Rocks. By JoHN G. FosTIER, Lieutenant-Colonel of Engineers, and ]3revet ajor-General, U. S. Army. Illustrated with seven plates. LIST O'F PLATES. —1. Sketch of the Narrows, Boston HIarbor. 2. Townsend's Submarine Drilling Machine, and Working Wessel attending. 8. Submarine Drilling M{achine employed. 4. Details of Drilling Machine employed. 5. Cartridges and Tamping used. 6. Fuses and Insulated WTires u;sed. 7. Portable Friction Battery used. 22 SJL'ET'XYT fIIC ~ vi OuAi P UBL ISHTEYD BY Y Barnes9 Submarine VWarfare. Svo. Cloth. $5.00. SUBiMARINA E WARFARE, DEFENSIVE AND OFFENSIVE. Comprising a full and complete History of the Invention of the Torpedo, its employment in War and results of its use. Descriptions of the various forms of Torpedoes, Submarine Batteries and Torpedo Boats actually used in WVar. Methods of Ignition by MIachinery, Contact Fuzes, and Electricity, and a full account of experiments made to determine the Explosive Force of Gunpowder under Water. Also a discussion of the Offensive Torpedo system, its effect upon Iron-Clad Ship systems, and influence upon Future Naval Wars. By Lieut.-Commander JoHN S. BARNES, U. S. N. With twenty lithographic plates and many wvood-cuts. " A book important to military men, and especially so to engineers and artillerists. It consists of an examination of the various offensive andl defellsivo engines that have been contrived for submarine hostilities, including a discussion of the torpedo system, its effects upon iron-clad ship-systemns, and. its probable influence upon future naval wars. Plates of a valuable character accompany the treatise, which affords a useful history of the momentous subject it discusses. A great deal of useful information is collected in its pages, especially concerning the inventions of SCHOLL and VE!RDU, and of JONES' and IHUNT'S batteries, as well as of other similar machines, and the use in submarine operations of gun-cotton and nitro-glycerine."-N. IY. Tianes. Randalls Quartz Operator's HandBook. 12mo. Cloth. $2.00. QUAIRTZ OPERATOR'S TEAND-BOOK. By 1P. M. RA!NDALL, New edition, revised and enlarged. Fully illustrated. The object of this work has been to present a clear and comprehensive exposition of mineral veins, and the means and modes chicfly employed for the mining and working of their ores-more especially those containing goldl and silver. Mitchell's Manual of Assaying. 8vo. Cloth. $10.00. A MANUAL OF PRACTICAL ASSAYING. By JOHN IITCHnrLL. Third edition. Edited by WVILLIAr l CR00KES, IF.R.S. In this edition are incorporated all the late important discoveries in A.ssaying made in this country and abroad, and special care is devoted to the very important Volumetric and Colorimetric Assays, as well as to the Blow-Pipe Assays. Ben6t's Chronoscope. SeconLdf Editiont. Illustrated. 4to. Cloth. $3.00.:ELECTRO-BALLISTIC MACHINES, and the Schultz Chronoscope. By Lieutelnant-Colonel S. V. BENEzT, Captain of Ordnance, U. S. Army. CONTENTS.-t. Ballistic Pendulum. 2. Gun Pendulum. 3. Use of Electricity. 4. Navez' l{Machine. 5. Vipgotti's lvIachine, with Plates. 6. Benton's Electro-Ballistic Pendulum, with Plates. 7. Leur's Tro-Pendulum Machine 8. Schultz's Chronoscope, with two Plates. Michaelis' Chronograph. 4to. Illustrated. Cloth. $3.00. THE LE BOUTLENGE CHRONOGRAPH. With three lithographed folding plates of illustrations. By Brevet Captain 0 E. MICOAELIs, First Lieutenant Ordnance Corps, LT. S. Army. "The excellent monograph of Captain Michaelis enters minutely into the details of construction and management, and gives tables of the times of flight calculated upon a given fall of the chronometer for all distances. Captain Michaelis has clone good service in presenting this work to his brother officers, describing, as it does, an instrument which bids fair to be in constant use in our future ballistic experiment's.'