LIBRARY OF THK UNIVERSITY OF CALIFORNIA Received. Accessions No.-&./j^ Shelf No. OUTLINES OF PROXIMATE ORGANIC ANALYSIS, BY THE SAME A UTHOR. 12mo, cloth, $1 50. CHEMICAL EXAMINATION * ALCOHOLIC LIQUORS. A MANUAL, OP THE CONSTITUENTS OF THE DISTILLED SPIRITS AZTD FERMENTED LIQUORS OF COMMERCE, AOT> TBOEIB QUALITATIVE AND QUANTITATIVE DETERMINATIONS. OUTLINES OF PROXIMATE ORGANIC ANALYSIS, FOB IDENTIFICATION, SEPARATION, AND QUANTITATIVE DETERMINATION MORE COMMONLY OCCURRING ORGANIC COMPOUNDS. ALBERT B. PEOFKSSOB OF OEGANIO AND APPLIED CHEMI8TBY IN THB UKITBBMTT OF THIRD EDITION. NEW YOEK: D. VAN NOSTRAND, PUBLISHER, 23 MURRAY STREET, AND 27 WARREN STREET. 1882. Main uS>. Agric. Dept Entered, according to Act of Congress, in the year 1874, by D. VAN NOSTKAND, y/x3^ In the Office of the Librarian of Congress, at Washington, D. C. PREFACE. THIS little work has been prepared more espe- cially for the use of a class of chemical students who devote a semester to the analysis of vege- table 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 con- venience of every general analyst. Proximate organic analysis is not altogether impracticable, and organic chemistry is not solely a science of synthetical operations even at pre- sent. 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 been PREFACE. 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 work- ers in inorganic analysis were unprovided with a comprehensive system, but they went on explor- ing 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 opportu- nity for its improvement hereafter. UNIVERSITY OF MICHIGAN, September, 1874. CONTENTS. frABAGRAPH. PAGE. PRELIMINARY EXAMINATIONS. 1. Carbon, uncombined, - 11 2. Carbon in combination, - 11 3. Preliminary examination of Solids, - - - - 11 4. Preliminary examination of Liquids, - 12 5. References for Solids and Liquids ; Fixed and Vola- tile ; Acid, Fatty, Basic, and Neutral, - 13 SOLID NON-VOLATILE ACIDS. 6. Tartaric acid, - 14 7. Racemicacid, - 18 8. Citric acid, - - - - 18 9. Aconitic acid, - 21 10. Malic acid, - 22 11. Meconic acid, 24 12. Digitalic acid, - 26 13. Tannicacid, - 26 14. Gallic acid, - - - 30 15. Pyrogallic acid, - 32 16. Quinotannic acid, - 33 17. Catechutannic acid, 33 18. Catechuic acid, - 34 19. Morintannic acid, - - 35 20. Caff etannic acid, - 35 21. Boheicacid, - 36 22. Quinicacid, ... 36 PARAGRAPH. PAGE. 23. Quinovic acid, - 38 24. Columbic acid, - 39 25. Gentianic acid, - 39 26. Carminic acid, - 40 27. Chrysophanic acid, - 41 28. Gambogic acid, - 41 29. Santalic acid, - 42 SOLID VOLATILE ACIDS. 30. Benzoicacid, - 42 81. Cinnamic acid, - 44 32. Succinic acid, - 45 33. Salicylic acid, - - - 47 34. Veratric acid; - 47 35. Phenicacid, - - 48 36. Nitrophenic acid, - 51 37. Sulphophenic acid, - - 53 LIQUID NON-VOLATILE ACID. 38. Lactic acid, - 53 LIQUID VOLATILE ACIDS. 39. Formic acid, - 55 40. Acetic acid, - - 58 41. Butyric acid, - 61 42. Valeric acid, - 63 43. Separations, - 67 44. Volatile Fat Acids of the acetic series, - 67 CONTENTS. PABAGBAPH. PAGE. FATTY ACIDS : LIQUID AND SOLID. 45. Non-Volatile Fatty Acids, 68 46. Bicinoleic acid, - 69 47. Oleicacid, - 69 48. Linoleic acid, - 69 49. Erucicacid, - - - 70 50. Laurie acid, - - - 70 51. Myristic acid, - - 70 52. Palmitic acid, - 70 53. Stearic acid, - - - 70 54. Cerotic acid, - - 70 55. Separations by Saponifica- tion, ----- 71 56. Separations by Fusion, - 71 57. Separations by Solvents, - 71 58. Quantitative Determina- tions, ----- 72 NEUTRAL SUBSTANCES : LIQUID OB FUSIBLE. 59. Fixed Oils: (a) Liquid; (6) Solid, - 72 60. Methods of Examination of Fixed Oils, - - - 74 61. Calvert's Methods, - 78 62. Tests with Argentic Ni- trate, 81 63. Analysis of Butter, - - 81 64. Analysis of Milk, - - 84 65. Separation of Fixed from Volatile Oils, - 85 66. Glycerin, - - - - 85 67. Methods of Analysis of Soaps, 87 68. Resins : general character- istics, ----- 92 69. Resins : how separated from other bodies, 93 70. Aloes resin, - 93 71. Amber resin, - 93 72. Ammoniac resin, - 94 73. Assafetida resin, 94 74. Benzoin resin, 94 75. Canaubawax, - - - 95 PAGE. - 95 - 95 - 96 PABAGBAPH. 76. Caoutchouc, - 77. Colophony, - 78. Copaiba resin, 79. Copal resin, 80. Dammara resin, - 81. Dragon's Blood resin, 82. Gamboge resin, - 83. Guaiacum resin, - 84. Hemp resin, 85. Indigo-blue resin, 86. Jalap resin, - 87. Jalapin resin, 88. Convolvulin resin, 89. Lac resin, - 90. Mastic resin, 91. Myrrh resin, - 92. Olibanum resin, - 93. Peru balsam resin, 94. Podophyllum resin, - 95. Sandarac resin, - 96. Scammony resin, 97. Storax resin, 98. Tolu balsam resin, 99. Separation of Resins, 100. Volatile Oils : Classes of, - 101. ' Properties of, 102. ' Solubilities of, - 103. ' How identified, - 104. ' How separated, - 105. ' List, with color andsp. gr., - 107 106. Examination by Alcohol, - 108 107. Examination by Iodine and Bromine, - 109 108. Examination by sulphuric acid, etc., - 111 109. Examination by Plumbic sulphide, - 97 97 98 98 100 100 101 101 103 103 102 102 102 102 103 103 104 104 105 105 105 - 114 110. Examination by Sodium, - 114 111. Resinified Volatile Oils, - 115 112. Turpentine oil, - - 115 113. Valerian oil, - - 115 114. Peppermint on, - - 115 115. Camphor, - - 116 116. Creosote, - - 116 CONTENTS. PABA.GKAPH. PAGE. 117. Anthracene, - 117 118. Alizarin, - - - - 117 119. Benzole; Petroleum, Naph- tha, ----- 118 120. Nitrobenzole, - - 119 BASES : LIQUID AND SOLID. 121. Anilin, - 120 122. Anilin of commerce, - - 120 123. Anilin Compounds, - - 121 124. Toluidin, - - - - 121 125. Methods of Determining Anilin, - - 121 126. Alkaloids : classes of, - 123 127. Conia, - - - - 123 128. Lobelina, - - 123 129. Nicotia, - - 123 130. Trimethylamia, - - - 123 131. Comparative reactions of Volatile bases, - - - 124 132. Non- Volatile Alkaloids: List, 125 133. Table of Solubilities of, - 128 134 Separation of , - - - 130 (1) Method of Stas-Otto, - 131 (2) Rodgers and Girdwood, - 132 (3) Uslar and Erdmann, - 133 (4) Graham and Hofmann, - 134 (5) by Dialysis, - - - 134 (6) Method of Dragendorff, - 134 (7) Dragendorff (Alkaloids and Glucosides), - - - 136 (8) by use of Alkalies, - - 137 (9) Ether, Water, Chloroform, 138 135. Identification as Alkaloids, 139 a. by Potassio Mercuric Io- dide, - - - - 139 6. Phosphomolybdic acid, - 140 c. Metatungstic acid, - - 141 d. Potassio Cadmic Iodide, - 141 e. Picric acid, - 142 /. Tannicacid, - - .143 g. Iodine in Iodide, - x 144 136. Alkaloids with Sulphuric acid and Frohde's reagent, 144 PAEAGEAPH. PAGB. 137. Sulphuric and Chromic acids, - 146 138. Nitric acid, - - - - 146 139. Sulphuric acid and Nitrate, 147 140. Chlorine, then Ammonia, - . 148 141. Ferric Chloride, - 148 142. Platinic Chloride (Quanti- tative), - 148 143. Auric Chloride (Quantita- tive), - - - 150 GLUCOSIDES AND OTHER SOLID NEU- TRAL SUBSTANCES. 144. Absinthin, - - - - 151 145. Aloin, - - - 151 146. Amygdalin, - 152 147. Asparagin, - - 152 148. Cantharidin, - - 153 149. Cathartin, - - 153 150. Colombin, - - - - 153 151. Cubebin, - - - 154 152. Elaterin, - - 154 153. Fraxin, - 154 154. Lactucin, - - 155 155. Phloridzin, - - 155 156. Populin, - 155 157. Quassin, - - - 155 158. Sarsaparillin, - 156 159. Taraxacin, - - 156 160. Vanillin, - - 156 161. Separation of Glucosides, etc., - - - - - 156 NITROGENOUS NEUTRAL BODIES. 162. Albumenoids, - - - 157 163. Ovalbumen, - 158 164. Seralbumen, - - - - 158 165. Casein, - - - - 159 166. Milk Albumen, - - - 159 167. Determ. Casein and Albu- men in Milk, - - - 159 168. Quantitative Anal, of Milk, 160 169. Commercial Examination of Milk, - - - - 160 10 CONTENTS. PARAGRAPH. 170. Gelatin, 171. Leather, - - - CARBOHYDRATES. 172. Gums, - 173. Gum Arabic, 174. Gum Tragacanth, 175. Dextrin, - 176. Starch, - - - 177. Pectous Substances, - 178. Pectose, 179. Pectin, - - - 180. Pectic acid, - - - 181. Parapectin, - 183. Parapectic acid, - 183. Metapectin, 184. Metapectic acid, 185. Cellulose, - - - 186. Nitrocellulose, - PAGE. PARAGRAPH. PAGE. - 160 187. Glucose, - 168 - 161 188. Lactose, - - 171 189. Sucrose, - 172 190, Mannite, - - 174 - 161 - 162 ALCOHOLS AND THEIR PRODUCTS. - 162 191. Methylic Alcohol, -. - 175 - 163 192. Ethylic Alcohol, - 176 - 163 193. Aldehyde, - - 177 - 166 194. Sulphethylates, - - 177 - 166 195. Ether, - - 179 - 166 196. Nitrous Ether, - - 180 - 166 197. Chloroform, - 180 - 166 198. Chloral Hydrate, - 182 - 166 199. lodoform, - - 184 - 167 200. Croton Chloral Hydrate, - 184 - 167 201. Amylic Alcohol, - 184 - 167 202. Fusel-Oil, - - 185 - 168 203. Nitrite of Amyl, - 186 OUTLI OF PROXIMATE ORGANIC ANALYSIS. PRELIMINARY EXAMINATIONS. 1. CARBON (uncombined) is recognized by its sensible pro- perties (as charcoal, graphite, or diamond), by not vaporizing when heated, and by resisting ordinary solvents neutral, alka- line or acid except that graphite is oxidized by digestion with chlorates and sulphuric or hydrochloric acid, or with bichro- mates and sulphuric acid, or with mixed nitric andT 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 OP CARBON except the alka- line 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 resi- due 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. n 12 PRELIMINARY EXAMINATIONS. (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 accord- ing to b. Also consider ammonium 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 CO a 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 car- bon 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 por- tion 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 accord- ing 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 chang- ing the receiver as often as the boiling point is seen to rise. Cool the residue and distillates. Test the solid portions accord- ing 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. PRELIMINAR Y EXAMINA TIONS. 13 5. a. SOLIDS. NON-VOLATILE. Acids: Aconitic 9. Boheic 21. Caffetannic 20. Catechuic 18. Catechutannic 17. Carminic 26. (Chrysophanic) 27. Citric 8. Columbic 24. Digitalic 12. (Gallic) 14. Gambogic 28. Gentianic 25. Malic 10. Meconic 11. Morintannic 19. (PyrogaUic) 15. Quinic 22. Quinotannic 16. Quinovic 23. Racemic 7. Tannic 13. Tartaric 6. Santalic 29. Fatty Acids : Cerotic 54. Erucic (melts at 34 C.) 49. Laurie 50. Myristic 51. Palmitic--52. Stearic 53. Fixed salts of volatile acids. Fixed Oils 59, b ; 60 to 63. Resins 99, and 68 to 98. Alkaloids (fixed) 132 to 143. Carbohydrates : Cellulose 185. Dextrin 175. Gum 172. Gun-cotton 186. Pectin, etc. 177 to 184. Starch 176. Sugars 187 to 190. Albumenoids 162 to 167. Gelatin 170, 171. VOLATILE. Acids : Benzoic 30. (Chrysophanic) 27. Cinnamic 31. (Gallic) 14. Nitrophenic 36. (PyrogaUic) 15. Salicylic 33. Succmic 32. Sulphophenic 37. Veratric 34. Camphors 115, 101, and 111. Anthracene 117. Alizarin 118. Anilin compounds 123. Chloral hydrate 198. lodoform 199. Salts of Volatile Alkaloids, b. LIQUIDS. NON-VOLATILE. Acid : Lactic 38. Fatty Acids : Linoleic (melts, 18 C.)-48. Oleic 47. Ricinoleic i6. Fixed Oils 59. (Soft Soaps) 67. Glycerin 66. VOLATILE. Acids: Acetic 40. Butyric 41. Formic 39. Valeric 42. Volatile Oils 105, 104, and 100 to 114. Creosote 116. Volatile Alkaloids 131 and 126 to 130. 14 SOLID NON-VOLATILE ACIDS. Anilin 121. Solvents: Ether-195. Solvents Continued. Co. Ethers 406, 416, 42a, 44, etc. Meth. Alcohol 191. Nitrobenzole 120. Petroleum Alcohol 193. Aldehyd 193. Amyl. Alcohol 201. Benzole 119. Chloroform 197. SOLID NON-VOLATILE ACIDS. 6. TART ABIC ACID. H 2 C 4 H 4 O 6 . Characterized by the form of its crystals and its rotation of polarized light (a) ; by its odor when 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). Separated (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 amyl-ic alcohol (e) ; from alcoholic solutions by the insolubility of tartrates in alcohol (c) ; from citric acid by the precipitation of calcium tartrate in cold water and of potassium tartrate in aqueous alcohol (c) ; from sub- stances not precipitable by oxide of lead by the method given under Acetic acid at g (40). Determined by acidimetry (f) ; gravimctrically as lead, calcium, or potassium tartrate (g) ; by. sp. gr. of water solutions (see Storer's " Dictionary of Solubilities "). a. Ordinary tartaric acid, or " dextrotartaric acid," crys- tallizes in colorless, transparent, hard, monoclinic (oblique rhombic) prisms, permanent 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 180 C., the crystals melt with formation of metatartaric acid, etc. ; by higher heat in the air, various distillation products are generated, and the mass burns with the odor of burnt sugar and the separation of carbon. TARTARIC ACID. 15 Pure tartaric acid dissolves in cold concentrated sulphuric acid, colorless, the solution turning black when warmed. c. The normal tartrates of potassium, sodium, and ammo- nium, and the acid tartrate of sodium, are freely soluble in water ; the acid tartrates of potassium and ammonium are spar- ingly 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 calcic tartrate (distinction from Citric acid, which precipitates only when heated). The same 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 concen- trated 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 15, 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 sepa- ration from Citric, Oxalic, and Malic acids). Tartaric acid is distinguished from citric acid, in crystal, and the former is detected in a crystalline mixture of the two acids, as follows : * * Hager's "Untersuchungen," B. 2, S. 103. 1C SOLID NON-VOLATILE ACIDS, 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 cen- timeters (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 a few minutes, 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 tar- trates 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 ammoniacal solution of tartrate of ammonium (distinction from 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. d. The copper sulphate with potassa is not reduced by tar- taric acid. Potassium permanganate solution is reduced very slowly by free tartaric acid ; but quickly by alkaline solution of tartrates, with separation of brown binoxide of manganese (dis- TARTABIC ACID. 17 tinction from Citrates which separate the brown binoxide of man- ganese slowly or not at all, leaving green solution of manganate). e. Tartaric acid may be extracted from tartrates by decom- posing with sulphuric acid and dissolving with alcohol, sulphates being generally insoluble in alcohol. Free tartaric acid may be extracted from water solutions by agitation with amylic alcohol, which rises to the surface. Quantitative. -f. Free tartaric acid, unmixed with other acids, may be determined volumetrically 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. g. 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. PbC 4 H 4 O 6 : H 2 C 4 H 4 O a :.:_!: 0.422535. In absence of acids forming insoluble calcium salts, tartaric acid may be precipitated from solution of neutral sodium tar- trate by chloride of calcium, If ammonium salts are present, the ammonia should first be mostly expelled by adding sodium 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 C 4 H 4 O 6 +4H 2 O : H 2 C 4 H 4 O 6 : : 1 : 0.577. In presence of citric acid, oxalic acid, sulphuric acid, phos- phoric acid, etc., the tartaric acid may be determined as potas- sium bitartrate. The solution of acid is made nearly neutral by addition of soda, or the solution of salt (tartrate) is made slightly acid by 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 concentrate,! solu- tion of acetate of potassium. The precipitate is washed with alcohol, and dried on the water bath. KH C 4 H 4 O 6 : H 3 C 4 H 4 O 6 : : 1 : 0.797. Results approximate. 18 SOLID NON- VOLATILE ACIDS. 7. KACEMIC ACID. Isomer of tartaric acid, from which it is distinguished as follows: By forming triclinic crystals., H 2 C 4 H 4 O 6 . H 8 O ; soluble in 5 parts cold water or 48 parts of alcohol of sp. gr. .809 ; slightly efflorescent on the surface ; losing the water of crystallization at 100. By its solution (uncom- bined) 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 in hydrochloric acid, precipitated again by ammonia, that is, not soluble in chloride of ammonium solution. By being inactive toward polarized light, 8. CITRIC ACID. H 3 C 6 H 5 O 7 . Characterized by the form, solubilities, and fusibility of its crystals (a) ; by the properties of its salts of calcium, barium, lead, silver, potassium (Z>) ; by the limits of its reducing power (c). Separated (as free acid) from sulphates and other substances insoluble in alcohol by its solu- bility in this menstruum (c? ) ; 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. Determined by acidimetry (/) ; by precipitation as barium citrate to be weighed as barium sulphate, or as barium citrate. a. The citric acid of commerce is crystallized (from rather concentrated solutions) as H 3 C 6 H 6 O 7 . H 2 O, in large, transparent, colorless, and odorless prisms of the trimetric system. These crystals slowly effloresce in the air between 28 and 50 C., and lose all their water of crystallization at 1 00 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, character- istic vapors, containing acetone (see Acetic acid, 40, c), while Aconitic acid (9) is formed in the residue. (The odor is dis- tinctly unlike that of heated Tartaric acid.) Citric acid is soluble in less than its' weight of water, in 1 .5 parts of 90 per CITRIC ACID. 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 water ; 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 precipita- tion 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, Kacemic, Oxalic acids) ; but on boiling a slight precipitate is formed (distinction from Malic acid). Solution of chloride of calcium does not precipi- tate 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 3 (C c H 5 O 7 ) 2 . 2H 2 O, 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 pre- cipitates from solutions of neutral citrates, and from even very dilute alcoholic solution of citric acid, the white citrate of lead, Pb 3 (C 6 H & O 7 ) 2 .|-H 2 O, 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 (for- mation 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 from Tartrate). Solution of permanganate of potassium is scarcely at all affected by free citric acid in the cold. 20 SOLID N ON- VOLATILE ACIDS. With free alkali, the solution turns green slowly in 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 barium citrate, which is then carefully decomposed with sul- phuric acid. From citrates soluble in water, the acid may be obtained by decomposing with sulphuric acid (not added in excess), then removing the water by evaporation at a tempera- ture 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, Eacemic, 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 grammes (fa of | of C 6 H 8 O 7 . H 2 O) 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 :f The citric acid is obtained as alkaline citrate ; if free, by neu- tralization 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. t J. CREUSE, American Chemist, I., 424 (1871). ACONITIC ACID. 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 sul- phuric acid several times, till the weight is constant. 3BaSO 4 : 2H S C 6 H 5 7 .H 2 : :1: 0.601. Hager directs that barium or calcium citrate (washed with alcohol) be dried at 120 to 150 and weighed. Ba 3 (C 6 H 5 O 7 ) a : 2H 3 C 6 H 5 O 7 . H 2 O : : 1 : 0.53232. 9. ACONITIC ACID. H 3 C 6 H 3 O 6 . A colorless solid, crystal- lizing 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. Calcic aconitate is soluble in about 10ft 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 aconitate is sparingly soluble in water, soluble in alcohol or ether, blackened by boiling with water. Free aconitic acid is precipitated by mer- curous nitrate, but not by most metallic salts until after neu- tralization. Aconitic acid is separated from Monkshood (Aconitum napelhts), Larkspur (Delphinium consolida), Equisetum, Black Hellebore, Yarrow (Achillea millefolium), and other plants, in which it exists as calcium salt, by evaporating the clear decoc- tion to crystallize. The crystals of aconitate of calcium are dis- solved and precipitated by acetate of lead, and the lead salt decomposed by hydrosulphuric 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 22 SOLID NON-VOLATILE ACIDS. 