-A-?2ny azwc Nevy JoZmrncatg 24 SIEivE NhIaC B 0 OJST f PLBLI~SIIE- D -BY Silversmith's and-Book. Illustrated. 12m1o. Cloth. $3.00. A PR2ACTICAL RH/AND-BOOKI FOR M INERS, lMetallurgists, and.Assayers, comprising the most recent improvements in tho disintegration, amalgamation, smelting, and parting of theo Precious Ores, with a Comprehensive Digesut of the lMiining Laws. Greatly augmented, revised, and corrected.:By JuLIVs SIvrVEuSITH. Fourth edition. Profusely illustrated. I vol. 1~2mo. Cloth. $3.00. One of the most important features of this work is that in which tho mnetallurgy of the precious metals is treated of. In it the author has endeavored to embody all the processes for the reduction and manipulation of the precious ores heretofore successfully employed in Germany, England, Mexico, and the United States, together with such as have been more recently invented, and not yet fully tested —all of which are profusely illustrated and easy of comprehension. Sin1m2s' Levelling. 8vo. Cloth. $2.50. A TREATTSE O1N THE PRINCIPLES AND PRACTICE OF LEVELLING, showing its application to purposes of Railway Engineering and the Construction of lRoads, &c. By FREDEICK WT. SI;xs, C. E. From the fifth London edition, revised and corrected, with the addition of Mr. Law's Practical Examples for Setting Out Railway Curves. Illustrated with three lithographic plates and numerous wood-cuts.'One of the most important text-books for the general surveyor, and there is scarcely a question connected with levelling for which a solution would be sought, but that would be satisfactorily answered by consulting' this volumne." -infinng Journal. "The text-book on levelling in most of our engineering schools and colleges. —Eng7yz~crs. "The publishers have reidered a substantial service to the profession, especially to- the younger members, by bringing out the present edition,of Mr. Simms' Lsceful wvork-.".niyee'rbZ.i. D. V'.zA,0N T./ANL4,D. 25 Stuart's Successful Engineer. 18Smo. Boards. 50 cents. HOW TO BECOMITE A SUCCESSFUL ENGINEER: Being Hints to Youths in-tending to adopt the Profession. By BERNARD STIART, Eniginleer. Sixth Edition. " A valuable little book of sound, sensible advice to young men awlo wish to rise in the most important of the professions."-Scie.lific American. Stuart's Naval Dry Docks. Twenty-four engravings on steel. 1'ourth Etd-itao',. 4to. Cloth. $6.00. THE NAVAL, DRY DOCKS OF THE UNITED STATES. By CARnLEs B. STU.ART'. Elgineer in Chief of the United States Navy. -List of' lllh strcstions. Pumping Engine and Pumps-Plan of Dry Dock and Pump-WTell-Sections of Dry Dock-Engine House-Iron Floating Gate-Details of Floating Gate-Iron Turning Gate- Plan of Turning Gate-Culvert Gate-Filling Culvert Gates-Engine Bed-Plate, Pumps, and Culvert-Engine House Roof-Floating Sectional Dock-Details of Section, and Plan of Turn-Tables — Plan of Basin and }lMarine Railways-Plan of Sliding Frame, and Elevation of Pumps-Hydraulic Cylinder —Plan of Gearing for Pumps and End Floats -Perspective View of Dock, Basin, and Railway-Plan of Basin of Portsmouth Dry Dock-Floating Balance Dock-Elevation of Trusses and the Machinery-Perspective View of Balance Dry Dock Free Hand Drawing. Profusely Illustrated. 1Smo. Boards. 50 cents. A GUIDE TO ORNA3MENTAL, Figure, and Landscape Drawing. By an Art Student. CONTENTS.-Materials employed in Drawing, and how to use them-On Lines and how to Draw them —On Shading-Concerning lines and shading, with applications of them to simplo element;ary subjects-Skotohes from Natr.lqt, 26 S'CIE'V2TII7C BOOKES PUBLIiHJJED B Y Minifie's Mechanical Drapwing. Royal 8vo. Cloth. $4.00. A TEXT-BOOK OF GEOMETRICAL DRAWnING for the use of Mechanics ancl Schools, in which the Definitions andi Ruless of Geometry are familiarly explained; the Practical Problems are arranged, from the most simple to the more complex, and in their description technicalities are avoided as much as possible. WVith illustrations for Drawing Plans, Sections, and Elevations of Buildings and M/iachinery; an Introduction to Isometrical Drawing, and an Essay on Linear Perspective and Shadows. Illustrated with over 200 diagrams engraved on steel. ]By WAnr, MINIFIE, Architect. Eighth Edition. With an Appendix on the Theory and Application of Colors. " Tt is the best work on Drawing that we have- ever seen, and is especially a text-book of Geometrical Drawing for the use of Mechanics and Schools. No young Mechanic, such as a Machinist, Engineer, Cabinet-3Maker, Millwright, or Carpenter, should be without it."-Scientzifc Arnerica'n. "One of the most comprehensive works of the kind ever published, and cannot but possess great value to builders. The style is at once elegant and substantial."'-Pennsylvania Inquirer. "Whatever is said is rendered perfectly intelligible by remarkably wellexecuted diagrams on steel, leaving nothing for mere vague supposition; and the addition of an introduction to isometrical drawing, linear perspective, and the projection of shadows, winding up with a useful index to technical terms." -Glasgow iecbhanics' Jour'nal.,kff- The British Government has authorized the use of this book in their schools of art at Somerset IHouse, London, and throughout the kingdom. Minifie's Geometrical Drawing. 2'ew Edition. BEniarged. 12mo. Cloth. $2.00. GEOMETRICAL DRAWING. Abridged from the octavo edition, for the use of Schools, Illustrated with 48 steel plates. New edition, enlarged. 4 It is well adapted as a text-bool of drawing to be used in our. High Schools and Academies where this useful branch of the fine arts has been hitherto too much neglected."-Beosto T Jonracld. D. VF4X 11\TOSTPAX.G 27 Bell on Iron Sm$.eltin g.,vo. Cloth. $6.00. CHEMiICAL PHENOMENA OF IRON SMIELTING. An experimental and practical examination of the circumstances which determine the capacity of the Blast Fulrnace, the Temperature of the Air, and the Proper Condition of the Materials to be operated upon. By I. LOWTHIAN BELL. "The reactions which take place in every foot of the blast-furnace have been investigated, and the nature of every step in the process, from the introduction of the raw material into the furnace to the production of the pig iron, has been carefully ascertained, and recorded so fully that. any one in the trade can readily avail themselves of the knowledge acquired; and we have no hesitation in saying that the judicious application of such knowledge will do muchl to facilitate the introduction of arrangements which will still further economize fuel, and at the samce time permit of the quality of the resulting metal being maintained, if not improved. The volume is one which no practical pig iron manufacturer can afford to be without if he be desirous of entaring upon that competition which nowadays is essential to progress, and in issuing such a work Mr. Bell has entitled himself to the best thanks of every member of the trade."-London MLining Journal. King's Notes on Steam. Tirteensh Brd2,ion. 8vo. Cloth. $2.00. LESSONS AND PRACTICAL NOTES ON STEAMl, the SteamEngine, Propellers, &c., &c., for Young Engineers, Students, and others. By the late V. R.. ING, U. S. N. IRevised by ChiefEngineer J. WT. IKING, U. S. Navy. "This is one of the best, because eminently plain and practical treatises on the Steam Engine ever published.'