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 2 C 4 H 4 O . Identified more especially by its deportment \vhen heated (a) ; by the deportment of its lead salt when heated under water (5), and of its calcium salt in water and in alcohol (d). Separated 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 solu- tions (d ) ; from tannic acid, also, by aqueous solubility of calcic malate, and from formic, acetic, benzoic acids by alcoholic inso- lubility of calcic malate (d). Determined 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 malic 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). Con- centrated sulphuric acid darkens malic acid very slowly after warming. Hydriodic acid changes it to succinic acid with sepa- ration 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-bath to 175 or 180 C., evolves vapors of maleic and fumaric acids, which crystallize in the retort and receiver. The fumaric acid forms slowly at 150 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 in alcohol or ether. If the temperature is suddenly raised to 200, the maleic acid is the chief product. MALIC ACID. 23 Maleic acid crystallizes in oblique, rhomboidal prisms, which melt at 130 and vaporize at about 160, and are readily soluble in water and in alcohol. The test for malic acid, by heating to 175 or 180, 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 100, and does not lose weight at 120 ; at the temperature of the test water- vapor is separated maleic and fumaric acids both having the composi- tion of malic anhydride (C 4 H 4 O 4 ). b. Solution of acetate of lead precipitates malic acid, more perfectly after neutralizing with ammonia, as a white and fre- quently 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 ammo- nia, 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 and moistened with alcoholic ammonia, and then treated with absolute alcohol, only the malate of ammonium dissolves (distinction from 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. d. Solution of chloride of calcium does not precipitate malic acid or malates in the cold (distinction from Oxalic and Tartaric acids) ; only in neutral and very concentrated solutions is a pre- cipitate 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 white bulky precipi- 24 SOLID NON-VOLATILE ACIDS. tate of calcic malate in even dilute 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 one or two volumes of alcohol, with chloride of calcium. In separation from Tannic acid, both acids may be precipitated by chloride of calcium, with a slight excess of ammonia and alcohol; the malate is then washed out of the precipitate with water. Quantitative. e. The alcoholic solution of malate of am- monium prepared as directed in c may be precipitated with acetate of lead, washed with alcohol, dried and weighed as malate of lead. PbC 4 H 4 O a : H 2 C 4 H 4 O 5 : : 1 : 0.3953. 11. MECONIC ACID. H 3 C 7 HO 7 . Identified by its physical properties and precipitation by hydrochloric acid (a) ; its reactions with iron and other metals (#) ; and by its products when heated (c). It is separated from opium through formation of the calcium salt or lead salt (d). a. Meconic acid crystallizes in white shining scales or small rhombic prisms, containing three molecules of crystallization water, fully given off at 100 C. It is soluble in 115 parts of water at ordinary temperatures, less soluble in water 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 meco- nates are mostly insoluble in water. Meconates are nearly all insoluble in alcohol. They are but slightly or not^at all decom- posed by acetic acid. Solutions of meconates are precipitated by hydrochloric acid, as explained above. b. Solution of meconic acid is colored red by solution of ferric chloride. One ten-thousandth of a grain of the acid in ME CONIC ACID. 25 one grain of water with a drop of the reagent acquires a distinct purplish-red color (WORMLEY). The color is not readily dis- charged by addition of dilute hydrochloric acid (distinction from Acetic acid), or by solution of mercuric chloride (distinction from sulphocyanic acid). Solution of acetate of lead precipi- tates meconic acid or meconates as the yellowish-white meconate of lead, Pb 3 (C 7 HO 7 ) 2 , insoluble in water or acetic acid. Excess of baryta water precipitates a yellow trimetallic meconate. Solution of nitrate of silver in excess precipitates free meconic acid on boiling, and precipitates meconates directly, as yellow trimetallic meconate ; if free meconic acid is in excess, the preci- pitate is first the white dimetallic meconate ; both meconates being soluble in ammonia and insoluble in acetic acid. Solution of chloride of calcium precipitates from solutions of meconic acid, and even from neutral meconates, chiefly the white mono- metallic meconate, CaH 4 (C 7 HO 7 ) 2 . 2H 2 O, sparingly soluble in cold water ; in the presence of free ammonia, the less soluble, yellow dimetallic salt, CaH C 7 HO 7 . H 2 O, is formed. Both preci- pitates are soluble in about 20 parts of water acidulated with hydrochloric acid. c. At 120 C. (248 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. Solu- tion of comenic acid gives a red color with ferric chloride, green pyramidal crystals with cupric sulphate in concentrated solu- tion, and a yellowish-white granular precipitate with acetate of lead. d. The separation of meconic, acid from opium is effected with least loss by precipitating the infusion with acetate of lead (leaving the alkaloids as acetates with some excess of lead in the filtrate). The precipitate is decomposed, in water, with hydro- sulphuric acid gas, and the filtrate therefrom is concentrated (and acidulated with hydrochloric acid) to crystallize the meconic acid. 26 SOLID NON-VOLATILE ACIDS. The crystals are purified by dissolving in hot water and crystal- lizing 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. Pharmacopoeial preparation of morphise 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 from calcium by repeated solution in the same solvent, used just below 100 C., and each time in a slightly diminished quan- tity. The acid may be further decolorized by neutralizing with potassic carbonate, dissolving in the least sufficient quantity of hot water, draining the magma of salt when cold, dissolv- ing again in hot water and adding hydrochloric acid to crys- tallize. 12. DIGITALIO ACID. Digitaleic acid. Digitoleic acid. A solid of a green color, crystallizing in slender needles, some- times 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 pre- cipitates crude digitalic acid. This is purified by crystallization from alcohol. 13. TANNIC ACIDS : Vegetable educts having an astrin- gent taste and an acid effect on test-papers, mostly amorphous, TANNIC ACIDS. 27 not 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 formulae, C 27 H 24 O 18 ; C 27 H 22 O 17 ; C 14 H 10 O 9 (SCHIFF). The tannic acids are further characterized by forming in solu- tions 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 com- pounds with many heavy metals. They all absorb oxygen, espe- cially in presence of alkalies, and act as powerful reducing agents quickly decolorizing solution of permanganate, and reducing the heated alkaline copper solution. Tannic acids are more per- manent 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^xlissolved 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 w r ill appear. f By oxidation the tannic acids acquire a dark color, brown, black, green, or red. Gallotannic 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. Oh. Pharm., clx., 40-56. t 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 gegilops), and in sumac. It is a glucoside, and it does not yield pyrogal- lic acid by dry distillation. The pathological tannic acid of Wagner, or gallotannic acid, is found in common or Turkish gall- nuts 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 gallo- tannic 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 ammonia precipitates ferric hydrate. Ferric salts give green precipitates with quinotannic acid, mori- tannic 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 CafFe- tannic acid. Tannic acids are removed from solution by digestion with oxide of copper, oxide of zinc, or animal membrane ; or by pre cipitation with 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 deter- mined 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 ammonium to prevent the precipitation of gallic acid) (d). TANNIC ACIDS. a. A water solution of gallotannic acid&t 17.5 C. (63.5 F.) contains as follows (after HAGER) : p -c. SPEC. GRAV. P. C. SPEC. GRAY. P. C. SPEC. GRAY. 20 1.0834 13 1.0530 6 1.0242 19.5 1.0803 12.5 1.0510 5.5 1.0222 19 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 4 1.0160 17.5 1.0719 10.5 1.0427 3.5 1.0140 17 1.0698 10 1.0406 3 1.0120 16.5 1.0677 9.5 1.0386 2.5 1.0100 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 14.5 1.0593 7.5 1.0304 0.5 1.0020 14 1.0572 7 1.0283 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 membrane. 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 ori- ginal 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), accord- ing to b. b. A weighed quantity of recently ignited oxide of copper . about 5 times that of the tannin is added to the prepared solu- tion ; 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 NO N- VOLATILE ACIDS. 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 dis- solved 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 precipi- tated, 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 C 4 H 4 O 6 r=325), is preci- pitated by one equivalent of tannic acid (C 27 H 24 O 18 =636) ; or, 0.002555 anhydrous tartrate is precipitated by 0.005 of the tannin. Dissolving 2.555 grams of anhydrous tartrate of antimony and potassium in water to make one litre of solution, each c.c of the same corresponds to 0.005 of tannic acid. The prepared solu- tion of tannic acid which may contain pectous substances with- out 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 ammo- nium is present (GERLAND). 14. GALLIC ACID. C 7 H 6 O 5 ; crystallizing with H 2 O. 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 but slightly soluble in absolute ether, inso- luble in chloroform or petroleum naphtha. Its non-alkaline metallic salts are insoluble in water but soluble in alcohol, and GALLIC ACID. 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 characterized by its physical properties (as above given) ; by its reactions with iron salts (a), with alkalies (5), with tartrate of antimony and potassa and with alkaline arsenate in the air (c), and with molybdate of ammonium (d)> It is distinguished from the tannic 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 determined, 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 car- bonate 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 tan- nomelanic 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 of arsenate 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 alkalies restores the green color, but it is destroyed by excess of alkali.* * PROCTOR : Jour. Chem. Soc., 1874, p. 509. 32 SOLID NON- VOLATILE ACIDS. d. Molybdate of ammonium reacts as with tannic acid. e. Gallic acid does not precipitate gelatin, albumen, or starch- paste, but it forms a precipitate with a mixture of gum-arabic and gelatin. f. Gallic acid does not reduce alkaline copper solution, but reduces salts of gold and silver, and quickly decolorizes perman- ganate solution. Quantitative. g. The prepared solution is fully preci- pitated with a filtered solution of cupric acetate ; the precipitate washed and then exhausted with cold solution of carbonate of ammonium. The last solution, containing all the gallate of cop- per with a very little tannate, is evaporated to dryness, 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). (Method -of FLECK modified by SACKUR and WOLF.) 15. PYROG-ALUC ACID. C 6 H 6 O S , Pyrogalline. Pyro- gallol. Characterized by its physical properties (a) ; its peculiar avidity for oxygen (6) ; its reactions with alkalies, lime, iron, copper, etc. (c). It is distinguished from tannic acid by not precipitating gelatin or moderately dilute tartrate of anti- mony and potassium or cinchonia, and by its different reactions with both ferrous and ferric salts : from gallic acid b;y 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 permanganate. a. Pyrogallic acid crystallizes in long prismatic plates or needles, of a white or yellowish-white color, and an acid and very bitter taste. At 115 C. (239 F.) it melts, and at about210 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. PrROOALLIC ACID. 33 f " ' b. It is permanent in dry air free from ammonia, but in moist or ammoniacal air it gradually darkens, and in water solution it turns brown to black, sooner if boiled, still mor-e^ rapidly in presence of alkalies, absorption of oxygen 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 lime 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 brown- green 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(C 6 H 5 O 3 ) 3 : 2C 6 H 6 O 3 : : 457 : 252 : : 1 : 0,55142, 16. QUIWOTANNIC ACID. Cinchotannic acid. Kino- tannic acid. See Tannic acids (13) for appearance, taste, solu- bilities, and reactions with alkalies and with iron salts. It pre- cipitates 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 quino- tannic 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 Cin- chona bark, see under Quinic Acid, d. 17. CATECHUTANMIC ACID. Has the properties of tannic acids in general, giving a grayish-green precipitate with 34 SOLID NON-VOLATILE 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 separated from 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 car- bonate 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 AGED. Catechucic acid. Catechin. Tanningenic 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 (iron- green) 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 from catechutannic acid). With strong sulphuric acid it forms a deep purple liquid. Catechuic acid may be separated from catechutannic acid and the other 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 washed) 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. TANNIC ACIDS. 35 19. MORINTAKNTC ACID. C 13 H 10 O 6 . Capable of crystallization ; yellow, with great tinctorial power, and of an astringent, sweetish taste. Melts at 200 C., and at higher tem- peratures distils phenic acid. In reactions with alkalies, oxidiz- ing 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 precipi- tate ; with stannous chloride a yellowish-red precipitate. It is separated from Fustic by spontaneous deposition from the concentrated decoction. 20. CAFFETANNIC ACID. Caffeotannic 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 oxy phenic acid as an oil which solidifies in the cold. With fixed alkalies in solution it turns yellow to reddish-yel- low, 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 dingy- yellow, crystallizable substance, heavier than water, in which it is but slightly soluble w T hen cold. Caffetannic acid gives the green color with ferric salts. It reduces nitrate of silver, in the specular form, when heated. 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 (distinc- tion from Catechuic acid). It gives a yellow precipitate with barium salts. By gradual addition of acetate of lead, in decoction of coffee, it is precipitated next after (the very little) citric acid. Decom- 36 SOLID NON-VOLATILE ACIDS. posing the precipitate with hydrosulphuric acid, and evaporating the filtrate, it is obtained in impure, yellowish mass. 21. BOHEIC ACID. C 7 H 10 O 6 . Boheatannic Acid. Amor- phous, 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, BaC 7 H 8 O 6 . H 2 O. With acetate of lead, in alcoholic solution, it forms a grayish-white precipitate, PbC 7 H 8 O 6 . H 2 O, which can be washed with alcohol and dried at 100 C. It is separated from the quercitannic acid, in Hack tea, by precipitating the latter with acetate of lead in the boiling decoc- tion, filtering ; after twenty-four hours filtering again, and neu- tralizing the clear solution with ammonia, when the yellow basic salt is precipitated, PbO.PbC 7 H 8 O 6 . The latter may be decomposed in alcohol by hydrosulphuric acid, and the filtrate concentrated in vacuum or over oil of vitriol. 22. QUTN1C ACID. C 7 H 12 O 6 . Kinic acid. Identified by its physical properties and reactions (a) ; by its generation of quinone (#) ; by its reactions with a few metals (c). Separated from cinchona bark, by crystallization from a solution freed from quinovic acid (d) ; from cinchona bark, coffee, or bil- berry, by precipitating its calcium salt from a sufficiently purified 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 161 C. (322 F.), at higher temperatures evolving combus- tible gas, phenic 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. QUINIC ACID. 37 b. Distilled with moderately dilute sulphuric acid and binoxide of manganese, it yields an abundant yellow crystalline sublimate of quinone, recognized in very small quantities by its irritating odor, exciting tears. Farther, aqueous solution of Quinone is colored brown by ammonia, and yellow-green by chlorine water ; it stains the skin brown. c. Quinic acid decomposes carbonates. Its metallic salts are soluble in water, except the basic quinate of lead, but are insolu- ble in alcohol. It prevents the precipitation of many metallic oxides by alkalies. Quinate of silver is white, and bears the heat of the water-bath. The quinate of calcium crystallizes well from water solution as Ca(C 7 H 11 O 6 ), . 5H 2 O, which loses all its water of crystallization at 120 C. (248 F.) Or, it may be precipitated from solution of alkaline quinates by adding chloride of calcium, ammonia, 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 bark 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 acetate of lead to precipitate the quino- vic 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 water, 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. 38 SOLID NON-VOLATILE ACIDS. With the crystals of quinic acid there will now finally deposit amorphous or oily quinotannic acid. This may be separated by washing 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 cin- chona bark with lime, according to the United States Pharma- copoeial preparation of quinise 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 plant (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 purification by recrystallization from water. Thoroughly dried or moderately roasted coffee beans, 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 quinate of calcium 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 put 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. C 30 H 48 O 8 . Kinovic Acid. Quinovin or Kinovin. Quinova bitter or Kinova bitter. An amorphous solid, having a very bitter taste, nearly insoluble in svater, very soluble in alcohol, slightly soluble in ether, soluble in chloroform. (According to DE VRII, chloroform dissolves GENTIANIC ACID. 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 compo- sition (C 24 H 38 O 4 ), and forms definite salts with metals. Quinovic acid forms a soluble calcium salt, and hence it is dissolved from cinchona 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 precipita- tion from alcohol by water. For the separation of quinovic, quinic, and quinotannic acids, each from the same portion of bark, see- Quinic Acid, d. In the manufacture of cinchona alka- loids, the acidulation of the water by which the decoction is made interferes with the solution of quinovic acid, which may be at least partly left in the residue. 24. COLUMBIC ACID. C 42 H 46 O 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 (C 42 H 44 O 12 ) 2 when dried at 130 C. Acetate of copper does not precipitate it. In columbo root, columbic 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. GENTIANIO ACID. C 14 H 10 O 5 . Gentisic acid. Gen- tianin. Gentisin. Light-yellow, tasteless, solid, crystallizing in slender needles, not decomposed at 200 C., but carbonizing with partial sublimation at 300 to 400 C. It is soluble in 36 parts 40 SOLID N ON- VOLATILE ACIDS. water at ordinary temperature, readily soluble in alcohol, and moderately so in ether. Its solutions are neutral to litmus. It dissolves in aqueous alkalies with a golden-yellow color. Strong sulphuric acid dissolves 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 C 14 H 8 O 5 . H 2 O, is an orange-colored precipitate. The lead salt is insoluble. Gentianic acid is separated from gentian 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 washed with a little ether to remove fat, and repeatedly crystallized from alcohol to separate from resin. 26. CAEMLN1C ACID. C 9 H 20 O 6 . 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 alco- holic solution it precipitates alcoholic potassa red changing to dark violet, and forms red precipitates with acetates of ]ead, zinc, copper, and silver. It is turned blue by sulphate of alumi- num, and yellow by stannous chloride. Carminic acid is a glucoside, boiling dilute mineral acids transforming it into carmine-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 GAMBOGIC ACID. 41 filtered. The filtrate is evaporated and dried on the water-bath, and the residue extracted with alcohol. 27. CHRYSOPHANTC ACID. Chrysophane. Rheic Acid. A pale yellow or orange-yellow solid, crystallizing in six- sided tables or moss-like aggregates of scales, subliming with partial decomposition when heated. Sparingly soluble in cold water, soluble in 1,125 parts of 86 per cent, alcohol at 30 C. (86 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 alkalies 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 alco- holic solution with alcoholic subacetate of lead it forms a reddish- white precipitate, becoming rose-red when boiled with water. In ammomacal solution it is precipitated filac by neutral acetate of lead, and rose-color by alum. Strong sulphuric acid dissolves it unchanged; strong nitric acid converts it into a red substance, containing chrysammic acid (produced from Aloes by nitric acid) . Chrysophanic acid is separated from Rhubarb 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 (Parmdia parietina), 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 Rumex, 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. GAMBOGIO ACID. A resinous solid, hyacinth-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 42 SOLID VOLATILE ACIDS. 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 preci- pitated yellow by acids. The solution of gambogiate of ammo- nia forms with barium salts a red precipitate ; with zinc salts, yellow ; lead salts, reddish-yellow ; silver salts, brownish-yellow ; and copper salts, brown precipitates. It is bleached and decom- posed by chlorine, and decomposed with formation of nitrophenic acid by nitric acid. It is dissolved with red color by cold con- centrated sulphuric acid; addition of water precipitating it unchanged. 29. SANTAUC ACID. Santalin. A fine red, tasteless, and odorless crystallizable solid, melting at 104 C. Insoluble in water, very 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 separated from Sandal- wood (red saunders) by obtaining, first, an ethereal extract, then from this an alcoholic extract, which is washed with water, dissolved again in alcohol, and precipitated therefrom by alcoholic solution of acetate of lead. The lead compound is washed by alcohol, then decom- posed in alcohol with dilute sulphuric acid. SOLID VOLATILE ACIDS. 30. BENZOIC ACID. HC 7 H 5 O 2 . Identified by its phy- sical properties, especially in sublimation (a) ; by its oxidation to nitrobenzole (&), and its deoxidation to bitter almond oil (c) ; by its reactions with metallic salts (d). Distinguished from BENZOIC ACID, 43 Cinnamic acid by the action of permanganate upon the latter (see 31, 1) ; from Hippuric acid by distillation with potassa; from Salicylic acid by the color of its ferric salt (d). Separated from non-volatile and highly volatile substances by sublimation (a) ; from Succinic and many other acids by the alcohol solubility of its barium salt (d) ; from Succinic and Hippuric acids by its solubility and extraction from water solutions by chloroform or ether (c). Gravimetrically determined 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. (59 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. Most 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 solu- bility of benzoic acid as already given. Sulphuric acid dissolves benzoic acid. Benzoic acid decomposes carbonates. Benzoic acid melts at 121 C. (250 F.), and sublimes at 240 to 250 C. (464 to 482 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 with phosphoric acid evolve benzoic 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, nitrobenzole (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 Devolved, 44 SOLID VOLATILE ACIDS. bitter almond oil (benzoyl hydride, C 7 H,OH) is produced, and recognized by its odor. d. 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 precipi- tates in solutions not too dilute. Ammoniacal chloride of barium with alcohol gives no precipitate (distinction and separa- tion 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 benzoate by acetate of lead, washed with cold water or alcohol acidulated with one-half per cent, of acetic acid, and dried at 100 C., may be weighed for determination of benzoic acid : Pb(C 7 H 6 O 2 ) 2 : 2HC 7 H 5 3 : : 1 : 0.54343. 31. CINNAMIC ACID. HC 9 H 7 O 2 . Characterized by its physical properties and reactions in the dry way (a) ; its reac- tions with oxidizing agents (b) ; its reactions with metallic salts (c). Distinguished from benzoic acid by action with oxidizing agents (), by the color of its ferric salt and by its precipitate with manganous salts (c) . Separated from non-vola- tile 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 laminae, melting at 129 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 from water solutions of its salts of alkali metals. SUC C INI C ACID. 45 When slowly distilled, cinnamic acid evolves 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. 1). A saturated hot-water solution, acidulated with sulphuric acid, is treated with a few cubic centimetres 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 apparent. 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 cinna- mic acid in most cases with simultaneous production of benzoic acid. Cinnamates with strong nitric acid give off odor of cinnamon oil and bitter almond oil. c. Ferric salts with cinnamates give a yellow precipitate ; manganous salts with excess of cinnamates give a white precipi- tate (none with benzoates) ; copper salts, a greenish-blue precipi- tate; acetate of lead, a precipitate not soluble in water, Pb (C 9 H 7 O 2 ) 2 , from which alcohol washes out a part of the cinnamic acid ; nitrate of silver, a stable white precipitate, AgC 9 H 7 O 2 , insoluble in boiling water ; baric and calcic salts, precipitates, easily soluble in hot water. 32. SUCCLNTC ACID. H 2 C 4 H 4 O 4 . Characterized and identified by its physical properties (a) ; its resistance to oxida- tion (b) ; its reactions with iron, manganese, lead, barium, calcium, etc. (c). Distinguished from cinnamic acid by the color of its iron salt and by not precipitating manganous salts (31, f). Separated from non-volatile materials by sublimation (a) ; from benzoic acid by insolubility of its barium salt in alcohol (30, ft *?*> f> I S I R O Ci5^ fl ' Green irty b' g! I is i Greenish irty b'wn I I s S I yel IS. 16 ,fj Q> ^ >c3 >o5 ^j ^rt ^>d3 >fl -2^ i3 o3 Ss 2 & II sg s ^ g fl| fi U ^& fl-g & 2| PQ-O C5 fi 4) l> |& S OS >iOJ fl * cu f3 fli Ss i ^ s8 Q ^ O h 5 sh- si I I II g8 Ii I ff s 1 ! 1 I EXAMINATION OF > . 62. TESTS WITH 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 almonds 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, from sweet almonds, Beech-nut oil, Castor oil, Cod-liver oil, Hemp-seed oil, Olive oil, Sesame oil. 63. Special examination of Butter. Separation of fats from non-fatty substances by melting (a), by benzole (b). Identification of butyrin, etc., by etherization after saponifica- tion (see Butyric acid, 41, b). Distinction from (mixtures of) lard by treatment with sulphuric acid (c), by treatment with ether at 18.5 C. (d), or with petroleum naphtha at 10 to 15 C. (e) ; from foreign color by borax solution (f). a. About 10 grams of the butter are melted in a large test- tube, by insertion in water of 50 to 60 C. (122 to 140 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 yel- lowish-white. (The bottom layer may be at most ; from good table butter should not be over -1.) b. In a large and strong test-tube place 5 grams of the butter, melt by dipping in water at 60 C. (140 F.), add fully an equal volume of benzole, cork securely, agitate, and leave at about 40 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, d, e). For the separation by benzole, a graduated tube may be used, as follows (HOORN) : A glass tube is prepared, 20 centi- metres (8 inches) long, its upper two-thirds having a diameter of 2 centimetres (0.8 inch), its lower third narrowed and gradu- ated 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 ben- zole 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 a, 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 be- coming 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 brown- red or brown-black. d. The butter is melted over the water-bath, and after stand- ing 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 EXAMINATION OF BUTTER. 83 dried on blotting-paper, introduced into a wide-necked flask, and covered with ether at a temperature of 18.5 C. (65.3 F.) If the butter was pure, the fat fully dissolves to a clear, lemon- yellow 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 tempera- ture 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 centi- metres (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 J inch) diameter, and 4 to 5 centi- metres (1J 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. Im- merse the test-tube in water at exactly 18.5 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. With 5 c.c. ether. With 10 c.c. ether. From 1.5 grams pure butter, remained insoluble, 0.18 grms. 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 NEUTRAL SUBSTANCES, LIQUID OR FUSIBLE. From equal parts tallow and butter, . 0.6 grms. Prom J- tallow and { butter, ... 0.3 0.8 grms. Prom 1 lard and f butter, .... 0.15 " 0.8 Prom | lard and | butter, . . . . 0.67 e. The fat of butter, separated according to a, is treated with 7 parts of petroleum naphtha at a low temperature 10 to 15 C. when the fat of butter dissolves, and tallow, or lard if over 10 per cent., remains in sediment. y. 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 sub- side. 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. THE PATS ARE DETERMINED in Milk by separation with ether, from the milk (a), from the residue (#) ; 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 volume of 10 per cent, solution of potassa (to hold the casein in solution), in a cylinder, and repeatedly extract with ether. Dry the ether residue at 110 C. [Partner, see Phar. Jour., 1874, Sept. 5, p. 188 ; also Wanklyn's Milk Analysis, New York, 1874, p. 24.] . Evaporate 10 grams of milk with 5 grams (^resh dried) charcoal powder or 15 grams (just ignited) ferric oxide or baric sulphate at 100 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 110 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.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 MILK. GLYCERIN. 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 from Volatile 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 separated 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. C 3 H 5 (HO) 3 . Characterized by its phy- sical properties (a) ; by the products of its decomposition when heated () ; by the limits of its reducing power and its inter- ference 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 86 NEUTRAL SUBSTANCES, LIQUID OR FUSIBLE. liquid during the freezing of its water mixtures ; distilling very slowly with steam at 100 C., slowly giving off vapor with partial decomposition at 120 C. (248 F.), boiling with decomposition of the most part at 290 C. (554 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 alcohol (separation from Sugar, Dextrin, Gum, Extractives the mixture not acid) ; not soluble in benzole, bisulphide of carbon, petro- leum 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 dis- solves one-fifth per cent., each, of sulphur and phosphorus, 20 per cent, of 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 decom- position, and is changed by chlorine and by nitric acid. It com- bines with strong sulphuric acid, without color or effervescence, as the instable glycerosulphuric acid. b. At its boiling point, as above, glycerin evolves suffocating vapors of acrolein, etc., which vapors may be condensed by ice to a liquid, chiefly acrolein, with some acrylic acid, acetic acid> 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 sand- bath, 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 reduce 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 empy- reumatic 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 in the air from a water- bath, glycerin retains about 5 per cent, of water. The U. S. Pharmacopoeia requires spec. grav. 1.25; the German Pharma- copoeia spec. grav. 1.23 to 1.25. GLYCERIN P. C. SP. GR. FREEZING. GLYCERIN P. C. SP. GR. FREEZING. 10 1.034 1C. 60 1.159 20 34 40 1.051 1.075 1.105 2.5 C. 6C. 17.5 C. 70 80 90 1.179 1.120 1.232 below 35 C. 50 1.127 31.34 C. 94 1.241 67. SOAPS. Alkali salts of Fatty acids (and of Resin acids). Characterized 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 dissolv- ing 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. 88 NEUTRAL SUBSTANCES, 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 palmltates 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 40 to 50 C., which is after some time increased gradually, so as not to fuse, to 100 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 determina- tion of the water is effected by dissolving 1 to 2 grams soap in the least sufficient quantity of strong alcohol, adding a weighed quantity of fine sand, just dried, then evaporating, with tritura- tion, and drying at 110 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. Z>. The amount of absolute soap is determined from the fat acids approximately (GR^EGER) as calcium precipitate after solu- tion 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 precipi- tated with calcic chloride. The precipitate is gathered in a tared filter, washed, dried at 100 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. grav. 1.1x54, 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 QUANTITATIVE ANALYSIS OF SOAPS., 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. News, 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 (Jour. Chem. Soc., 1872, 934) separates the fat acids (and resin) by a limited quantity of petroleum naphtha. 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 100 C., and the residue weighed as fat acids. As to Resins in this process, see g. d. The fat acids may be approximately determined by the volume of their supernatant layer, after acidulation, in a gradu- ated cylinder (BUCHNER). 1 c.c. equals 0.93 gram. The weight of fat acid plus ^ equals the weight of fat ; and 1 00 parts of fat correspond to 155 parts average hard. soap. e. PONS recommends a volumetric determination of fat 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 gram 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 nitration, and washing and distilled water is added to make the liquid measure 1,000 c.c. In a stoppered flask of 60 to 80 90 NEUTRAL SUBSTANCES, LIQUID OR FUSIBLE. 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 Caters). 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. TTncombined fat 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. Resin can be extracted from dried and pulverized soap by means of benzole, 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 w r ith a mixture of water and a nearly equal volume of alcohol, the resin is dissolved out. h. Soap may be precipitated 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 uncombined 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 uncombined alkali of the soap, in- cluding alkaline carbonate. If the soap is dissolved in alcohol, alkaline carbonates remain undissolved and may be determined by adding volumetric solution of acid to the residue. Free alkali may be precipitated from alcoholic solution of soap by passing through a stream of carbonic acid gas. A qualitative QUANTITATIVE ANALYSIS OF SOAPS. 91 test for free alkali or alkaline carbonate is made by adding mercuric chloride to the soap solution; a red-brown to red- yellow precipitate indicates free alkali the fat acid salts forming only white precipitates. i. Then, for volumetric determination of the combined 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 solu- tion 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. / Determination 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 (SENIER). 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 plan for determination of the constituents of soap, 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 water-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 car- bonic acid gas ; if a precipitate forms, continue until its forma- : " A Process," etc., Am. Jour. Phar., 1874, 92 FUSIBLE NEUTRAL SUBSTANCES. tion ceases ; filter and wash and determine the alkali in the preci- pitate by a volumetric solution of (oxalic) acid. (See A.) 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 subsi- dent 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 g.) For (6) : Proceed according to the first method under j. For (7) : Estimate by difference ; or by evaporation of another portion with alcohol and sand, as directed in a. 68. BESINS. Compounds of C, H, and O. Vitreous and mostly brittle solids (when unmixed), softening and melting when gently heated, but not vaporizable (distinction from cam- phors) ; 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 combi- nation as resin-soaps ; and in alcoholic solution show the acid reaction. XESINS. 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, mix- tures 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 Me- dicinal resins and the Color resins. And, third, resins obtained from liquid plant juices which are dried as a part of the manu- facture ; these including two bodies insoluble in alcohol, Caout- chouc 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 solu- tion into water is by far the most generally applicable process ; solution with aqueous alkali and precipitation by acid may some- times be employed. 70. THE RESINOUS MATTER OF ALOES is fusible on the water- bath ; 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 paracumaric acid, 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 material 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 SUBSTANCES. matic when rubbed or warmed, of various colors, chiefly yellow or orange. Subjected to gradually increasing heat, it softens ; at 110 to 260 C., evolves a volatile oil colored blue by hydrochloric acid ; at about 235 C., evolves succinic anhydride ; at 287, it fuses; at higher temperatures, yields first a colorless oil, then a yellowish wax. Amber resin is insoluble in \vater, alcohol (except -^ 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 con- sistence " 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 sweetish- bitter and acrid taste and strong peculiar odor. Ammoniac is partly soluble in water, alcohol, ether, acetic acid, and aqueous alkalies. Ammoniac Resin is wholly soluble in alcohol, in fixed and volatile oils, in sulphuric acid, acetic acid, and aqueous alka- lies, 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 dis- tillation with water, contains sulphur, and boils at 140 C. Assafetida resin is readily soluble in alcohol, not wholly insolu- ble in water, nearly all soluble in ether, mostly soluble in alkalies. 74. BENZOIN Resins. Benzoin or " benzoin-gum " consists of about three-fourths part resin's, 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 carbon- ate of sodium, or in ammonia, but soluble in ether. Resin-J has the solubilities above given for a, 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. grav. 