-Philadelphia Press. This is the thirteenth edition of a valuable work of the late V. H. King, U. S. N.. It contains lessons and practical notes on Steam and the Steam Engine, Propellers, etc. It is calculated to be of great use to young marine engineers, students, and others. The text is illustrated and -explained -by numerous diagrams and representations of machinery.,-Boston Daily Advertiser. Text-book at the UT. S. Naval Academy, Annapolis. S CIYFV'ITTFI _1 OBO~ 0 0 PUBLISIJED ) Y Burgh's Modern Marine Engineering. One thick 4to vol. Cloth. o?25.00. Half morocco. $30.00. AMODERN MIARINE ENGINEERING, applied to Paddle and: Screrw Propulsion. Consisting of 36 Colored Plates, 259 Practical Wood-cut Illustrations, and 403 pages of Descriptive Ml~atter, tilo whole- being an exposition of the present practice of the followingo firms: Mi[essrs.. J. Penn & Sons; Messrs. Maudslay, Sons CL Field; MIessrs. James Watt & Co.; Afessrs. J. & G. Rennio; Messrs. It. Napier & Sons; }Messrs. J. & WV. Dudgeon; MIessrs. Ravenhill & IH-odgson; Messrs. IHiumphreys & Tenant; Mr. J. T. Spencer, and Messrs. Forrester & Co. B3y N. P. BUrGou, lEngineer. PRINCIPAL CONTENTS.-General Arrangements of Engines, 11 examples -General Arrangement of Boilers, 14 examples - General Arrangegement of Superh'eaters, 11 examples-Details of Oscillating Paddle [Engines, 84 c8 - amples-Condensers for Screw Engines, both Injection and Surface, 20 examples-Details of Screw Engines, 20 examples-Cylinders and Details of Screiw Engines, 21 examples-Slide Valves and Details, 7 examples-Slid6 Valve, Link Motion, 7 examples -Expansion Valves and Gear, 10 examples-Details in General, 30 examples —Screw Propeller and Fittings, 13 examples [Engine and Boiler Fittings, 28 examples - In relation to the Principles of the Marine Engine and Boiler,;83 examples. ZYrotices of zlie Press. "Every conceivable detail of the Mlarine Engine, under all i*s various forms, is profusely, and w-e must add, admirably illustrated by a multitude of engravings, selected from the best and most modern practice of the first Marine Engineers of the day. The chapter on Condensers is peculiarly valuable. In one word, there is no other work in existence which will bear a moment's comparison with it as an exponent of the skill, talent and practical experience to which is due the splendid reputation enjoyed by many British Marine Engineers."-Engineer.'" This very comprehensive work, which was issued in Monthly parts, ]has just been completed. It contains large and full drawings and copious descriptions of most of the best examples of Modern iMarine Engines, and it i3 a complete theoretical and practical treatise on the subject of Marine En$gineering."-American Artisan. This is the only edition of the above work with the beautifully colored i)lates, a-nd it is out of print in England. J). }-,L ~f-O6'2:ZL,1 4 V. 29 Bourne's Treatise on the Steam. En, gine. Ninth BEtiotit Illustrated. 4to. Cloth. $15.00. TREATISE ON THE STEAi, ENGINE in its various applicoa tions to ]Mlines, Mills, Steamn Navigation, Rtailways, and Agricul, ftlre, with tho theoretical investigations respectingl the Motiva Plower of Heat and the proper Proportions of Steaml ]Engines. Elaborate Tables of theo right dimensions of every part, andl Practical Instructions for the Manufacture anltd ~Management of every species of Engine in actual use. ]By JouH BDouRNr, beinig the ninth edition of "A Treatise on the Steam Engine," by the " Artisan Club." Illustrated by thLirty-eight plates and five hundred and forty-six wood-cuts. As IM]r. Dourne's work has the great merit of avoiding unsound and immature views, it may safely be consulted by all who are really desirous of acquiring trustworthy information on the subject of which it treats. During the twenty-two years which have elapsed from the issue of the first edition, the improvements introduced in the construction of the steam engine have been both numerous and important, and of these