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 alka- lies. It is not changed by sulphuric acid, but is stained deep yellow by nitric acid. 76. CAOUTCHOUC. Fusible at 120 C. (248 F.) ; not vapor- izable. T}ie 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 95 FUSIBLE SUBSTANCES. "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, preci- pitate white metallic copaivates, more or less freely soluble in alcohol. The silver precipitate is crystalline, and the lead preci- pitate slightly so. The other resins are soluble in alcohol, ether, fixed and volatile oils, and aqueous alkalies. 79. COPAL. Spec. grav. 1.045 to 1.139. Brittle, softening at 50 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 caout- chouc." 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 solu- tion to form a soap soluble in water not containing free alkali. 80. DAMMARA Resin. Australian. Dammaric acid with Dammaran that is, an acid and a neutral resin. Both 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 Indian dammara (ordinary dammara). Spec. grav. 1.04 RESINS. 97 to 1.09, brittle, melting when heated. Partially soluble in absolute alcohol, about T 3 ^ soluble in ether, fully soluble in fixed and volatile oils, benzole, and bisulphide of carbon, and in con- centrated sulphuric acid with a red color. It is not soluble in aqueous alkalies. 81. DRAGON'S BLOOD. A brittle, dark-brown, opaque, odor- less, and tasteless solid ; soluble (with 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 Eesin. 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; red- dish-yeljow in mass, 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 after-taste when chewed, causing a flow of yellow-colored saliva. Gamboge is easily emulsified with water, which dissolves gum from it, the resin being slowly deposited ; is readily soluble in alcohol (with a little starchy residue), is soluble in aqueous alkalies, and yields its resin (only) to the solvent powers of ether, chloroform, bisul- phide of carbon, and benzole (slowly) . Boiling solution of sodic carbonate dissolves gamboge gelatinous. Gamboge is wholly dissolved by the successive action of ether and water (separation from commercial impurities) . Gamboge Resin (" gambogic acid " usually extracted from gamboge by ether) is soluble in cold, concentrated, sulphuric acid, with a red color, and precipi- tated unchanged by adding water to this solution (a characteris- tic reaction). Boiled with nitric acid of 10 to 15 per cent, anhy- dride, the mixture then dissolved in alcohol and then treated with water, a yellow precipitate is obtained (distinction from Saffron or Turmeric). The aqueous alkaline gambogates are precipitated red by common salt, and give red precipitates with baric salts, yellow precipitates with zincic and plumbic salts, brown precipi- tates with cupric salts, and brownish-yellow with argentic salts 98 FUSIBLE SUBSTANCES. most of these precipitates being somewhat soluble in water and in alcohol. For the separation of gamboge resin from associated medi- cinal resins (HAGER) the material is triturated with 98 per cent, alcohol (and pulverized heavy spar) at a gentle heat, and the extract so obtained is dried and digested with chloroform. Aloes resin, Convolvulin, and Colocynth resin are left behind (with a part of Agaric) ; while the gamboge resin is dissolved, with Jalapin, Guaiac resin, Myrrh, Tolu resin, Senna resin (and a part of Agaric). The residue from this chloroform solution is now digested with boiling solution of sodic carbonate ; when, of those named above as in the chloroform solution, only the gamboge resin will dissolve (with traces of senna and agaric). Acids separate the gamboge resin from its soda solution. 83. GUAIACUM. A brittle, pulverizable solid, of spec. grav. about 1 .2, melting at a moderate heat ; of a faintly fragrant odor and persistent acrid after-taste. Its color is yellowish-green to reddish-brown ; the former color induced by exposure to the air. Water dissolves a one-tenth of guaiac resin, strong alcohol about nine- tenths, alcohol of 83 per cent, slowly dissolves it all. Ether and oil of turpentine dissolve about as much as alcohol ; benzole does not dissolve it. It nearly all dissolves in aqueous alkalies. Sulphuric acid dissolves it with a fine red color (and formation of glucose and guaiaretin) ; the solution is precipitated violet with water, or violet- blue to blue-green by alcohol. Guaiac resin is easy to suffer oxidation, whereby bright colors are produced. The powder and the alcoholic solution turn green by exposure to the air, or blue by exposure to ozone. The alcohol solution is also turned green by nitric acid, and blue by nitrous acid, chlo- rine, ferric chloride, or by ethereal solution of binoxide of hydro- gen in presence of blood-stains. Hyposulphite of sodium changes the blue color to violet and then bleaches it ; sulphurous acid bleaches it slowly or promptly if zinc has been placed in the acid. 84. HEMP RESIN. Cannabin. Resin of Indian hemp. A light-brown, lustrous solid or soft solid, melting at 68 C., and RESINS. 99 of a fragrant odor and bitterish, acrid taste. Insoluble in water, scarcely soluble in cold alcohol of 80 per cent., soluble in hot, strong alcohol, in ether, spirit of nitrous ether, chloroform, bisul- phide of carbon, cold volatile oils, and warm fixed oils. Insolu ble in aqueous alkalies ; having a neutral reaction. 85. INDIGO BLUE. C 8 H 6 NO. Inodorous, tasteless, an4 neutral. Sublimes from the solid state, at about 288 C., witk out decomposition if in a current of air or in vacuum, forming purple-red vapors in open vessels, and condensing in right rhombic prisms. It is insoluble in water, cold alcohol, ether, fixed and volatile oils when cold ; hot alcohol and hot oil of tur- pentine and hot fixed oils dissolving it very sparingly. Insoluble in aqueous alkalies. Soluble in creosote and in hot phenic acid ; soluble in concentrated sulphuric acid (as sulphindigotic acid). Indigo blue is separated from fixed substances by , sublimation from platinum foil (good indigo having 7 to 10 per cent, of ash) ; and by the use of solvents which leave it in residue. It is valued 1 , in numerous processes, by the quantity of chlorine or other bleaching agent necessary to decolorize it. 86. JALAP RESINS. Eesin of Jalap, of the pharmacopoeias. A brownish, brittle, opaque, fusible mass, or yellowish-gray to yellowish- white powder ; of a repulsive odor, slight at ordinary temperatures, but much increased on heating, and a pungent, acrid taste. It is soluble in alcohol (with neutral reaction), in aqueous fixed alkalies and alkaline carbonates, and in acetic acid ; insoluble in volatile and fixed oils. Resin of jalap consists of two distinct resins, Jalapin and Convolvulin ; that of pharmaco- pceial or Tuberose jalap being about one-ninth jalapin and eight- ninths convolvulin ; that of Fusiform jalap, mostly jalapin. 87. JALAPIN (or Scammonin) is a soft amorphous solid, brittle at 100 C., melting at 150 C., white in powder, tasteless, inodorous, and nearly neutral in reaction. It is very slightly soluble in water ; freely soluble in ether, chloroform, methylic alcohol, benzole, petroleum naphtha, and oil of turpentine. Cold concentrated sulphuric acid dissolves jalapin; the solution be- 100 FUSIBLE SUBSTANCES. coming purple in five or ten minutes, then brown, and lastly black. It dissolves in aqueous alkalies or their carbonates, and, on acidulating these solutions, Jalapic (Scammonic) acid is liberated as a body soluble in water and having a strongly acid reaction. The salts of jalapic acid are nearly all soluble in water, but subacetate of lead precipitates it. On heating Jalapin (or Jalapic acid) with dilute mineral acids, glucosic fermentation occurs, with formation of jalapinol and glucose. Jalapinol is in- soluble in cold, sparingly soluble in hot water, soluble in alcohol and in ether; soluble in aqueous alkalies with combination as jalapinolic acid. Jalapinolic acid, liberated from its alkali salts by acidifying, is insoluble in water, but soluble in alcohol and in ether. Its lead and barium salts are nearly insoluble in water. Jalapin and jalapic acid are amorphous ; jalapinol crystallizes in white cauliflower-like masses, melting at 62 C. ; jalapinolic acid crystallizes in tufts of needles (four-sided prisms), melting at 62 C. 88. CONVOLVULIN (the larger portion of Tuberose jalap and a very small proportion of Fusiform jalap) is a brittle, vitreous solid, melting below 100 C. when moist, or at 150 C. when dry, colorless and transparent in mass, or white in powder, inodorous and tasteless, and of a slight acid reaction. Nearly insoluble in water ; soluble in alcohol, acetic acid, and aqueous alkalies and alkaline carbonates (as convolvulinic acid) ; not soluble in ether (separation from Jalapin). It dissolves slowly in cold concen trated sulphuric acid, with a fine carmine-red color, afterward changing to brown ; this change being a glucosic fermentation, with formation of convolvulinol and glucose. But dilute sul- phuric acid has no effect. Convolvulic acid is formed in acidify- ing the alkaline solutions of convolvulin ; it is a white solid, fusing above 100 C., having a strong acid reaction, and freely soluble in water and alcohol, insoluble in ether. Its metallic salts are soluble, except that formed with basic acetate of lead. 39. LAC Resin. Stick Lac consists of about two-thirds resin, one-tenth coloring matter, with wax, gluten, etc. Seed > mama. 101 X <5> ^ x ^ Lac contains more resin and less coloring and nitrogenous matter. Shell Lac is about 90 per cent, resins, 5 per cent, wax, 2.5 per cent, gluten, and 0.5 per cent, coloring. The coloring matter of lac is soluble in water ; is bright red with acids and deep violet with alkalies ; is precipitated by alum. Shell Lac is insoluble in water ; soluble in alcohol ; mostly soluble in methylic alcohol ; wholly soluble in aqueous alkalies, and in water solution of borax, and in hydrochloric and acetic acids. Lac resin is separated from most other resins, and from many natural and commercial impurities, by dissolving in a solu- tion of J part borax and 20 to 30 parts water to one part of lac. The solution may be diluted farther. (Good shell lac leaves not over 1.5 per cent, residue ; poor, as much as 8 per cent.) By 10 per cent, ammonia at 25 to 30 C. lac is not dissolved, while Colophony dissolves and appears, after acidulation, as a precipi- tate. Cold ether (of 0.720 spec, grav.) does not dissolve more than 5 to 6 per cent., chloroform not over 7 J per cent, from good lac, the dissolved part being wax with a very little resin (separa- tion from Colophony and other resins). 90. MASTIC. A translucent solid, brittle and inodorous at ordinary temperatures, but soft and ductile when chewed and fragrant when heated, of a faintly terebinthinate taste. Alcohol dissolves about four-fifths, leaving Masticin undissolved. Ether, chloroform, and oil of turpentine dissolve it wholly. It is largely soluble in benzole. 91. MYRRH Resin. Consists of resins, about -J- part ; gums, about -| part; with a very little soluble extractive. Myrrh forms an emulsion and partial solution with water, a nearly com- plete solution with much aqueous potassa, and yields its resin to alcohol, ether, and chloroform. The Resin of Myrrh is readily soluble in alcohol, ether, chloroform ; slightly soluble in hot solution of sodic carbonate ; about one-half part soluble in bisul- phide of carbon. That part extracted with bisulphide of carbon, when dissolved in alcohol and warmed with 25 per cent, nitric acid, gives a violet color. 102 FUSIBLE SUBSTANCES. 92. OLIBANUM Resin. Frankincense. Incense. Olibanum is about one-half part resin, one-third part gum, one-twelfth part volatile oil. The gum is soluble in water ; the resin is soluble in alcohol. 93. Resin of PERU Balsam. About resins, f volatile oil, less than -^ cinnamic acid. The Balsam is of thick-syrupy con- sistence; spec. grav. 1.15 (sinks in an 18 per cent, solution of common salt). Soluble in absolute alcohol in all proportions, or in 6 parts of 90 per cent, alcohol with slight turbidity ; perfectly soluble in all proportions of absolute ether, chloroform, and amylic alcohol. Bisulphide of carbon dissolves the greater part; benzole and petroleum naphtha dissolve about one-half. It mixes with about -J part of castor oil, and with 1 part copaiba balsam. Sulphuric acid converts the balsam into a thick red mass. Aqueous alkalies dissolve out the resin. 10.0 of the bal- sam requires over 0.7 grams crystallized sodic carbonate to neu- trallize its cinnamic acid. 94. PODOPHILLUM RESIN. Consists of two resins. Insoluble in water ; wholly soluble in alcohol ; about J part soluble in ether ; wholly soluble in aqueous alkalies, from which solutions acids precipitate it (distinction from resins of Jalap and Scam- mony). Insoluble in benzole. 95. SANDARAC. A brittle, yellow solid. Contains three resins. Sandarac is insoluble in water; wholly soluble in alcohol- j- part dissolving easily in cold ordinary alcohol, a small part requiring boiling alcohol, and a still smaller part a large quantity of this solvent for solution. It is easily soluble in ether and in oil of turpentine, imperfectly soluble in bisulphide of carbon, benzole, petroleum naphtha, or linseed oil. Nitric acid colors it clear brown. 96. SCAMMONY Resin. Convolvulin. See Jalapin (87). 97. Resinous part of STORAX. Consists of (two) resins, and Styracin or Cinnamate of Cinnyl (C 9 H 9 C 9 H 7 O 2 ) . Alcohol and ether dissolve the whole. In cold alcohol, the styracin crystal- lizes in tufts of prisms. Styracin is tasteless and odorless, more 103 freely soluble in ether than in alcohol. Treated with hot nitric acid, or with chromic acid, or with sulphuric acid and binoxide of manganese, it yields benzoyl hydride (oil of bitter almonds). 98. Resins of TOLU Balsam. The Balsam consists of 80 to 90 per cent, of resin, about 12 per cent, of cinnamic acid, and less than 1 per cent, of volatile oil. It is wholly soluble in alcohol, chloroform, volatile oils, and aqueous alkalies ; partly soluble in ether ; insoluble in benzole, petroleum naphtha, bisul- phide of carbon, and solution of carbonate of sodium. The Resins of Tolu balsam are soluble in cold concentrated sulphuric acid, without change. 99. Separation of Resins by Solvents. Recapitulation. Water dissolves a part of the resin of Assafetida, a part of Gamboge, about -^ of Guaiac resin, and slightly dissolves Jalapin. a. Alcohol fails to dissolve -^ of Amber, Canatiba wax, Caoutchouc, a part of Copal, -^ of Guaiacum, Indigo blue (dis- solving slightly with heat), and -J of Mastic. b. Aqueous Alkalies (potassa or soda) dissolve Aloes resin, Amber, Ammoniac, Assafetida (mostly), Benzoin, Colophony, Convolvulin (with change), Dammara (Australian), Dragon's Blood (mostly), Guaiacum, Jalapin (with change), Lac resin, Myrrh, and resins of Podophyllum and of Peru and Tolu bal- sams. These solvents do not dissolve Canatiba wax, Caoutchouc, Copal, Dammara (East Indian), Hemp resin, Indigo blue. c. Ether dissolves resin of Aloes, Ammoniac (in part), Assafetida resin (mostly), Benzoin (in part), Canatiba wax (with difficulty), Caoutchouc (mostly), Colophony, Copal (with diffi- culty), Dammara (in part), Dragon's Blood, Gamboge, Guaiacum (in greater part), Hemp resin (Cannabin), Jalapin, Mastic, resin of Peru balsam, |- of Podophyllum resin, Sandarac, Styracin, and resin of Tolu balsam. Ether does not dissolve Amber, Indigo, and j- of Podophyllum resin. d. Chloroform dissolves Caoutchouc, Colophony, Gamboge, Guaiacum, Hemp resin (Cannabin), Jalapin, Mastic, Myrrh, 104 NEUTRAL SUBSTANCES, LIQUID OR FUSIBLE. resin of Peru balsam, resin of Senna, resin of Tolu balsam. Chloroform does not dissolve Agaric (in chief part), resin of Aloes, resin of Colocynth, Convolvulin. 6. Bisulphide of Carbon dissolves Canatiba wax, Caoutchouc, Copal (slowly), Dammara, Gamboge, Hemp resin, J of Myrrh, resin of Peru balsam, Sandarac (in part). It does not dissolve Amber, Indigo blue, \ of Myrrh, resin of Tolu balsam. f. Benzole dissolves Caoutchouc, Colophony, Dammara, Gamboge, Jalapin, Mastic (mostly), of the resins of Peru balsam, Sandarac (in part). Benzole does not dissolve Amber, Guaiacum, resin of Podophyllum, resin of Tolu balsam. g. Oil of Turpentine dissolves Ammoniac, Benzoin resin (in part), Canaiiba wax, Caoutchouc, Colophony, Copal (slowly), Dammara, Dragon's Blood, Guaiacum (mostly), Hemp resin, Jalapin, Mastic, Sandarac, resin of Tolu balsam. It does not dissolve Amber, Indigo (without heating). h. Sulphuric Acid, concentrated, cold, dissolves Amber (with red color), Ammoniac, Benzoin resin, Convolvulin (with red color turning brown), Copal, Dammara (with red color), Gam- boge (with red color), Guaiacum (with red color, etc.), Indigo blue. It does not dissolve Caoutchouc. 100. VOLATILE OILS. In composition, 1st, Hydrocar- bons, or " elaeoptenes," mostly of the formula (C 10 H 16 )ft-, a large class; 2d, Oxidized oils (C, H, O), including (1) hydrates of hydro- carbons, the " stearoptenes " or camphors, a moderate number being found alone and a large number in mixtures with the else- optenes, (2) aldehydes, (3) compound ethers, generally in natural mixture with elseoptenes, (4) of irregular composition ; 3d, Sulphurized oils (C, H, O, S) , a small class, products of natural fermentation, and having odors resembling each other. 101. Mostly liquids, a few oils and stearoptene parts of oils melting at a little above ordinary temperature ; the greater number lighter, a few heavier, than water ; very slowly volatile VOLATILE OILS. 105 at ordinary temperatures, mostly having boiling points above 150 C., but all distilling, slowly, with steam at 100 C., and leaving a transient oil-spot on paper. They are noted for strong and persistent odors ; colorless, or with pale colors, in a few instances tinted blue with coerulein, transparent and possessed of strong refractive powers. The volatile oils are neutral in reac- tion not generally liable to decomposition or combination except with oxygen. By air and light many of them alter and form resinous bodies ; the elaeoptenes forming stearoptenes, and (by oxidizing agents) aldehydes forming acids. 102. Volatile oils are very sparingly soluble in water, requir- ing intimate mixture and generally from 600 to 1,000 parts of water for solution ; soluble in alcohol, and in all proportions of absolute alcohol, ether, chloroform, benzole, petroleum naphtha, bisulphide of carbon, fixed oils and other volatile oils. Alkalies do not affect them. Certain oils, after distillation with water, retain traces of water in solution. This occurs with oils of ber- gamot, cinnamon, cloves, juniper, lavender, lemon, rosemary, sassafras, spike, wintergreen ; not with oils of amber, cedar, rue, turpentine. The presence of water is shown by turbidity on mixture with several volumes of petroleum naphtha (LEUCHS). Volatile oils are scarcely at all soluble in aqueous solutions of chloride, nitrate or sulphate of sodium. 103. The volatile oils are characterized by their individual odors, their physical properties (as stated above and in 105 and 106), by various special reactions (the most of which are stated in 107 to 114), by their refractive indices and their absorption spectra, and by their cohesion-figures when dropped upon a still surface of pure water.* 104. Volatile Oils are separated from substances more or less volatile by their distillation with steam ; from many sub- stances by their slight solubility in water (farther lessened by * TOMLINSON, MOFFAT : Chem. News, 1869. CRANE : Am. Jour. Phar., 1874, Sept., and Phar. Jour., 1874, p. 242, et. seq. 106 NEUTRAL SUBSTANCES, LIQUID OR FUSIBLE. common salt) and ready solubility in alcohol, ether, etc. From Fixed Oils they may be separated by distillation with water ; by solution in alcohol (not from castor oil) ; or by alkaline saponification of the fixed oil. From Alcohol, they may be separated (in greater part) by addition of water ; (in part) by addition of fixed oil ; (in part) by addition of dry chloride of calcium, and (with a little loss) by repeated distillations with water. Also (qualitatively) by adding to 5 or 10 drops of the oil, in a test-tube, a fragment of dry tannic acid, agitating, and leaving several hours at ordinary temperature. In absence of alcohol, the tannin remains solid, porous, and floats ; in presence of alcohol, it becomes pasty or liquid, and adheres to the glass or sinks (HAGER). Farther, volatile oils may be (quantitatively) separated from alcohol by glycerin (HAGER) : In a graduated cylinder place 10 parts of the mixture of oil and alcohol and 10 parts of a mixture of -| gly- cerin and -^ water, agitate, and set aside a few hours for separa- tion. Eead off at about 17.5 C. (Oil of Balm is soluble in glycerin.) Separation of volatile oils (or of Camphor) from alcohol may be made by water solution of nitrate or sulphate of sodium much more nearly than by water alone, and for approximately quantitative purposes. In a flask with a graduated neck, or a wide cylinder having its upper third narrowed and graduated, place about 3 vols. of a half-saturated solution of the salt and add 1 vol. of the alcohol solution of oil or camphor, agitate thoroughly, add enough of the salt solution to adjust the surface to graduated portion of the measure, and set aside at 20 to 25 C. until the liquids separate clear. The c.c. of oil multiplied by its spec. grav. equal the grams. For camphor (and if desired for oils) the process may be completed gravi- metrically, by adding about 3 parts of exactly weighed paraffin, fusing (inserting a platinum hook), and weighing when cold. Compare 67, c. VOLATILE OILS. 107 105. COLOR AND SPECIFIC GRAVITY OF VOLATILE OILS. Volatile Oils. Color of the Crude Oil. Color after Rectifica- tion. Spec. Grav. Amber, Yellowish or reddish-brown. Colorless or 0.800.88 yellowish. Anise, . Pale yellow to yellow. .98 .99 Balm, . Yellowish. ' .85 .89 Bergamot . Yellowish-green or brown-yel- Colorless or .88 .95 low. yellowish. Bitter Almond, . Yellowish, growing darker. 1.04-1.06 Cajeput, Green. Colorless. .91 .94 Calamus, Pale yellow. .89 .95 Camphor (oil of). Yellowish to reddish-brown. .94 Caraway, . Pale yel'w, growing brownish. Colorless. -.91 .94 Cardamom, Greenish-yellow. .93 .95 Cascarilla, . Dark yellow. .90 .93 Chamomile, Dark blue. .91 .94 " Roman, . Light blue. Cinnamon, . Yellow, becoming darker. 1.031.06 " (Cassia), . Light yellow to dark yellow. 1.031.08 Cloves, Bro wnish-y ello w. 1.031.06 Copaiba, Colorless or yellowish. Colorless. .87 .91 Coriander, . Yellowish. Colorless. .87 .89 Cubeb, Colorless. .92 .94 Cummin, Yellowish. .90 .97 Dill, . . . Yellowish, becoming red-br'n. .88 .93 Eucalyptus, Fennel, Galbanum, . Colorless. Colorless, growing yellowish. Yellowish. .88 .93 .90 .99 .90 .92 Galangal, . Yellowish. .91 .92 Geranium, . Yellowish. .90 .91 Hedeoma, . Light yellow. .94 Hops, . Pale brownish yellow. .90 .91 Jasmin, Yellowish. Juniper wood, . " berries, . Lavender, . Lemon, Colorless or yellowish-green. Colorless, yel' wish or greenish. Colorless, growing darker. YeUowish. Colorless. Colorless. .84 .89 .87 .90 .845- .865 Mace, . Pale yellow. Colorless. .87 .95 Marjoram, . Ulear yellow. .89 .92 Myrrh, Colorless or yellowish. 1.101.12 Nutmeg, Pale yellow, darkening. .90 .93 Orange flowers, . Orange peel, Uolorless, growing yellowish. Yellowish. Colorless. .85 .90 .83 .85 Origanum, . Yellowish to brown-yellow. .80 .90 Parsley, Yellowish. 1.021.04 Pepper (black), . Yellowish to clear-brown. .85 .89 Peppermint, Pale yellow, or greenish iri- descent. Pimento (allspice) Rosemary, . Roses, . Dolorless to yellowish. Colorless or pale yellow-green. Colorless, reddish, or yerwish; .89 .92 .88 .92 .83 .84 concrete below 20 C. Rosewood, . Pale yellow. 103 NEUTRAL SUBSTANCES, LIQUID OR FUSIBLE. 1O5. COLOR AND SPECIFIC GRAVITY OF VOLATILE OILS.- Continued. Volatile Oils. Color of the Crude Oil. Color after Rectifica- tion. Spec. Grav. Rue, . Yellowish. .85 .90 Sage, . . Green-yellow or yellowish. .86 .92 Sassafras, . Yellowish to red-yellow. 1.061.08 Savine, Colorless or yellowish. .89 .93 Spearmint, . Yellowish, becoming dark, .91 .98 red-brown. Tansy, Turpentine, Pale yellow or green yellow. Colorless. .90 .95 .87 .89 Thyme, Yellow-green, red-brown. .87 .89 Valerian, . Yellow-brown, green-brown. .90 .96 Wintergreen, . Wormseed (San- Reddish. Colorless. 1.141.17 [ tonica), Brownish-yellow. .91 .96 Wormwood, Green. .88 .93 Yarrow, Ylang-Ylang, . Dark-blue. .87 .92 .98 106. Solubility of Volatile Oils in Alcohol of sp. gr. O.822 (90 per cent:) Take, in a test-tube, from a minim measure, 5 or 10 minims of the oil, and then as many minims of the alcohol as required, with agitation, to dissolve. The oils which form solutions more or less turbid are given with figures in heavy type. It will be borne in mind that oils are less soluble when old than when fresh. Also, that mixtures of oils usually have solubilities mid- way between those of the individual oils therein. Alcohol required, at 17 to 20 (7., for 1 vol. of oil of Amber, Anise, Balm, .... Bergamot, . Bitter Almond, . Cajeput, Calamus, Caraway, . Cardamom, Chamomile, 3# vols. Cinnamon, . . 1 vol 1 " (Cassia), . . 1 3 Cloves, . 1 # Copaiba, . 1 Cubeb, . 25 11 Cummin, . 1 1 Fennel, . Ito2 iftol Juniper berries, . 10 tf tol Lavender, . . 1 8 Lemon, . 50 * VOLATILE OILS. 109 Mace, Marjoram, . Orange flowers, . Orange peel, . 5 vols. . 1 " . Ito2 . 5 Rue, .... Sage, .... Savine, Tansy, . 1 vols . 1 . Ito2 1 Parsley, Peppermint, Rosemary, . Roses, . 3^ . 1 . Ito2 50 to 70 Turpentine, " rectified, . Valerian, . Wormwood, . 9 10 to 12 . 1 . 1 107. Eeaction of Volatile Oils with Iodine and Bro- mine. (1) When about 0.1 gram of dry pulverized iodine is placed at ordinary temperature in a watch-glass and 4 or 5 drops of the oil are dropped upon it : (a) Giving instantaneous reaction, with much heat and strong effervescence ,' Oils of Lemon, Savine, Mace, Turpentine, Orange flowers, Wormwood (old). Orange peel, slight heat, with gentle effervescence: Bergamot, Eucalyptus, Hops, Lavender, (b) Generating Oils of Anise, Dill, Balm, Fennel, Caraway, Jumper, Chamomile, Marjoram, Cubeb, (c) Giving no reaction, or very slight, Amber, , Cinnamon (Cassia), Bitter Almond, Cloves, Cajeput, Mustard, Calamus, Parsley, Cascarilla, Peppermint, Cinnamon (Ceylon), Roses, (2) Upon 5 or 6 drops of the oil, on a watch-glass, one drop of bromine is let fall (MAISCH). (a) Giving detonation with Oils of Amber, Juniper wood, Bergamot, Lemon, Hedeoma, Turpentine. Juniper berries, Rosemary, Sage, Sassafras, Thyme. Oils of Rue, Sassafras, Thyme, Valerian, Wormwood (fresh). 110 NEUTRAL SUBSTANCES, LIQUID OR FUSIBLE. (b) Giving a hissing sound with Oils of Anise, Sassafras, Caraway, Wormseed. (3) To 5 or 6 drops of the oil, on a watch-glass, add 5 drops of ether solution of bromine (1 vol. bromine to 5 vols. officinal ether, added slowly, while cooling, just before use).* (a) Vapors evolved with Oils of Copaiba (green color ; afterward brownish-green with brown sediment). Cubeb (violet color, deepening ; afterward dark greenish-blue, with violet- black sediment). Orange peel (yellow color soon appears ; afterward pale brown and transparent). Patchouli (deep violet color, deepening ; sediment dark brown). ^ Sassafras (at first cloudy ; afterward pale brownish-yellow). Spearmint, old, yellowish-red (color changes to yellowish-brown ; sediment lighter). Wintergreen (formation of a resinous white substance, spreading over the (b) Vapors not evolved with Oils of Anise (white color ; with more bromine, yellowish-red). Bergamot (color greenish-brown yellow, then reddish-brown yellow). Bitter Almond (dissolves without reaction ; after evaporation of the ether, two liquids separate one deep, the other light red). Cajeput (supernatant liquid scarcely colored ; appearance of green droplets). Calamus (colors red-brown, brown-green ; finally a dark sediment). Caraway (little reaction ; sediment yellowish-brown). Cinnamon (color lemon-yellow, turning to amber-brown). Cloves (color greenish ; lower stratum alters to pale grayish-black). Hedeoma (color changed to purplish and darkened ; liquids not miscible). Lavender (light greenish, darkening to deep sea-green). Lemon, old (brisk reaction ; colors reddish-yellow and greenish). Mustard (miscible, colorless ; afterward milk-white). * MAISCH : Proc. Am. Phar. A., 1859, 338. VOLATILE OILS. Ill Nutmeg (at first colorless ; the lower stratum then brownish and milky to clear). Peppermint (colors yellowish, then reddish, then brown thickening). Rosemary (colorless ; afterward lower stratum is light-brown). Rue (at first cloudy, then pale brownish yellow). Valerian (at first purplish-black ; then upper stratum deep violet, lower greenish-black, marginal blue and red spots). Wormseed (reaction is slow ; heavier liquid red to brown ; lighter liquid light brown and almost clear). Wormwood (darkens a little without movement). 108. Reaction of Volatile Oils with Sulphuric Acid and Alcohol (HAGER'S Method). In a test-tube of about 1.3 centim. (0.5 inch) diameter, 5 or 6 drops of the oil are agitated with 25 to 30 drops of concentrated sulphuric acid, after which it is noted how much heat and how much turbidity, if any, have* been produced. When the liquid, if heated, has cooled again, 8 or 10 c.c. of 90 per cent, alcohol are added, with brisk shaking while the test-tube is closed by the finger. Now the production of celor and of turbidity are noted. In case of turbidity, after standing, a subsident layer usually appears, having a character- istic color, and being soluble in cold or in hot alcohol or in chloroform. (a) The mixture of oil with acid and alcohol, is clear and transparent, or ~but very slightly turbid, in case of Oils of Amber (with sulphuric acid, not heated, dark yellow and turbid ; after add- ing alcohol, yellow, slightly turbid, made clear by boiling). Anise (with the acid, in part dark red and thick, and in part clear and lim- pid ; with the alcohol the thick part remains dark and undissolved, while the liquid part is clear and nearly colorless). Bitter Almond (with the acid, a brown color and much heat without turbi- dity ; with the alcohol, a clear and nearly colorless mixture). Cloves (with the alcohol, the mixture is nearly or quite clear). Dill (with acid, generation of heat and vapors, with dark yellow-red color and some turbidity ; with alcohol, a pale cinnamon-brown mix ture, nearly or quite clear fully clear on boiling). 112 NEUTRAL SUBSTANCES, LIQUID OR FUSIBLE. Fennel (with acid, heat and vapors, the mixture dark red and pretty clear ; with alcohol, yellowish, clear solution). Mustard (with acid, very little heat, yellowish tint, clear ; with alcohol, colorless and clear). Nitrobenzole or "artificial oil of bitter almonds " (without turbidity). Peppermint, best (with the acid, slight heat and yellow-red color ; with the alcohol, light red, slightly turbid mixture, made clear by boiling). Peppermint, American .(with the acid, heat and dark brown-red color ; with the alcohol, brownish and turbid, made clear by boiling). Roses (with acid, heat, thick vapors, and dark brown-red color ; with alco- hol, brown, clear, and transparent). Valerian (with the acid, heat and slight vaporization, dark red color, slight turbidity ; with the alcohol, red, turbid, but rendered clear by boiling). (fj) The mixture of oil with acid and alcohol is left more or less turbid, in case of Oils of Balm (with acid, heat, vapors, brown-red color, and turbidity ; with alco- hol, cinnamon-brown, somewhat turbid ; after boiling becomes clear with separation of dark drops). Bergamot (with acid, heat and vapors ; the alcohol solution pale grayish- yellow turbid, with flocculent separate after shaking ; after one or two days, the residue is but slight and divisible on shaking, the liquid being clear yellow). Cajeput (with acid, heat and vapors, light yellow color and turbidity ; with alcohol, pale rose-gray turbidity, made clearer by boiling). Caraway (with acid, heat and vapors, dark yellow to red-brown color, tur- bidity ; with the alcohol, a red and turbid mixture, made nearly clear by boiling). Cascarilla (with acid, heat and vapors, dark brown-red color, turbidity ; with alcohol, the same ; an hour after boiling, dark brown-violet to bluish-red). Cinnamon (Cassia) (with acid, a strong heat and vaporization, dark black- brown, very thick mixture ; after the alcohol, the dark viscid mass remains mostly insoluble, with a milky olive-green liquid above). VOLATILE OFL& 113 Copaiba (with the acid, heat and vapors, the color dark yellow-red, with turbidity ; with alcohol, red and turbid, not made clear by boiling). Coriander (with sulphuric acid, heat and vapors, dark red color, scarcely turbid ; with alcohol, dark brown, with green shade, and turbid). Eucalyptus (with sulphuric acid, heat and vapors, light reddish-yellow color, with turbidity ; with alcohol, very turbid, with whitish- peach-blow or pale rose-gray color). Geranium (with acid, much heat and thick vapors, turbid, dark yellow-red ; with alcohol, turbid and dark brown ; after boiling, turbid and red-brown). Juniper berries (with acid, heat and vapors, turbid, dark-yellow-red ; after the alcohol, very turbid, sometimes flocculent, of blackish-rose color ; after boiling, turbid ; after a few hours, a light-colored resinous mass separates). Juniper wood (with acid, heat and vapors, turbid, orange-red ; with alcohol," pale yellowish, turbid before and after boiling). Lavender (with acid, heat and vapors, turbid and brown-red ; with alcohol, turbid, dark brown with green tint). Lemon (like Bergamot oil : after one or two days, the slight residue forms opaque yellow drops not divisible by shaking). Mace (with acid, heat and vapors, turbid, dark red ; with alcohol, turbid and dark reddish-brown, not made clear by boiling). Marjoram (with acid, heat without vapors, turbid and yellow-red ; with alcohol, very turbid, peach-blow and almost milky ; turbid after boiling). Orange flowers (with acid, heat and vapors ; after alcohol, turbid and brown, approaching red ; after boiling, a little darker and less turbid). Orange peel (with acid, a strong heat, turbidity and red-brown color ; with alcohol, whitish-yellow; turbid before and after boiling). Parsley (with acid, a moderate heat and a little vapor, very dark red ; with alcohol, very turbid, red, with swimming flocks). Rosemary (with acid, strong heat but no vapors, yellow-red and turbid ; with alcohol, milky turbid ; turbid after boiling). Rue (with acid, heat and vapors, dark red, turbid ; with alcohol, raspberry- red, turbid ; clear after boiling). Sage (like Oil of Rue). 114 NEUTRAL SUBSTANCES, LIQUID OR FUSIB1:E. Savine (with acid, strong heat without vapors, moderately tu.-bid, dark red; with alcohol, turbid, reddish-clay-colored ; after boiling, less tur- bid, pale red). Tansy (with acid, heat and vapors, dark red, turbid with alcohol, yellow- red, less turbid ; after boiling, clear). Thyme (with acid, heat and vapors, red, turbid after alcohol ; after boiling, clear, with swimming oil-drops). Turpentine (deviating greatly from differences of production and of age). Wormseed (Santonica) (with acid, moderate heat and vapors, dark red, tur- bid ; with alcohol, cinnamon-brown, turbid ; becoming clear on boiling). Wormwood (with acid, heat and vapors, red-brown, turbid ; with alcohol, dark, green-violet, opaque, turbid ; becoming clear with more alcohol). Ylang-Ylang (with acid, heat and vapors, turbid and dark red ; with alco- hol, pale brick-red and very turbid, less turbid after boiling). 109. Eeaction of Volatile Oils on Sulphide-of-Lead- Paper (G. WILLIAMS). Blotting-paper is wetted in a dilute alcoholic solution of acetate of lead and dried in an atmosphere of hydrosulphuric acid. A few drops of the oil are let fall on a strip of this paper, which is placed in a (dry) dark place for 5 or 10 or 15 hours, when the degree of bleaching is noted. The paper is bleached by Oils of Lavender, Peppermint, Eosemary, Turpentine. The paper is not bleached by Oils of Anise, Bergamot, Cajeput, Cinnamon, Juniper berries, Lemon, Orange peel, Sage, Thyme. 110. Reaction of Volatile Oils with Sodium (DRAGEN- DORFF). The Hydr3carbons are not affected; the Oxidized oils are more or less readily decomposed. Ten drops of the oil are treated with a small piece of the metal. The result is discovered after 5 or 10 minutes. (Alcohol causes a prompt reaction, with evolution of hydrogen.) Little or no change occurs with Oils of Amber, Bergamot, Copaiba, Lavender, Lemon, Nutmeg, Pepper, Peppermint, Rosemary, Sage, Turpentine. Oil of Mus- tard evolves hydrogen. VOLATILE OILS. 115 111. Identification of Resinified or Old Oils, or of Resins or Fixed Oils in mixture with^ volatile oils. Evaporate 1 gram of the oil, on a tared watch-glass, at 70 to 90 C. (or over the water-bath). Fresh and unchanged oils, free from mix- ture, leave only a scarcely perceptible and not weighable residue. This residue, fully freed from volatile oil, may be tested for Castor Oil, by treatment for cenanthyc acid, as described under Ricinoleic Acid (46). 112. Identification of Turpentine Oil. The sparing solubility of this oil in aqueous alcohol affects its mixtures with other oils, but does not enable it to be separated. The alcohol should be 75 to 90 per cent. HEPPE'S test is with nitroferri- cyanide of copper prepared by precipitating solution of sulphate of copper with solution of nitroferricyanide of sodium, and washing and drying the precipitate. In a test-tube place a bit of this reagent as large as a pea, then about 25 drops of the oil, and heat, so as finally to boil for a few seconds, and set aside to subside. Turpentine oil (also lemon oil) does not suffer change, or more than slight change while the sediment of nitroferricy- anide is green or blue-green. Other volatile oils are darkened to different colors ; while the sediment of copper salt is gray, brown, or black. 113. Identification of Valerian Oil. One drop of the oil is dissolved in 15 drops of bisulphide of carbon, then shaken with sulphuric acid, and afterward one drop of nitric acid, of spec.'grav. 1.2, is added. A fine blue color results when even slight portions of the oil are present (FLUCKIGER). 114. Identification of Oil of Peppermint. 50 to 70 drops of the oil, with 1 drop of nitric acid, of spec. grav. 1.20, turns faintly brownish, and after an hour or two becomes fluores- cent blue-violet or green-blue by transmitted and copper-color by reflected light (FLUCKIGER). Chloral- hydrate, on contact with oil of peppermint, colors it reddish.. The tint deepens to cherry-red, is intensified by sulphuric acid, and varied to dark 116 NEUTRAL SUBSTANCES, LIQUID OB FUSIBLE. violet by chloroform. (No color is obtained with oils of lemon, bergamot, juniper, rosemary, cloves, anise, or fennel.) For qualitative separation of Benzole from volatile oils, see 119; of Nitrobenzole from Bitter Almond Oil, see 120. 115. CAMPHOR. C 10 H 16 O. Laural Camphor. A slightly unctuous, pellucid solid, friable with cleavage, of specific gravity 0.985 to 0.996; melting at 142 C. (288 F.), slowly vaporizable at ordinary temperatures, condensing in hexagonal plates, boiling at 204 C. (400 F.) It is soluble in 1,000 parts of water applied by ordinary contact, or in 150 to 200 parts of water by tritura- tion with an insoluble powder ; freely soluble in alcohol, ether, chloroform, benzole, petroleum naphtha, methylic alcohol, amylic alcohol, creosote, acetic acid, mineral acids, bisulphide of carbon, fixed and volatile oils, and forms a liquid mixture with solid chloral hydrate. Minute particles of camphor, dropped upon water, rotate, with velocity in proportion to their smallness. If an oiled pin-point is then touched to the water, the rotations are stopped, and the camphor particles carried out by the enlarging circular oil-film. By prolonged boiling with concentrated nitric acid or per- manganate of potassium, camphor is changed into Camphoric Acid. The latter is sparingly soluble in water, from which it crystallizes in colorless scales or needles, of sour and bitter taste, melting at 70 C., and forming insoluble salts with lead and many other metals. By heating in a closed vessel with bromine, Bromated Camphor is formed, as a crystallizable solid, not soluble in water. 116. CREOSOTE. Chiefly Creosol, C 8 H 10 O 3 , and Guaiacol, C 7 H 8 O 2 . An oily limpid liquid, of spec. grav. 1.060 to 1.085, colorless or yellowish (growing brownish in the light), boiling at 200 to 206 C. (392 to 403 F.), having a neutral reaction, a strong and persistent smoky odor, and a very caustic and smoky taste. It is soluble in 60 to 90 parts of water, in all proportions CREOSOTE. ANTHRACENE. ALIZARIN. 