Mr. Bourne has taken care to point out the more prominent, and to furnish the reader with such information as shall enable him readily to judge of their relative value. This edition has been thoroughly modernized, and made to accord -with the opinions and practice of the more successful engineers of the present day. All that the book professes to give is given with ability and evident care. The scientific principles -which are permanent are admirably explained, and reference is made to many of the Inore valuable of the recently introduced engines. To express an opinion of the value and utility of such a work as The Atisan 6Cub's Treatise on the Steam Engine, which has passed through eight editions already, would be superfluous; but it may be safely stated that the work is worthy the attentive study of all either engaged in the manufacture of steanm engines or interested in economizing thLe use of steam. —31iniJng Jourqnal. Isherwood's Engineering Precedents. Two Vols. in One. 8vo. Cloth. $2.50. tENGiNEERING PRIECEDENTS FOR STEAMI li MACHINERY. Arranged in the most practical and useful manner for Engineers. 13y 13. F. IsEnWOOOD, Civil Engineer, U, S. Navy. With illustrations. 2 50 S J( if7 I Pi C'6S I 0 0Bi ) ) (| SS P EJ I If BYWarcL's S-teaam Lor the Miillion. Newv amtl 1Rezlisez EhIzt son, Svo. Cloth. $,1.09. STEAM FOR THE MILLION. A Popular Treatise on Steam and its Application to the Useful Arts, especially to Navigation. By J. HI. WamRD, Commander U. S. Navy. Neow alnd revised edition. A most excellent work for the yroung engineer and general reader. Many facts relating to the management of the boiler and engine are set forth %vithl a simplicity of language and perfection of detail that bring the subject homo to the reader. —xAneri otU Efngzineer. Walker's Screw Propulsion. 8vo. Cloth.;5 cents. NOTES ON SCREWT PROPULSION, its Rise and IHistory. By Capt. W. I. WiAL:KER, U. S. Navy. Commander W~alker's book contains an immense armount of concise prattical data, and every item of information recorded fully proves that the various points -bearing upon it have been well considered previously to eipressing.an opinion.-Leondoan iliiinbng Jour'zal. Page's Earth's Crust. 18mo. Cloth. 75 cents. THE EARTH'-S CRUST: a HIandy Outline of Geology..y D.kVID PA&s GE. " Such a work as this was much wanted-a work giving in clear and intelligible outline the leading facts of the science, without amplification or irksome details. It is admirable in arrangement, and clear and easy, and, at the same time, forcible in style. It will lead, we hope, to the introduction of Geology into many schools that have neither time nor room for the study of large treatises."- The iuszseum. 12. YAK IWOST-IND. 31Rogers' Geology of Pennsylvania. 3 Vols. 4to, with Portfolio of Maps. Cloth. $30.00. THE GEOLOGY OF PENNSYLVANIA. A Government Survey. With a general view of the Geology of the United States, Essays on the Coal Formation and its Fossils, and a description of the Coal Fields of North America and Great Britain. By IIENRY DI1RWIN ROGERS, Late State Geologist of Pennsylvania. Splendidly illustrated with Plates and Engravings in the Text. It certainly should be in every public library throughout the country, and likewise in the possession of a11 students of Geology. After, the final sale of these copies, the work will, of course, become more valuable. 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APP1ENDIX.-Report on the Application of Gun-Cotton to W;arlike Purposes-British Association, 1863; Manufacture and Experiments in England; Guns looped with Initial Tension-History; How Guns Burst, by Wiard, Lyman's Accelerating Gun; Endurance of Parrott and Whitworth Guns at Charleston; tooping old United States Cast-Iron Guns; Endurance and Accuracy of the Armstrong GOO-pounder; Competitive Trials with 7-inch Guns. 34 -SUI,nN INI. FIC B 0 S, P IP.LISJ'1]) I? Y Peirce's Analytic Mechanics. 4to. Cloth. $10.00. SYSTE{3 OP ANALYTIC M{ECHiANICS. Physical and Celestial Mi echanics. By BENJAMIN PnEInck, Perkins Professor of Astronomy and Mathematics in Hiarvardl University, and Consulting Astronomer of the Americanl Ephemeris anc Nautical Almanac. Developed in four systems of Analytic Mfechanics, Celestial Mlechanics, Potential Physics, andl Analytic Morphology. 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It is the intention of the Publislher of tlhis Series to issue them at intervals of about a month. They will be put up in a uniform, neat and attractive form, 18mo, fancy boards. Thle subjects will )be of an eminently scientific character, and embrace as wide a range of topics as possible, all of the highest character. Price, 50 Cents Each. 1., CHIMNEYS FOR lFURNACES, FIRE-PLACES, AND STEAM BOILERS. By R. ARMSTRONG, C. E. 2. STEA'M BOILER- EXPLOSIONS. By ZEIAxr COLlBURN. 3PRACTICAL DESIGNING OF RETAINING WALLS By ARrTHUR JACOB, A. B. Wit- Illustrations. PROPORTIONS OF PINS USED IN BRIDGES. By CHARLES E. BENDER, C. E. With Illustrations. VENTILATION OF BUILDINGS. ByW'T. F. BUTLER. With ~Illustrations. 6. ON THE DESIGNING AND CONSTRUCTION OF STORAGE RESERVOIRS. By ARTHIUR JACOI. With Illustrations. 7SUPRCHARGED AND DIFFERENT FORMAS OF RETAINING WALLS. By JAMES S. TATE, C. E. A TREATISE ON THE COMPOUND E1NGINE. By JOHN TURNBULL. With Illustrations. FUEL. By C. W. SIEMENs to which is appended the Value of Artificial Fuels as compared with Coal. By J. WORMALD, C. E. ** Other works in preparation. D. VA N 1 0 TRiA ND. 47 10. COMPOUND ENGINES. Translated fromn the French of A. MALLET. Illustrated. 11. THIEORY OF ARCHES. By Prof. W. ALLAN, of tho Washington and Lee College. Illustrated. 12. A PRACTICAL THEORY OF VOUSSOIR ARCHES. By WILLIA3IM CAIN, C.E. Illustrated. 13. A PRACTICAL TREATISE ON THE GASES MET WITH IN COAL-MINES. By the late J. J. ATKINSON, Govern nt Inspectorof Mines for the County of Durham, Enmglant 14. FRICTION OF A IR IN MINES, By J. J. ATKrISON, Author of "A Practical Treatise on the Gases met with in Coal-AMines." 1a. SKEW ARCHES. By Prof. E. W. HYDE, C.E. Illustrated witlh numerous engravings and three folded plates. 48 D. VI.ANT NVOSTWRANVD. SILVER MINING tREGIONS OF COLORADO, with some account of the different Processes now being introduced for working the Gold Ores of that Territory. By J. P. WHITNEY. 12mo. Paper. 25 cents. COLORADO: SCHEDULE OF ORES contributed by sundry persons to the Paris Universal Exposition of 1867, witlh sonio information about the Region and its Resources. B]y J. P'. WHITNEY, Commissioner friom the Territory. 8vo. Paper, witl Maps. 25 cents. THE SILVER DISTRICTS OF NEVADA. ATith Map. Svo. 5Paper. 35 Cents. ARIZONA: ITS RESOURCES.AD PROSPECTS. Ily IIon. R. C. Mi[CcConrtcic, Secretary of the Territory. WVitl IXap. Svo. lPaper. 25 cents. MONTA.NA AS IT IS. Being a general description of its Resources, botLh 3iineral and Agricultural; including a complete description of the face of the country, its climate, etc. Illustrated with a AMap of the Territory, showing the different Roads and the location of the different Mining Districts. To which is appended a complete Dictionary of TuE SXNAKE tLANGUNtGE, and also of the famous Chinnook Jargon, with numerous critical and explanatory Notes. By GRANtVILLE STUART. 8vO. Paper. $82.00. RIAILWAY GAUGES. A Review of the Theory of Narrow Gauges as applied to Main Trunk Lines of RIailway. By SILaLS SEYMOUR, Genl. Consulting Engineer. 8vo. Paper. 50 cents. iREPORT made to the President and Executive Board of the Texas Pacific Railroad. By Gen. G. P. BUELL, Chief Engineer. 8vo. Paper. 75 cents.