117 of alcohol, ether, chloroform, benzole, petroleum naphtha, fixed and volatile oils, anhydrous glycerin, acetic acid, sulphuric acid (with combination and brown color), and in an equal part of bisulphide of carbon. It is soluble in aqueous alkalies forming instable salts. It dissolves (and in commerce usually contains) about 8 per cent, of water, from which it is separated by mixture With a large quantity of benzole. Creosote resembles Phenic Acid, in most of its physical properties, and in its reactions with nitric acid, ferric salts, bro- mine, gelatin, and albumen. It is distinguished from Phenic acid by not crystallizing when pure ; by gelatinizing collodion; by not giving a blue color with 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, ammo- nia, or with 5 volumes of ordinary (slightly aqueous) glycerin, or with a greater volume of bisulphide of carbon; and by more sparing solubility in water, 117. ANTHRACENE. C 14 H 10 . A colorless solid, crys- tallizing in the monoclinic system, often in four or six-sided tablets, having spec. grav. 1.147, melting at about 212 C., sub- liming slowly from the solid, and distilling rapidly at 300 C. When pure, the crystals show blue or violet fluorescence. It is tasteless and odorless, but its vapor at the distilling point is dis- agreeable 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. ALIZARIN. C 14 H 8 O 4 . A yellow to red-yellow solid ; by sublimation (at 215 C.) crystallizing anhydrous in red prisms, and from solutions crystallizing in golden scales of the 118 NEUTRAL SUBSTANCES, LIQUID OR FUSIBLE. hydrate. Slightly soluble in water ; soluble in alcohol and ether (with yellow color) and 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 ammo- niacal 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. BENZOLE. C 6 H 5 H with traces of its homologues. Coal-tar naphtha. Benzene. A colorless limpid liquid, of about 0.85 spec, grav., crystallizing at C., melting at 5.5 C. a boiling at 80 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 distinguished 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. grav. 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 with ten times its bulk of water (which separates drops of nitro- benzole). Agitate with ether, which takes up the nitrobenzole ; PETROLEUM NAPHTHA. NITROBENZOLE. 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). 119J. PETROLEUM NAPHTHA. Gasolene. "Ben- zene." The rectified distillate of petroleum, having a boiling point of about 49 C. (120 F.) specific gravity about 0.665. Consists chiefly of C H H, with a little C H H and other / 511' 613 homologues. Characterized by an agreeable odor and anaesthetic -effect ; by a wide range of solubilities ; and by resisting the action of alkalies and most acids, while decomposed by heating with nitric acid. Distinguished from Benzole by a lower specific gravity (even when both are of the same boiling point), and, more accurately, by not forming nitrobenzole (119). 120, NITROBENZOLE. C 6 H 5 (NO 2 ). Essence of Mir- bane." " 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.) Jt 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 odor coinciding with its reaction for anilin. When a few drops are digested in a test-tube with zinc, acetic acid, and iron or magne- sium 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 filte?^ed through a wet filter, and the filtrate tested (with chlorate of potassium) for anilin. Both the above methods are applicable in pre$encA *>f 120 BASES, VOLATILE. Bitter Almond oil ; also the following : Two or three cubic cen- timetres 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 100 C. for a day or two, reduces nitro- benzole to anilin. Nitrobenzole is distinguished from bitter almond oil and other Volatile Oils by its specific gravity. BASES: LIQUID AND SOLID. 121. ANILIN. (C 6 H 5 )H 3 N. Monophenylamin. 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, aro- matic 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. " Kuphanilin " contains about 90 per cent, of phenylamin, and has a boiling point of 180 to 190 C. " Bara- nilin " is mostly toluidin, with a little cumidin and cymidin, boiling at 195 to 215 C.* * (Mono)phenylainin, (Ce Hs ) H2 N. Toluidin, (C: H 7 ) Hs K Xylilin, (C 8 H9)H 2 N. CumidiB, (C 9 Hii)H 2 N. ANILIN. 12 123. Phenylamin with acids forms salts, crystallizable, 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 chlo- roform. Anilin salts are readily decomposed by fixed alkali, j when the anilin may be separated by ether. In the cold, anilin is displaced by ammonia ; with heat, ammonia is displaced by anilin. 124. TOLUIDIN has, with most solvents, nearly the same solubility as phenylamin. It forms few salts ; the oxalate is sparingly soluble in water. 125. Anilin is identified, through formation of Anilin Red (rosanilin, fuchsin, or magenta), by chlorinated lime or chlo- rinated soda (a), by ferric chloride (5), by binoxide of manga- nese 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 distinguished from, Alkaloids (including Conia and Nicotia) by giving no precipitates with potassio mercuric iodide solution, or with iodine in iodide of potassium solution, or picric acid in presence of sulphuric. It coincides with Alkaloids in giving precipitates with phosphomo- lybdate (f), and with tannic acid (g). It is characterized by a moderate reducing power (h). Anilin is examined as regards its proportion of Toluidin, as explained in a. It is separated from benzole, nitrobenzole, and other associated impurities by fractional distillation. Anilin Red is a term for various salts and compounds of ROSANILIN (C ao H 19 N 3 .H 2 O). 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 insoluble in water and insoluble in ether. It forms 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 agents, rosanilin has a rich violet-purple color, changed to red by acids, and restored to violet-purple by alkalies. In proportion as 122 BASES, VOLATILE. formed from toluidin, the color becomes brown. Ether extracts the brown, leaving a blue. a. 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, leaving a blue liquid below. t>. To a small portion (10 c.c.) of a very dilute solution of anilin, strongly acidulated with hydrochloric acid, add of a concen- trated 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 60 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 50 or 60 C. d. Chlorate of potassium with hydrochloric or sulphuric acid, when strong, forms a red resinous substance; 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 aci- dulated 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. h. Anilin reduces permanganate solution buf no* cupric sulphate. CONIA TRIMETHYLAMIA. 123 126. ALKALOIDS. Volatile and 'Non-volatile. The volatile alkaloids are. composed of C, H, and N, without O ; 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; Com- parative reactions, 131 and 135 to 143.) ANILIN (121). 127. CONIA.* C 8 H 16 !N". A colorless liquid, of spec.- grav. 0.89, wasting slightly at ordinary temperatures, distilling almost wholly with steam at 100 C., boiling at 160 to 180 C. It has a mouse-like odor, sharp taste, and strong alkaline reaction. It resinifies, yellowish, in the air. Its administration causes enlarg- ment 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 reac- tion. Its administration dilates the pupils. 129. NICOTIA. C & H 7 K". A transparent, oily liquid, of spec, grav. 1.048, distilling with steam at 100 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 3 H 9 N. Propylamin. Secalin. A colorless liquid below 5 C., its vaporizing point. (Soluble in water and alcohol.) It has an odor of herring and of ammonia, a sharp, bitter taste, and an alkaline reaction. Its salts are crys- tallizable, 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. 324 BASES, VOLATILE. i ill i ft 08 " W I *** & *S ! fl ^ la il3 I ipi ? i i. ^i fl; ^o ! Hi own recl Bro pr slow all. Orange- cipitate. 1 ^ f," 3 23 K 2! * ~ CO dine In so- lution of KI. o o s flS &o a 1! COMPOSITION ; CRYSTALLINE FORM; COLOR. 125 132. Non-volatile Alkaloids and accompanying Glucosides. (For Solubilities, 133; Separations, 134; Reactions common to alkaloids, 135, 142, 143.) (For Determinations of Quantity. 135, 142, 143.) ACONITA. C 30 H 47 NO 7 . Glacial mass or white powder. Crys- tallizes with difficulty. 136 (135, e, /). ATROPIA. ) C 17 H 23 NO 3 . Prisms; stellated tufts ; white powder ; DATURIA. [ fusible at 90 C. 136, 135. BERBERINA. C 21 H 19 ]N"O 6 (H 2 O) 5 . Light-yellow silky needles, or grouped prisms. 136, 138. BRUCIA. C 23 H 26 N 2 O 4 . Colorless ; delicate needles ; four-sided prisms. 136, 137, 138, 140, 139. CAFFEINA. C 4 H 5 W 2 O. White, silky needles ; fusible at 178 C. ; subliming at 185 C. 136, 140 (135, a, e, g). CINCHONIA. C 20 H 24 N 2 O. Four-sided prisms or needles ; fusible at 165 C. 136. CINCHONIDIA. C 20 H 24 !N" 2 O. Hard rhombic prisms, with striated faces. Melts at 175 C. CODEINA. C 18 H 21 NO 3 . Rectangular octahedrons ; or (in presence of water) trimetric. 136, 138, 139. COLCHICIA. C 17 H 19 ]SrO 5 . Colorless prisms or needles; yellow- ish-white powder; glacial. 135, 136, 138, 140. DAPHNIN. C 31 H 38 O 19 . Rectangular prisms. Odorous above 100 C. ; above 200 C., Daphnetin. 138, 141. DELPHINA. Amorphous ; powder white with yellow tint. Melts to resinous mass. 136 (135, e). DIGITALIN. C 10 H 18 O 4 . Difficult to crystallize. A Glucoside. 136 (135a) (142). EMETIA. C 30 H 44 N 2 O 4 . Yellow-white powder. Melts at 50 C. 136, 138 (135, e). ERGOTINA. C 50 H 52 N 2 O 3 . Red-brown powder. 136. HYDRASTIA. Colorless, shining, four-sided prisms. Above 100 C., melts. 136, 137, 140. HYOSCYAMIA. C 15 H 23 K"O 3 . Stellate groups of silky needles; amorphous and pasty. Fusible. 136. IQASURIA. Colorless, lustrous prisms. Fusible. 136, 138, 140. 126 NON-VOLATILE ALKALOIDS. MORPHIA. C 17 H 19 NO 3 (H 2 O). Short, transparent, trimetric prisms. Anhydrous at 120. 136, 138, 141. NARCEINA. C 23 H 29 WO 9 . Colorless, delicate needles. Fusible. 136, 137, 138, 139. NARCOTINA. C 22 H 23 NO 7 . Colorless, rhombic prisms. Fusible. -136, 138, 139. OPIANIA. C 66 H 72 N 4 O 21 . Eight rhombic prisms. 138, 139. . PAPAVERINA. C 20 H 21 NO 4 . Colorless, acicular crystals. 136, 138. PAYTINA. C 21 H 24 N 2 O. Colorless crystals. PHYSOSTIGMIA. C 15 H 2i ;W 3 O 2 . Amorphous, brownish-yellow ; solutions, red to blue. 136, 140. PICROTOXIN. C 12 H 14 O 6 . Needles ; stellate ; laminae. Eeduces cupric hydrate.^137. PIPERIN. C 17 H 19 NO 3 . Colorless, monoclinic prisms. Melts at 100 C. 136, 138. PSEUDOMORPHIA. C 17 H 19 NO 4 . Fine, lustrous crystals. 136, 138, 141. QUINIA. C 20 H 24 N 2 O 2 . Hydrate, in fine needles. - Solutions, blue-fluorescent. 136, 140. QUINIDIA. C 20 H 24 N 2 O 2 . Transparent, monoclinic prisms, efflo- rescent. 136, 140. EHCEADIA. C 21 H 21 NO 6 . Small, white prisms. Melts at 232 C. Purple-red with acids. SABADILLIA. C 20 H 26 N 2 O 5 . Cubic crystals (Needles?). Eeacts with sulph. acid like Veratria (136) 135, e. SALICIN. C 13 H 18 O 7 . Tabular or scaly crystals. Melts at 120 C. A Glucoside. 136. SAPONIN. C 32 H 54 O 18 . Amorphous. Aromatic odor, sweet taste, burning after-taste. A Glucoside. SOLANIA. O 43 H 69 NO 16 . Silky needles ; right, four-sided prisms. A Glucoside. 136, 138. STRYCHNIA. C 22 H 24 N 2 O 2 . Four-sided prisms, trimetric, white. Fusible. 136, 137. THEBAINA. C ]9 H 21 NO 3 . Thin, square tablets of silvery lustre. Fusible. 136, 138. SOL UBILITIES. 1 27 THEOBROMINA. C 7 H 8 N 4 O 2 . Microscopic, trimetric crystals, in club-shaped groups. 136, 140. . VER ATRIA. C 32 H 52 N 2 O 8 . White or greenish- white crystallized powder. Warmed with HC1, violet. 136. 133. Solubilities of the Alkaloids. In alcohol they 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 nearly insoluble. Solania in 150 parts hot or 500 parts cold alcohol. Strychnia difficultly soluble in absolute, soluble in 115 parts of 95 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 80 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 from acid solutions Colchicin, Digitaiin, Picrotoxin in general not the (other) alkaloids. Petroleum Naphtha, as used below, distils at from 40 to 60 C. (104 to 140 F.), leaving no residue. Amylic Alcohol should be strictly free from ethylic alcohol. The acid used with chloroform, benzole, etc., is sulphuric acid, added just to an acid reaction, and forming sulphates of the alkaloids. SOLUBILITIES OF ALKALOIDS. S-d 3-3 i s .1 <] o 50 o _Q QJ f* 3 .00*! rt -oj 33 1 case 5 1 1 1 i ! !lf 5? S o 02 02 3 5 i ^ d S^g I s OJ 43 woo 1 .3*5 II s Km dd d III S 3 S 5 d & & "o p| II I III O O O g 2 00 >5 >-H Mh-l h-t HHMI-H 53 o"^ a> o "3 i oi a eJ o rO "o 33 *. o 3 C3 V oj3 3 3 3 3 li ll| !! 3 3 35 d o 9 d p rS"* * on S h-ll-l CO 5 5 02 02h-( a d d 03 ,3 oj a o &T fe * ^=^3 C) J3 ^3 3 3 a a ~~~ o 2 3 O ^3 5 3 ^ 35 533 Kv *O Y^t 1 H ggs o o QQ QQ flfl 1 1 fl 3 1 02 d o la I S55 SS5 g 3 II S 3 ill 1 | o d a a 3 sssl 33 d 4i 13 11 II 1 5 . ^ g S ^ j3 t0 1 * fi 3 a d d"^ 005 pd M "*-* 1? a d d i a s O2 M 1 5 | .25^ S a f "3S | ^ 1 1! 1 1 ti a a 1 1 o 1 ,2 3 _d 3 ^ d 5S^ S- ^a ,Q o .;3 -g-ld&e 3.^3 55 W r-I^ NI -* lil 2^5 C O 1 "^ o ^ 020Q M S 5 O 02 02 02 02^102 5^& P,0 020202 s^ 1 ! Ammonia with water. i! 0202 1 1 i (As water) Soluble. Soluble. Soluble. Spar'g. sol. (As water) Slight, sol. Slight, sol. Insoluble. 49 2 < Fixed Al- kali with water. (As water) Soluble. Soluble. ! 1 1 1 1 1 0- 02 5 (As water) 33 "3 0202 Soluble. te M Soluble. (As water) Insoluble. * o o 28 S5S -Moo 00 55 I 55s 00 II 33 m V l wo 4} 111 s .s SS5 s^|. TdiW 1 1 i 5 ^ b & I i 1 * :- 1 in I 1 ??; b_i jj ft; IH .a o ^a ; - S o o 5x3 P, O2 O J--S M . s ^l p I S? I- 1 * !^?> 5 as 1 1 11 r! . 02 oSw: "^-~o-5 liflfljfl o2 l0 |j->a^^ 1ISI1SI3 f ' 130 NON- VOLATILE ALKALOIDS. 134. Separation of Alkaloids from (solid) Albumenoid, Fatty, and Extractive Matters. (1) The alkaloids are dis- solved out, as salts (tartrates, sulphates, or acetates) by alcohol, at a gentle heat ; the filtered solution is evaporated to drjness, and the residue dissolved as before, etc. For removal from Fats, the residue 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 w T ith 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 princi- ple, for non-volatile alkaloids only, with use of chloroform instead 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 amy lie-alcohol- solution of alkaloids is washed with acidulated water, whereby the alka- loids 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 only to those alkaloids not soluble in amylic alcohol from acid see Table, 133 (USLAR and ERDMANN, 1861). (4) The use of animal charcoal to withdraw an alkaloid (strychnia) from a solvent ; after which the alkaloid is extracted METHODS OF SEPARATION. 131 from the charcoal by a more effective solvent. (GRAHAM and HOFMANN, 1853.) (5) Dialysis of the alkaloids, as salts, from colloid matters (GRAHAM, 1862). (6) Separation of Alkaloids from each other, as well as from 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 Erdmann) when necessary to purify. Division of the alkaloids into about eight groups. (DRAGENDORFF, 1868.) (7) Separation of alkaloids from each other and from associated Glucosides, by an extension of the method last named. (8) Separation of alkaloids from each other by their solu- bility in alkali. (9) Separation of pure alkaloids from each other by successive use of ether, water, and chloroform. (PRESCOTT.) (1) Otto's and jStas* Method. An aliquot part of the mate- rial 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 tubu- lated retort. Fat is separated by filtration through a wet filter, and the filtrate evaporated nearly or quite to dryness, in vacuum or over sulphuric acid. Macerate the residue in absolute alcohol (for 24 hours), and evaporate the filtrate at a heat not above 40 C. (104 F.) Moisten the residue with water, and * PRESCOTT : Chem. News, xx., p. 232 (1870, Jan ) 132 ALKALOIDS. add bicarbonate of sodium or potassium as long as there is effer- vescence. 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 streaks, collecting into droplets, having a pungent odor and alka- line 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 por- tion of ether taken after adding bicarbonate, and treat as follows : For non-volatile alkaloids, evaporate the (first) ether-extract, dissolve in a very little very dilute sulphuric acid (leaving a decided acid reaction) and wash with ether (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 with water acidified by sulphuric acid ; then the concentrated aqueous sulphate is treated with carbonate of potassium in excess and extracted with absolute alcohol. At each evaporation the appearance of crystals is watched. Crystallization from ethereal solutions is greatly promoted by adding alcohol. (2) Rodgers and Girdivood's method. The material is digested with dilute hydrochloric acid at a moderate heat for about two hours ; the filtered extract evaporated to dryness on the water-bath ; the residue extracted with water and filtered ; -=~ 8EPAEA TION B Y SOL VENTS./f' 1 33 if -#" * .?* IV^n * E* and the filtrate supersaturated with ammonia and then extracted, in a flask, with chloroform. The solid residue from the chloro- form 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 ammonia and again extracted with chloroform. 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) Method of Uslar and Erdmann. Digest the material, brought to the consistence of a thin paste and acidified with hydrochloric acid, for an hour or two, at 60 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, repeat- edly, 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 alka- loids, in solution. Transfer the filtrate to a cylindrical vessel, add ten or twelve times its volume of water acidified with hydrochloric acid and nearly boiling, agitate vigorously 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 amylic 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 ALKALOIDS. (4) Method with Animal 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 separa- tion 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 Naphtha, Benzole, Chloroform, and Amylic Alcohol, each in Acid and in Allcaline Solutions. Dragen- dorff's Method. The finely-divided material is extracted several times with water acidulated with sulphuric acid, digesting several hours at a temperature of 40 to 50 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 suffi- cient 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 frequent agitation, for 24 hours, at about 30 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 35 C. Fats, colors, etc., and, if present, Piperin are dissolved : solution B. The watery-acid 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 magne- sia or ammonia (leaving a distinctly acid reaction) and then SEPARATION BY SOLVENTS. 135 thoroughly extracted with the benzole : solution C. This benzole solution is evaporated in glass dishes, for examination of the residue. It may contain Caffeina, Colchicin, Cubebin, Delpliina, Digitalin (and traces of Berberin, Physostigmin, and Veratria). See also under (7), 134. The watery-acid residue from solution C is now extracted with amylic alcohol: solution D. In this solution there may be Berberin (traces in C), Narcotina (perhaps only in part), Physostigmia (traces in C), Theobromina, Veratria (and traces of Aconitina and Atropina) . The watery-acid residue from solution D is now extracted with chloroform : forming solution E. This may contain Papaverina, Narcotina (if not wholly in D), Thebaina, and perhaps Veratria left from the benzole of C. The watery -acid residue of E is now made slightly alkaline by ammonia, and extracted at about 35 C. with petroleum naphtha. If a little portion of this solution gives a colored residue, the whole of it is thoroughly washed with much water acidulated with sulphuric acid, thus transferring the alkaloids to watery-acid solution, from which they are again extracted by making alkaline and washing with petroleum naphtha. This, solution F, in petroleum naphtha, may contain Brucia, Coma, Emetia, 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, and vera- tria, 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 benzole 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 Aconitia, Atropia, Cinchonia, Codeina, Hyoseyamia, Physostigmia, Quinidia. These alkaloids are all soluble in ether, except cin- chonia. If the residue of the others is dissolved ir. 136 ALKALOIDS. acidulated with sulphuric acid and then supersaturated with am- monia, aconitia and quinidia are precipitated ; while atropia, codeina, hyoscyamia, and physostigmia are (for a brief time) dis- solved. 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 with ainylic 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 H (in amylic alcohol) contains Morphia, Narceina, Solania. Nar- ceina is dissolved from the residue by warm water. The watery alkaline residue of H, which may be termed solution I, may contain Curarin, and traces of Berberina (Digitalin) and Narceina. The solution (I) evaporated to dry- ness, with pulverized glass, yields its alkaloids to alcohoL (7) Separation of Alkaloids and Glucosides from each other. Dragendorffs scheme. Use of the solvents and opera- tions 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. B. Benzole dissolves, from alkaline (ammoniacal), aqueous solutions Aconitia, Atropia, Brucia, Cinchonia, Codeina, Coma, Delphina, Emetia, Hyoscyamia, Narceina (imperfectly), Narco- tina, Nicotia, Papaverina, Physostigmia, Quinia, Quinidia, Strych- nia, Thebaina, Veratria. c. Benzole fails to dissolve, more than traces, from alkaline solutions Morphia, Salicin, Solania, Syringin, Theobromina. D. Benzole does not dissolve, either from acid or alkaline water solutions Curarin, Picrotoxin, Salicin, Theobromina. SEPARATION BY SOLVENTS. 137 E. Benzole, Petroleum Naphtha, Amylic Alcohol, and Chlo- roform, all fail to dissolve, from acid or alkaline solutions, Curarin. F. Amylic alcohol dissolves, from acid (sulphuric) water solutions, more readily when warm Aconitia (very sparingly), Berberina (in greater part), Brucia (in traces), Caffeina, Cantha- ridin, Colchicin, Cubebin, Delphina, Digitalin, Narceina (spar- ingly), Narcotina, Picrotoxin, Piperin, Salicin, Santonin, Theo- bromina, Veratria. G. Petroleum Naphtha leaves undissolved, from acid or alka- line solutions Aconitia, Berberina, Caffeina, Curarin, Narceina, Salicin, Syringin, Physostigmia, Theobromin. H. Petroleum Naphtha dissolves from acid (sulphuric) watery solutions Piperin, Populin. i. Petroleum Naphtha dissolves from alkaline (ammoniacal) solutions Brucia, Conia, Emetia, Nicotia, Papaverina, Quinia, Strychnia, Veratria, and traces of aconita, berberina, cinchonia, delphina, narcotina. j. Petroleum Naphtha does not dissolve, from alkaline solu- tion Caffeina, Colchicin, Delphina. K. Chloroform dissolves from the add (sulphuric) water solu- tion Caffeina, Colchicia, Colocynthin, Cubebin, Delphina (spar- ingly), Digitalin, Narcotina, Papaverina, Piperin, Picrotoxin, Santonin, Thebaina, Theobromina. L. Chloroform dissolves from the alkaline (ammoniaeal) water solution Aconitia, Atropia, Berberina (sparingly), Brucia, Caffeina, Cinchonia, Codeina, Colchicin, Conia, Cubebin, Del- phina, Digitalin, Emetia, Hyoscyamia, Morphia (sparingly), Narcotina, Narceina (sparingly), Nicotia, Papaverina, Piperin, Quinia, Strychnia, Thebaina, Theobromina, Veratria. (8) Separation of certain alkaloids from each other by solubility in alkali. A. Solutions of Fixed Alkalies precipitate, and by excess redissolve, in dilute solution Atropia, Berberina, Codeina, 138 ALKALOIDS. Conia, Hyoscyamia (partly), Morphia, Nicotia, Solania Colchi- cin 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 Aconitia, Colchicin, Hyoscyamia, Physostigmia, Strychnia. (9) Separation by successive use of Ether, Water (and Chloroform). 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 a stoppered flask. The water is applied hot, and in proportion of fully 100 parts to one of solid. The chloroform should be nearly or quite free from alcohol, and 20 to 40 parts used. Alkaloids which are appre- ciably 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). Treat residue (a) with water. Treat Residue (b) with water. Flit. (A) Res. (B). Filtrate (c). Residue (D) Eoap.to res. Evap. to residue (c). (A). Treat (c) with chloroform. Treat (D) with chloroform. Flit. (C). Res. (D). " Flit. (E) "~ResT (F). " Evap. to resid. Evap. to res. (C) (E). (A) (B) (C) (D) (E) (F) Sol. in Ether. Sol. in Ether. Ins.in Ethtr. I us. in Ether. Ins. in Ether. Ins. in Ether. " Water. Ins.inWater. Sol. i~i Water, Sol. in Water. " Water. " Water. " Chl'm. Ins. in Chfm. Sol. in ChVm. " Ch?m. Aconitia. Delphlna. (Berberina). (Berberina). Cinchonia. (Digitalin.) Atropla. (Hydrastia). Brucia. Ergotina. (Digitalin). Pseudoraor- Codeina. (Lobelina). Caffeina. (Narcelna). (Hydrastia). phia. Colchicin. Narcotina. Emetia. (Salicin). Morphia. Solania. Conia. Paytina. (Igasurla). (Saponin). (Narcelna). (Theobromlna). Hyoscyamia. Physostigmia. (Narceina). Papaverina. (Igasuria). Piperin. (Picrotoxin). Rhreadia. Nicotia. Qulnla. (Salicin). Strychnia. (Picrotoxin). Quinidia. (Saponin). (Theobromlna) Thebalna. Veratria. GENERAL REAGENTS. 139 135. 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, the alkaloids are precipitated by potassio mercuric iodide (also a means of volumetric determination) (a) ; by phosphomolybdic acid (per- mitting 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) (/) ; by solution of iodine with iodide (^7). a. The potassio mercuric iodide reagent is prepared by add- ing 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 Caffeina, Colchicin, Digitalin, Theobromina / 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 stan- nous chloride and enough potassa solution to give a strong alka- line 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 volumetric determination by potassio mercuric iodide (MAYER), the reagent is prepared with 13.55 grams mer- curic 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. Atropia, 0.0145 " Brucia, 0.0233 " Cinchonia, 0.0102 gram. Conia, 0.0042 " Morphia, 0.0200 " 140 ALKALOIDS. Narcotina, 0.0213 gram. Mcotia, 0.0040 " Quinia, 0.0108 " Quinidia, 0.0130 gram. Strychnia, 0.0167 " 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 of the clear liquid is placed on a blue or black glass plate, and treated with a drop of the reagent to learn whether further addition is necessary. 1). Phosphouiolybdic acid solution* SONNENSCHEIN'S Re- agent 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. Atropia. Berberina. Blue, then yellow. Yellow. <( tt it Blue to colorless sol. Colorless. Blue solution. Brucia. Caffeina. Orange. Yellow. Yellow-green solution. Brown. Colorless solution. Cinchonia. Codeina. Colchicin. Conia. Whitish-yellow. Brownish-yellow. Yellow. Yellow-white. u Green solution. Orange-red. Bluish solution, in # hr. greenish. Bluish or greenish pre. Colorless. * The yellow precipitate formed on mixing acid solutions of molybdate of ammonium and phosphate of sodium the phosphomolybdate of ammo- nium 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 REAGENTS. 141 PRECIPITATE. WITH AMMONIA. Delphina. Gray-yellow. Digitalin. Yellow, on warm- Blue solution, ing dissolves gr'n. Emetia. Yellowish. Ergotina. (A precipitate.) Morphia. Yellowish. Dark blue sol., in % hr. a blue residue falls. Narceina. Brown-yellow, be- coming resinous. ON BOILING. Green, then colorless. Narcotina. Brown-yellow. Nicotia. YeUow. 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. tt (C Solaiiia. Yellow. Colorless solution. Strychnia. Yellow-white. n Theobromina. u Veratria. YeUow. 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 and 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. d. Fotassio 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 40 parts iodide of potassium in 120 parts of water. 142 ALKALOIDS. 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, Physostigmia, No precipitates are obtained (in dilute solutions) from Col chicin, Solania, Theobromina, or from other known glucosides and neutral substances. The alkaloids are obtained from 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 from water solutions the larger number of the alkaloids, especially as sul- phates. 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, Morphia, 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. Sabadillia in 150 parts of water is not precipitated. Full precipitates are obtained from the strongly acid sul- phates 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 solution of picric acid (WORMLEY) : GENERAL REAGENTS. 143 Least quantity of alkaloid Precipitate. showing precipitate. Aconitia. Yellow, amorphous. WOTTO g ram - Atropia. Yellow, crystalline. Brucia. Yellow. Codeina. Yellow, amorphous. Conia. Yellow, crystalline. nro~o Morphia. Yellow, amorphous. Narceina. " " Narcotina. " " Nicotia. -^^ Solania. " T -J W Strychnia. Yellow, crystalline. 2 g * " Veratria. Yellow, amorphous. ToVo" " The alkaloids may be extracted from their picrates by addi- tion 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 precipi- tates with nearly all the alkaloids. In the larger number of instances these precipitates are easily soluble in acids, frequently dissolving in excess of the tannic acid ; on the contrary, some of the alkaloids are precipitated by tannic acid only in strong acid solutions. Ammonia dissolves the tannates of the alkaloids. No precipitates 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 hydrochloric acid does not dissolve the precipi- tates of tannates of Aconitia, Berberina, Brucia (slightly dis- solves), Caffeina, Cinchonia, Colchicin (dissolves slightly), Del- phina, Digitalin, Narcotina, Papaverina, Thebaina, Soiania, Strychnia (dissolves sparingly), Veratria. 144 ALKALOIDS. Cold dilute sulphuric acid does not 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 in solu- tions strongly acidulated with sulphuric acid, by Aconitia, Physostigmia, Solania, Veratria. Concerning the reactions of the Volatile Alkaloids with tannic acid, see 131. Alkaloids are separated from 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 potassium precipi- tates 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 brown. No precipi- tates are obtained with (Ammonia), Caffeina (in neutral solution), Digitalin (or but slight turbidness), Solania, Theobromina. Yellow precipitates are given by Atropia (sparingly saturated), Hyoscyamia, Physostigmia, and Trimethy lamia (orange-yellow). Red-brown precipitates are obtained with Aconitia, Codeina, Conia, Lobelina, Morphia, Narceina, Narcotina, Nicotia, Quinia, Strychnia, and Veratria. 136. Concentrated sulphuric acid gives characteristic reac- tions with some of the alkaloids ; and a greater number of good indications are given by FROZHDE'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. CONG. SULPHURIC ACID. FRCEHDE'S REAGENT. Aconitia. Slight yellow to yel.-br'n. Yellow-brown ; colorless. Amygdalin. Light violet-red. Atropia. Colorless solution. Colorless. REACTIONS WITH SULPHURIC ACID. 145 CONG. SULPHURIC ACID. FRCEHDE'S 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. YeUow. Colocynthin. Cherry-red (slowly). Colombin. Orange, turning red. Conia. Colorless (pale reddish ?). Pale yellow. Cubebin. Bright red, then crimson. Curarin. Lasting blue. Delphina. Brownish. Red-brown. Digitalin. Brown to red-brown. Orange ; cherry-red ;br'wn. Elaterin. Red. YeUow. Emetia. Brownish. Ergotina. Red-brown. 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. jColorless. Yellowish ; reddish. Ononin. Red. Papaverina. Violet ; blue. Violet ; blue ; yel'w ; color- less. 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. Yellow-red. 146 ALKALOIDS. CONC. SULPHURIC ACID. FRCEHDE'S REAGENT. Smilacin. Yellow-red. Solania. Reddish-yellow. Cherry-red ; red-brown ; yellow. Strychnia. Colorless. Colorless. Syringin. Blood-red, then violet-red. Tannicacid. 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 Strychnia, a brilliant play of changing colors, blue turning soon to violet and then red-violet, then slowly fading (delicate and distinctive). With Brucia, an orange or brown- ish-orange color. With Narceina, a dirty-red mixture. With Hydrastia, a brick-red to carmine-red color; with Picrotoxin, red- brown. With anilin, a yellowish to greenish tint first ap- pears, 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 136). 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 strychnia test, may be made with substitution of other oxidizing agents for the bichromate, the crystallized per- manganate of potassium perhaps giving the best results. SON- NENSCHEIN advocates the use of ceroso-ceric oxide. 138. Concentrated Nitric acid, of spec. grav. 1.42, gives a red or reddish-yellow color with the greater number of the alka- loids. 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 warm* ing, or standing, the color changes to yellow : if now a drop of REACTIONS WITH NITRIC ACID. 147 solution of stannous chloride is added, a purple color appears. The purple is discharged by either nitric acid or excess of stan- nous 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. Morphia in somewhat concentrated solutions is colored yel- low to orange-red the color is either not changed or is altered toward the yellow by stannous chloride (distinction from brucia). Codeina, Narceina, and Papaverina are colored red to orange-yellow by nitric acid ; and Narcotina, Pseudomorphia, Opiania, Thebaina, and Rhceadia, yellow, Emetia is changed to a yellow, resinous mass, with partial decomposition. Colcliicin is colored violet by nitric acid : the most concen- trated 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 colchicin is treated with concentrated nitric acid, a violet-red color is formed and taken up by the chloroform layer. Curarin is colored purple by nitric acid. Nitric acid produces no color with Atropia (brown tint, fad- ing), Caffeina, Cinchonia, Conia (sometimes yellowish), Quinia, Quinidia, Solania (becoming faint rose-red with bluish rim), Theobromina. Berberina 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 Narcotina gives a deep blood-red color (delicate and distinguishing). The color is discharged by much excess of nitric acid. In the same test, Brucia gives an orange- red, and Opiania a scarlet-orange color. Codeina becomes first greenish, then reddish. Narceina turns reddish-brown. 140. Chlorine water followed by ammonia. Quinia (or 148 ALKALOIDS. Quinidia) treated first with fresh chlorine water 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, re- turning 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 Quinidia a bulky precipitate). A better result is obtained by adding the ferricy- anide 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. Colchicin, when treated with chlorine and ammonia, gives an orange solution. Caffeina and Theobromina, treated with chlorine water (or nitric acid), then evaporated to dry ness, on addition of ammonia give a purple-red color. CJilorine, alone, with Brucia and w r ith Igasuria gives a light red color; with Hydrastia,) blue fluorescence. Pliysostigmia, with solution of chlorinated lime, gives an intense red color, turning nearly black by farther addition. 141. Solution of Ferric chloride (dilute) colors solid Mor- phia, and Pseudomorpliia blue. Also Daphnin blue in the cold, turning yellow when warmed. Morphia 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, whitish- " yellow or grayish-yellow, and some of them being soluble in cold hydrochloric acid. Anilin, Digitalin, Physostigmia, and Solania, are not precipitated ; and Aconitia, Atropia, Codeina, Hyoscyamia, Narcotia, Nicotia, Sabadillia, and Veratria only from concentrated solutions. The alkaloids next named give precipitates ; each precipitate, after ignition, leaving a weight of pure platinum bearing a fixed ratio to the weight of the alka- loid in accordance with the formula given. DETERMINATION BY PLATINIC CHLORIDE. 149 S . use strict precautions in the manipulation tf its vapor. 5. Ether is p^prox ; mately separated from alcohol by means of glycerin (or water). A test-tube of over 20 c.c. capacity is from the point of 10 c.c. contents (marked 0) to the r/ 40 c.c. contents (marked 10). Ten c.c. of glycerin or 180 ALCOHOLIC PRODUCTS. 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. C 2 H 5 NO 2 . Nitrite of ethyl. Characterized by its sensible and physical properties (a) and by reactions of nitrites. Estimated, in its alcoholic mixtures, by their boiling point (6), and by volumetric trial with permangan- ate (c). 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 im- mersed 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 taken. 197. CHLOROFORM. CHC1 3 . Identified by its sensible and physical properties (a) ; its liberation of chlorine when de- composed (>), and its production of isonitril (c). It acts as a reducing agent (d). It is separated by washing with concentrated sulphuric acid and with water, and rectification from alkaline carbonate, lime, calcium chloride, animal charcoal (e). It may CHLOROFORM. 181 he estimated from the chloride it gives after digestion with alcoholic fixed alkalies. a. Chloroform is a colorless liquid, of spec. grav. 1.497 (at 15 C.), boiling at 61 C. (142 F.). It is neutral in reaction, and has an agreeable sweet ethereal odor 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, petroleum naphtha, bisulphide of carbon, fixed and volatile oils not in concentrated sulphuric acid. It dissolves sulphur, phosphorus, iodine, iodoform, resins, caout- chouc, and gutta percha. b. Chloroform is decomposed, with production of chlorine and hydrochloric acid, when it is passed in vapor through a red- hot tube ; or, with production of chloride and formate, when digested with alcoholic solution of potassa (slowly by aqueous potassa). (Alcoholic ammonia produces ammonium cyanide and chloride the better with help of potassa.) CH C1 3 4-4KH 0=3K Cl-j-K CH O 2 +2H 8 O CH C15N H =3NHCl]Sr 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 alco- holic chloroform affects silver nitrate.) c. Chloroform, even in solution with 5,000 parts of alcohol, when treated with anilin (or other monamine) and then with alcoholic soda, forms an isonitril, recognized by its characteris- tic odor (HOFFMANN). This test distinguishes chloroform from Chlorcethylidene (C 2 H 4 C1 2 ) . Iodoform, Bromoform, Chloral, etc., react in the test, the same as chloroform. 182 ALCOHOLIC PRODUCTS. d. Chloroform readily reduces the hot potassio cupric solu- tion (distinction from chlorcethylidene and from alcohol) . e. Chloroform may be separated from slight mixtures of Ether, Alcohol, water, etc., as follows : To 10 parts of the impure chloroform, add 2 parts of concentrated sulphuric acid, and shake together occasionally for 24 hours. Remove the upper layer, add to it -| part of (crystallized) carbonate of sodium previously dissolved in 1 part of water, agitate and digest (cold) for half an hour, then remove the lower layer and distil it from -gL part of freshly-burned lime. Distillation from dry calcium chloride separates chloroform from alcohol. To separate from Ethe- real Oil (ethyl and ethylene sulphates), distil from animal charcoal. 198. CHLORAL HYDRATE. C 2 HC1 3 O.H 2 O. Charac- terized by its sensible and physical properties (a), and its forma- tion of chloroform (5), and of chloralide (c). It has, with alkalies, considerable reducing power (d). Separated from chloral alco- holate by its slight solubility in cold chloroform and its greater solubility in cold water. Estimated from the amount of chloro- form 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 95 C. (203 F.) (the Alcoholate boils at 116 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 1J 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 mix- tures with camphor, and with phenic acid, and a crystalline mixture with glycerin. CHLORAL HYDRATE. 183 b. Fixed and volatile alkalies, and their carbonates, in solu- tion, decompose chloral hydrate the chloroform subsiding from the milky mixture'. C 2 HC1 3 O.H 2 0+KHO=CHC1 3 +K:CH0 2 +H 2 (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 formed when chloral hydrate (con- centrated, if necessary, by distillation from 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 (C 5 H 2 C1 6 O 3 ) 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, d. ' 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 ALCOHOLIC PRODUCTS. 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. CHI 3 . A sulphur-yellow solid, crys- tallizing in hexagonal plates, stars, and rosettes; melting, at 115 to 120 C., with partial vaporization and partial decomposition into carbon, hydriodic acid, and iodine. It has a saffron-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 parts 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 decom- posed by boiling aqueous potassa, but (WITTSTEIN) alcoholic potassa decomposes it, forming iodide and formate (see chloro- form, b). 200. CROTON-CHLORAL HYDRATE. C 4 H 3 C1 3 O. 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 (C 3 H 2 C1 2 ). 201. AMYLIC ALCOHOL. C 5 H 12 O. Characterized by its sensible and physical properties (a) ; by its production of red sulphamylic acid (b) ; by its formation of odorous ethers (c). It is separated from alcohol by fractional evaporation or distilla- tion, or by adding water and extracting with ether (d) ; from water, in the slight proportions miscible, by adding petroleum naphtha or benzole, or \iy adding common salt (e). AMYLIC 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 solution of common salt, soluble in all pro- portions of alcohol, ether, chloroform, benzole, petroleum naph- tha, 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, sulphamylic acid, or amyl sulphuric acid is formed having a red color and 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 and a little water and bichromate of potassium, the apple-odor of valeric aldehyde is first generated, and then the peculiar odor of valeric acid (42). d. It is separated from (aqueous) ethylic alcohol, by adding an equal volume of pure ether, and 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 petro- leum 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 fusel-oil. taken. 202. " FUSEL-OIL " contains, besides amylic alcohol, small proportions of Butyric, Valeric, and volatile Fatty Acids, and 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 c.c. of sulphuric acid and nearly as much water : 186 ALCOHOLIC PRODUCTS. when, if the acids in question are present, their odor will be apparent.* 203. NITRITE OP AMYL. C 6 H n NO 2 . A light-yellow- ish liquid, darkening when heated, of spec. grav. 0.877, boiling at about 96 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 combus- tion. Alcoholic potassa decomposes it quickly, forming potassic nitrite : aqueous potassa decomposes it slowly. * Farther, see Prescott's Examination of Alcoholic liquors, New York, 1875. INDEX. ABSINTHIN, 151, 156. Acacia, 162. Acetic Acid, 13, 58. Acetic Ether, formation of, 59. Acids, 13. Separated as lead salts, 59. Aconitia, 125, 128, 135, 137 to 140, 142 to 144, 148, 150. Aconitic Acid, 13, 21. Acrolein, formation of, 86. Acrylic Acid, formation of, 86. Agaric Resin, separated from Gam- boge, 98. Separated by Chloroform, 104. Albumen, 158. Albumenoids, 13, 157. Alcohol, 13, 176. Alcohols, 175. Aldehyd, 13, 177. Aldehyds, as Volatile Oils, 104. Alkaloids, Fixed, 13. Volatile, 13, 120. AUspice Oil See Pimento Oil. Almond Oil, 73, 76, 78, 81. Almonds, Oil of Bitter See Bitter Almond Oil. Aloes Resins, 93, 103. Separation of Gamboge from, 98. Aloin, 151, 156. Amber, 93, 103. Amber Oil, 107, 108, 109, 111, 114. Ammonia, 124. Ammoniac, 93, 103. Amygdalin, 144, 152. Amylic Alcohol, 13, 184. Amyl, Mtrite of, 186. Amyloid, 168. Anilin, 120, 140, 142, 146, 148. Compounds, 13, 14. Anise Oil, 107 to 111, 114. Anthracene, 13, 117. Arabic Acid, 162. Arabin, 162. Asparagin, 153, 156. Assaf etida, 94, 103. Atropia, 125, 128, 135, 137 to 140, 142 to 144, 147, 148, 150. Auric Chloride, as Reagent for Al- kaloids, 150. BALM Oil, 107, 112. Balsams, 93. Balsam of Copaiba, 96. Peru, 102, 103. Tolu, 103. Baranilin, 120. Bases, Volatile, 120. Beech-nut Oil, 73, 76, 81. Benzene, 119. Benzoin, 94, 103. Benzole, 13, 118. Benzoyl Hydride see Bitter Al- mond Oil. Berberina, 125, 128, 135 to 138, 140, 142, 143, 145, 147, 149, 151. BergamotOil, 107 to 110, 112, 114. Bitter Almond Oil, 107 to 111. Artificial see Nitrobenzole. Formation of, 62. Boheic Acid, 13, 36. Bone OiL 76, 81. British Gum see Dextrin. Bromated Camphor, 116. Brucia, 125, 128, 135, 137 to 140, 142, 143, 145 to 150. Butter, 74, 81. Butyric Acid, 13, 60, 61. Ether, Formation of , 62. Butyrin in Butter, 81. CACAO Butter, 74. Cacodyl, Formation of, 59. Caffeina, 125, 127, 128, 135 to 140, 143 to 145, 148 to 150. Caffetannic Acid, 13, 28, 35. Cajeput Oil, 107 to 110, 112, 114. Calamus Oil, 107 to 110. Calvert's Tests for Fixed Oils, 78. Camphor Oil, 107. Camphors, 13, 116. CanaubaWax, 95, 103. Cane Sugar see Sucrose. Cannabin, 98. Caoutchouc, 95, 103. Capric Acid, 67, 68. Caproic Acid, 67, 68. Caprylic Acid, 67. Caramel, 173, 174. Caramelane, 174. Caramelene, 174. Caramelin, 174. Caraway. Oil of, 107 to 110, 112. Carbazotic Acid see Nitrophenic Acid. 187 188 INDEX. Carbohydrates, 13, 161. Carbolic Acid see Phenic Acid. Carbon, uncombined, 11. Compounds of, 111. Cardamon Oil, 107, 108. Carminic Acid, 13, 40. Carmine see Carminic Acid. Cascarilla Oil, 107, 109, 112. Casein, 159. Castor Oil, 73, 76, 78, 80, 81. Catechu, 34. Catechuic Acid, 13, 28, 34. Catechutannic Acid, 13, 28, 33. Cathartic Acid, 153, 156. Cathartin sea Cathartic Acid. Cellulose, 13, 167. Cephselic Acid, 28. Ceroso-ceric oxide, as Reagent, 146. Cerotic Acid, 13, 70. Chamomile Oil, 107, 108, 109. Chloral Hydrate, 13, 182. with Oil of Peppermint, 115. Chloralide, 182. Chlorine, as Reagent for Alkaloids, 148. Chloroform, 13, 180. Chrysammic Acid, 152. Chrysophanic Acid, 13, 41. Chrysophane see Chrysophanic Acid. Cinchona Bark, separation of Acids from, 37, 39. Cinchonia, 125, 128. 136 to 140, 142, 143, 145, 149, 150. Cinchonidia, 125, 128, 149, 150. Cinchotannic Acid see Quinotannic Acid. Cinnamate of Cinnyl, 102. Cinnamon Oil, 107 to 110, 112, 114. Citric Acid, 13, 18. Citric Acid, distinguished from Tar- taric, 15. Cloves, Oil of, 107 to 111. Cochineal, separation of Carminic Acid from, 26. Cocoa-nut (Coco-nut) OH, 80. Codeina, 125, 127, 128, 136 to 138, 140 to 143, 145, 147 to 150. Cod-liver Oil, 73, 77, 78, 80, 81. Coffee, separation of Caffetannic Acid from, 35. Cohesion-figures of Oils, 74, 105. Colchicia (Colchicin), 125, 127, 128, 135 to 140, 142 to 150. Colocynth, separation from Gam- boge, 98. Colocynthin, 136, 137, 145. Colombic Acid see Columbia Acid. Colombin, 145, 151, 156. Colombo Bitter see Colombin. Colopholic Acid, 96. Colophony, 95, 103. Separation from Lac, 101. Color Resins, 93. Columbic Acid, 13, 39. Columbo Root, separation of Acid from, 39. Colza Oil, 73. Conia, 123, 128, 135 to 138, 140, 142 to 145, 149. Convolvulic Acid, 100. Convolvulin, 100, 103. Separation from Gamboge, 98. Convolvulinol, 100. Convolvulinolic Acid, 100. Copaiba Oil, 107, lOa 110, 113, 114. Copaiba Resins and Balsam, 96. Copaivic Acid, 96. Copal, 96, 103. Coriander Oil, 107, 113. Cotton-seed Oil, 73, 76, 81. Creosol, 68. Creosote, 13, 116. Cresylic Acid, separation of Phenic from, 48, 50. Croton Chloral Hydrate, 184. Oil, 73, 77. Cubebin, 135 to 138, 145, 154, 156. Cubeb Oil, 107 to 110. Cumidin, 120. Cummin Oil, 107, 108. Curarin, 136, 137, 142, 145, 146, 147. Cymidin, 120. Cytisin, 142. DAMMARA (Dammaran, etc.), 96, 103. Daphnin, 125, 128, 148. Daturia see Atropia. Delphina, 125, 128, 135 to 138, 141 to 145, 149, 150. Dextrin, 13, 162. Dextrose see Glucose. Dextrotartaric Acid, 13. Dialysis of Alkaloids, 131, 134. Digitaleic Acid see Digitalic Acid. Digitalic Acid, 13, 28. Digitalin, 125, 127, 128, 135 to 139, 141, 143 to 145, 149, 150. Digitoleic Acid see Digitalic Acid. Dill Oil, 107, 111. Distillation, Fractional, 66. Dragendorff's Method with Alka- loids, 131, 134, 136. Dragon's Blood, 97, 103. ELATDIN, formation of, 75 Elseoptenes, 104. Elafcerin, 136, 145, 154, 156. INDEX. 189 Emetia, 125, 128, 135 to 138, 141, 142, 145, 149, 150. Emulsions, formation of, 74. Ergotina, 125, 128, 141, 145. Erucic Acid, 13, 70. Essence of Mirbane see Nitroben- zole. Ether, 13, 179. Ethers, Compound, 13. Ethylic Alcohol, 176. Ethyl Sulphates, 177. Eucalyptus Oil, 107, 109, 113. FATTY Acids, 13. Separation from Neutral Fats, Non-volatile, 68. Volatile, 67. Fats, 72. Fennel Oil, 107, 108, 109, 112. Ferric Chloride, as Reagent for Al- kaloids, 148. Fixed Oils, 72. Formic Acid, 13, 55, 60, 75. Ether, formation of, 56. Fractional Crystallization, 68. Fusion, 71. Saturation and Distillation, 66. Frankincense, 102. Fraxin, 154, 156. Frohde's Reagent, 144, Fuchsin, 120. Fusel-Oil, 185. Fustic, separation of Morintannic Acid from, 35. GALANGAL Oil, 107. Galbanum Oil, 107. Gallic Acid, 13, 3O. Gallotannic Acid, 28. Gamboge, 97. Resin of, 97, 103. Gambogic Acid, 13, 41, 97. Gasolene, 119. Gelatin, 13, 16O. Gentianic Acid, 13, 39. Gentianin see Gentianic Acid. Gentian Root, separation of Gen- tianic Acid from, 40. Gentisic Acid see Gentianic Acid. Gentisin see Gentianic Acid. Geranium Oil, 107, 113. Glucose, 168. Glucosides (with Alkaloids), 125. Glue see Gelatin. Glyceric Acid, resemblance to Lac- tic, 53. Glycerin, 13, 85. Determined in Soap, 91. Graham and Hof mann's Method, 131, Grape-seed Oil, 72. Grape Sugar, 168. Guaiacol, 116. Guaiac Resin, Separation from Gam- boge, 98, 103. Guaiacum, 98, 103. Guaiaretin, formation of, 98. Gum, 13, 161. Arabic, 161. Tragacanth, 162. Gum-resins, 93. Gun Cotton see Nitrocellose. HAGER'S Method with Volatile Oils, 111. Hazel-nut Oil, 73. Hemp Resin, 98, 103. Hemp-seed Oil, 72, 77, 80, 81. Hesperidin, 145. Hippuric Acid, distinguished from Benzoic, 43. Hop Oil, 107, 109. Hydrastia, 125, ,128, 138, 145, 146, 148. Hyoscyamia, 125, 128, 135 to 138, 142, 144,145, 148 to 150. IGASURIA, 125, 128, 138, 145, 147, 148. Incense see Olibanum. Indian Hemp see Hemp Resin. India Rubber see Caoutchouc. Indigo Blue, 99, 103. Iodine Solution, as Reagent, 139, 144. lodoform, 13, 177, 184. JALAP Resins, 99. Jalapic Acid, 100. Jalapin, 99, 103. Separation from Gamboge, 98. Jalapinol, 100. Jalapinolic Acid, 100. Jasmin Oil, 107. Juniper Oils, 107, 108, 109, 113, 114. KINIC Acid see Quinic Acid. Kinotannic Acid, 33. Kinovic Acid see Quinovic Acid. Kinovin see Quinovic Acid. Kuphanilin, 120. LAC (resin), 100, 103. Lactic Acid, 13, 53. Lactoscope, Vogel's, 84. Lactose, 171. Lactucin, 154, 156. Lard, 74. In Butter, 83. Oil, 73, 76, 78, 80, 81. 190 INDEX. Laurie Acid, 13, 70. Lavender Oil, 107, 108, 110, 113, 114. Lead Salts of Acids separated, 59. Leather, 161. Lemon Oil, 107 to 110, 113, 114. Limonin, 145. Linoleic Acid, 13, 69. Liquid Non- volatile Acid, 53. Volatile Acids, 55. Liquids, Preliminary Examination of, 12. MACE, 107, 109, 113. Magenta, 121. Maisch's tests for Volatile Oils, 110. Marjoram Oil, 107, 109, 113. Malic Acid, 13, 32. Mannite, 174. Mastic, 101, 103. Masticin, 101. Mayer's tests with Volatile Alka- loids, 124. Meconic Acid, 13, 24. Meconin, 145. Metachloral, 183. Metapectic Acid, 167. Metapectin, 167. Metatungstic Acid, as Reagent, 141. Methylic Alcohol, 13, 174. Milk Albumen, 159. Commercial Examination of, 160. Determination of Fats in, 84. Casein in, 159. Quantitative Analysis of, 160. Sugar see Lactose. Mirbane, Essence of see Nitroben- zole. Molybdate, as Reagent, 141. Monophenylamin see Anilin. Morintannic Acid, 13, 28, 35. Morphia, 126 to 128, 136 to 139, 141 to 145, 147 to 150. Mustard Oils, 73. Myristic Acid, 13, 70. Alcohol, 95. Myrrh Oil, 107. Resin, 101, 103. Separation of, from Gamboge, 98. NABCEINA, 126 to 128, 136 to 138, 141 to 150. Narcotina. 126 to 128, 135 to 138, 140 to 145, 147 to 149. Nicotia. 123, 124, 128. 135 to 138, 141 to 145, 148, 149. Nitric Acid, as Reagent for Alka- loids, 147. Nitrite of Amyl, 186. Ethyl, 180. Nitrobenzole, 13, 112, 119. Nitrocellulose, 168. Nitrogenous Neutral Bodies, 157. Nitrophenic acid, 13, 49, 51. Nitrous Ether, 180. Non-drying Oils, 73, 75. Non-volatile Alkaloids, 125. Fat Acids, 68. Nutmeg Oil, 107, 111, 114. OENANTHYC Acid, 67, 68. Oenanthylic Acid see Oenanthyc. Oils, Fixei, 13, 72. Volatile, 13, 104. Oleic Acid, 13, 69. Oleo-resins, 93. Olibanum (resin), 102. Olive Oil, 73, 76, 77, 80, 81. Ononin, 145. Opiania, 126, 127, 129, 148. Opianyl see Meconin. Opium, Separation of Meconic Acid from, 24, 25. Orange Flower Oil, 107, 109, 113. Peel Oil, 107, 109, 110, 113, 114. Organic Compounds, determined as such, 11, 12. Origanum Oil, 107. Otto-Stas' Method with Alkaloids, 130, 131. Ovalbumen, 158. PALMITIC Acid, 13, 70. Papaverina, 126, 127, 129, 135 to 138, 141 to 145, 149, 150. Paracumaric Acid, formation of, 93. Parapectic Acid, 166. Parapectin, 166. Parmelia Parietina, Chrysophanic Acid from, 41. Parsley Oil, 107, 109, 113. Patchouli Oil, 110. Paytina, 126, 129, 138. Pectic Acid, 166. Pectin, 13, 166. Pectose, 166. Pectous Substances, 166. Pelargonic Acid, 67. 68. Peppermint Oil, 107, 109, 111, 112, 114, 115. Pepper Oil, 107, 114. Peru Balsam, 102, 103. Petroleum Naphtha, 13, 119. Phenic Acid, 48. Phenol see Phenic Acid. Phenylamin see Anilin. Phenylic Alcohol see Phenic Acid. Phenyl Sulphuric Acid see Sulpho- phenic. INDEX. 191 Phloridzin, 145, 155, 156. Phosphomolybdio Acid, as Reagent, 139, 140. Physostigmia, 126, 139, 135, 136, 138, 141 to 145, 148, 150. Picramic Acid, 52. Picric Acid, as Reagent, 139. See Mtrophenic Acid. Picrotoxin, 126, 127, 129, 136 to 138, 146. Pimaric Acid see Colopholic Acid. Pimento Oil, 107. Pinic Acid, in Colophony, 96. Piperidin, 141. Piperin, 126, 129, 134, 136, 137, 138, 141 to 145, 147. Platinic Chloride, as Reagent for Alkaloids, 148. Podophyllum Resin, 102, 103. Poppy-seed Oil, 72, 77, 78, 80. Populin, 137, 145, 155, 156. Potassio Mercuric Iodide, as Re- agent, 139. Cadmic Iodide, as Reagent, 141. Propylamin see Trimethylamia. Pseudomorphia, 126, 127, 129, 138, 142.145,148. Pyrogalljc Acid, 13, 32. Pyrogalline Pyrogallol see Pyro- gallic Acid. Pyroxyllon see Nitrocellulose. QUASSIN, 155, 156. Quercitannic Acid, 27, 28. Quinia, 126, 129, 135 to 138, 140 to 142, 144, 145, 148, 149, 150. Quinic Acid, 13, 36. Quinidia, 126, 129, 135, 136, 138, 140, 141, 142, 145, 149, 151. Quinone, Formation of, 37. Quinotannic Acid, 13, 38, 33. Quinovic Acid, 13, 38. Quinovin see Quinovic Acid. RACEMIO Acid, 13, 18. Rape-seed Oil, 73, 76, 78, 80, 81. Resinifled Oils, 105, 115. Resins, 13, 92. Determined in Soaps, 90. Roeadia, 126, 129, 138. Rhubarb, Chrysophanic Acid from, 41. Ricinoleic Acid, 13, 69. Rodgers and Girdwood's Method, 130, 132. Rosanilin, 121. Rosemary Oil, 107, 109, 111, 113, 114. Rose Oil, 107, 109, 111, 113, 114. Rosewood Oil, 107. Rosin Oil, 96. Rue Oil, 108, 109, 111, 113. SABADILLIA, 126, 129, 142, 148. Sabadilla Seeds, V eratric Acid from, 47. Saccharose see Sucrose. Salicin, 126, 129, 136, 137, 138, 145. Salicylic Acid, 13, 47. Sandarac, 102, 104. Sanguinarin, 142. Santalic Acid, 13, 42. Santalin see Santalic Acid. Santonin, 137. Saponification, Means of, 75. Saponin, 126, 129, 138. Sarcolactates, 54. Sarsaparillin, 146, 156. Sassafras Oil, 108, 109, 110. Saturation, Fractional, 60. Savine Oil, 108, 109, 114. Scammonin see Jalapin. Scammony, 102. Seal Oil, 80. Secalin see Trimethylamia. Senagin, 146. Senna Resin, Separation from Gam- boge, 98, 104. Separation of Acids, x as Lead Salts, 59. Alkaloids from other matters, 130. each other, 156. G-lucosides, 156. Fixed Oils, 85. Non-volatile Fat Acids, 71. Resins, 103. Solids from Liquids, 12. Volatile Fat Acids, 66, 68. Volatile Oils, 105. Seralbumen, 158. Sesame Oil, 73, 76, 80, 81. SheU Lac, 101. Soaps, 13, 87. Solania, 126, 127, 129, 136, 138, 141 to 145, 147, 148, 151. Solids, Preliminary Examination of, 11. Solid Volatile Acids, 42. Non-volatile Acids, 14. Soluble Starch, 164. Smilacin, 146. Spermaceti, 74. Spearmint Oil, 108, 110. Spirit of Nitrous Ether, 180. Starch, 13, 164. Starch Sugar see Glucose. Stas and Otto's Method with Alka loids, 130. Stearic Acid, 13, 7O. 192 INDEX. Stearoptenes, 104. Storax Resin, 103. Strychnia, 126, 137, 139, 135, 137, 138, 140 to 144, 146, 151. Test, 146, 149. Styracin, 102, 103. Succinic Acid, 45. Sugars, 13, 1G8. Sulphuric Acid, as Reagent, 144, 155, 156. See, also, under Glucosides. Sunflower Oil, 73, 77. Sweet Spirits of Nitre see Spirits Nitrous Ether. Sylvic Acid, in Colophony, 96. Syringin, 136, 146. TALLOW, 74. in Butter, 83, 83. Tannic Acid, 13, 18, 146. distinguished from Gallic, 31. as Reagent, 139, 143. Tannic Acids, 26. Tanoxylic Acid, 27. Tansy Oil, 108, 109, 114. Taraxacin, 156. Tartaric Acid, 13, 14. Tea, Black, Separation of Boheic Acid from, 36. Thebaina, 126, 137, 139, 135 to 138, 143, 143, 146, 149, 151. Theobromina, 127, 129, 136 to 139, 141, 143, 146, 148, 149, 151. Thyme Oil, 108, 109, 114. Tolu Balsam. 103. Toluidin, 120, 121. Tolu Resin, Separation from Gam- boge, 98. Tragacanth, 162. Trimethy lamia, 123, 124 Trinitrophenic Acid see Nitro- phenic. Trommer's Sugar Test, 169. USLAR and Erdmann's Method, 130. 133. VALERIANIC Acid see Valeric. Valerian Oil, 108, 109, 111, 113, 115. Valeric Acid, 13, 60, 63. 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By WILLIAM CART, C.E. Illustrated. D. VAN NOSTEAND. 23 XIII. A PRACTICAL TREATISE ON THE GASES MET WITH IN COAX. MINES. By the late J. J. ATKINSON, Government Inspector of Mines for the County of Durham, England. XIV. FRICTION OF AIR IN MINES. By J. J. ATKINSON, author of " A Practical Treatise on the Gases met with in Coal Mines." XV. SKEW ARCHES. By Prof. E. W. HYDE, C.E. Illustrated with numerous engravings and three folded plates. XVI. A GRAPHIC METHOD FOR SOLVING CERTAIN ALGEBRAIC EQUA- TIONS. By Prof. GEORGE L. VOSE. With Illustrations. XVH. WATER AND WATER SUPPLY. By Prof. W. H. CORFIELD, M.A., of the University College, London. XVIH. SEWERAGE AND SEWAGE UTILIZATION. By Prof. W. H. CORFIELD, M.A., of the University College, London. XIX. STRENGTH OF BEAMS UNDER TRANSVERSE LOADS. By Prof. W. ALLAN, author of " Theory of Arches." With Illustrations XX. BRIDGE AND TUNNEL CENTRES. By JOHN B. MCMASTERS^ C.E. With Illustrations. XXI. SAFETY VALVES. By RICHARD H. BUEL, C.E. With Illustra- tions. XXn. HIGH MASONRY DAMS. By JOHN B. MCMASTERS, C.E. With Illustrations. XXfll. THE FATIGUE OF METALS under Repeated Strains, with various Tables of Results of Experiments. From the German of Prof. LUDWIG SPANGENBERG. With a Preface by S. H. SHRKVE, A.M. With Illustrations. XXIV. A PRACTICAL TREATISE ON THE TEETH OF WHEELS, with the theory of the use of Robinson's Odontograph. By S. W. ROBIN- SON, Prof, of Mechanical Engineering, Illinois Industrial University. XXV. THEORY AND CALCULATIONS OF CONTINUOUS BRIDGES. By MANSFIELD MERRIMAN, C.E. With Illustrations. XXVI. PRACTICAL TREATISE ON THE PROPERTIES OF CONTINUOUS BRIDGES. By CHABLES BENDER, C.E. 2i V. VAN NO STRAND. XXVII. ON BOILER INCRUSTATION AND CORROSION. By F. J. ROWAN. With Illustrations. ^SXVIII. ON TRANSMISSION OF POWER BY WIRE ROPE. By ALBERT W. STAHL. With Illustrations. XIX. INJECTORS. The Theory and Use. Translated from the French of M. LEON POCHET. With Illustrations. XXX. TERRESTRIAL MAGNETISM AND THE MAGNETISM OF IRON SHIPS. By Prof. FAIRMAN ROGERS. With Illustrations. XXXI. THE SANITARY CONDITION OF DWELLING HOUSES IN TOWN AND COUNTRY. By GEORGE E. WARING, Jr. With Illustrations. XXXII. CABLE MAKING OF SUSPENSION BRIDGES AS EXEMPLIFIED IN THE EAST RIVER BRIDGE. By WILHELM HILDENBRAND, C. E. With Illustrations. XXXIII. MECHANICS OF VENTILATION. By GEORGE W. RAFTER, Civil Engineer. XXXIV. FOUNDATIONS. By Prof. JULES GAUDARD, C. E. Translated from the French, by L. F. VERNON HARCOURT, M. I. C. E. XXXV. THE ANEROID BAROMETER, ITS CONSTRUCTION AND USE, Com- piled by Prof. GEORGE W. PLYMPTON. Illustrated. XXXVI. MATTER AND MOTION. By J. CLERK MAXWELL, M. A. XXXVII. GEOGRAPHICAL SURVEYING. Its Uses, Methods and Results. By FRANK DE YEAUX CARPENTER, C. E. XXXVIII. MAXIMUM STRESSES IN FRAMED BRIDGES. By Prof. WM. CAIN, A. M., C. E. Illustrated. XXXIX. A HAND BOOK OF THE ELECTRO MAGNETIC TELEGRAPH. By A. E. LORING. Illustrated. XL. TRANSMISSION OF POWER BY COMPRESSED AIR. By ROBERT ZAHNER, M. E. Illustrated. XL1 ON THE STRENGTH OF MATERIALS. By WM. KKNT, C. E. XLII. VOUSSOIR ARCHES APPLIED TO STONE "BRIDGES, TUNNELS, ETC. By Prof. W. Cain. UNIVER$IT$W CALIFORNIA LIBRARY BERKELEY Return to desk from which borrowed. This book is DUE on the last date stamped below. DEC 6 1947 28De U DEC 18 1961 LD 21-100m-9,'47(A5702sl6)476