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I
POISONS:
THEIR EFFECTS AND DETECTION.
!r«r„
BY THE SAME AUTHOR
Fifth Edition, Thoroughly Reyiaed, Greatly Enlarged and Re*written.
With additional Tables, Plates, and IlluatrationB. 21s.
POODS:
THEIR COMPOSITION AND ANALYSIS.
By a. WYNTER BLYTH, M.R.C.S., F.I.C., F.C.S.,
Barri8ter-at-Law, Public Analyit for the Coanty of Devon, and Medical Officer of Health
for St Marylebone,
And M. WYNTER BLYTH, B.A., B.Sc, F.C.S.
" Simply IMDI8PKMSABLK in the Analyst's laboratory."— TA« Laneet.
" A new edition of Mr Wynter Blyth's SUndard work, kmriohkd wrrn all thk RaoxMT
DfSCOYKRlxs AND iMPROVKiiKiiTS. will be accepted as a boon."— ChenUeal HetM.
OTHER STANDARD WORKS.
Crown 8vo, Handsome Cloth. With Diagrams. 7s. 6d. net.
TOXINES AND ANTITOXINES.
By CARL OPPENHEIMER, Ph.D., M.D.,
Of the Physiological Institute at Erlangen.
TRANSLATED FROM THR GERMAN BY
C. AINSWORTH MITCHELL, B.A., B.Sc, F.I.C., F.C.S. I
With Notes, and Additions by the Author since the publication of the German Edition. |
Deali wUh the theory qf Bacterial and other Toxinei, tueh at Tuberculin, Ridn, Cobra Poiton, etc.
I
Third Edition, Thoroughly Revised and Enlarged. 21s. ■
FORENSIC MEDICINE AND TOXICOLOGY.
Br J. DIXON MANN, M.D., F.R.C.P.,
Physician to the Sal ford Royal Infirmary ; Professor of Medical Jurispradence and
Toxicoloflry, Owens College, Manchester ; Examiner in Forensic Medicine,
London University, and Victoria University, Manchester.
" We consider this work to be one of the best tkxt.books on forknsio mkdioink and
TOXiooLOOT NOW tN PRINT, and we cordially recommend it to students who are preparing for
their examinations, and also to practitioners who may be, in the course of their professional
work, called upon at any time to assist in the investigations of a medico-legal case."— 7A« Laneet
With Illustrations. Handsome Cloth. 8s. 6d. net.
THE PHYSIOLOGY AND PATHOLOGY OF
THE URINE.
Bt J. DIXON MANN, M.D., F.R.C.P.
** Dr Dixon Mann is to be congratulated on having produced a work which cannot fail to be
of inestimable value alike to medical men and students, and which is in every respect worthy
of his high reputation."— JBnt. Med. Joum.
In Pocket size. Leather. With Frontispiece. 8s. 6d.
A HANDBOOK OF
MEDICAL JURISPRUDENCE AND TOXICOLOGY,
FOR THE USE OF STUDENTS AND PRACTITIONERS.
By WILLIAM A. BREND, M.A.Cantab., M.B., B.So.Lond,
Late Scholar of Sidney Sussex College, Cambridge, of the Inner Temple, Barrister*at-Law.
"We recommend it as a trustworthy work .... one specially suitable for students and
practitioners of medicine .... the neceAsary facts only are stated."— La?ic»t.
London: CHARLES GRIFFIN & CO., Ltd., Exeter St., Strand.
POISONS:
THEIR EFFECTS AND DETECTION.
BY
ALEXANDER WYNTER BLYTH,
M.B.C.S.. F.I.a, F.C.S., &0., ^
BARRI8TKR-AT-LAW: PUBUO ANALYST FOR THK OOUNTT OF DKYOM ; MKDIOAL OFFIOKR OF HKALTH
AND PUBLIC ANALYST FOR TH8 BOROUGH OF ST. MARYLVBONX ;
AND
MEREDITH WYNTER BLYTH,
B.A. (CanUb)., B.SO. (Lend.), F.I.C., F.C.8., Ao.,
PDBLIO ANALYST FOR THB BOROUGH OF BRIOBTON, AND ALSO FOR THB
BOROUGH OF SASTBOURNK.
FOUETH EDITIOH, THOROVOHLT RSVISED, ENLAKOED, AHD aXWEITTEH.
SRtt^ Sablts anb Illustrations.
LONDON:
CHARLES GRIFFIN AND COMPANY, LIMITED,
EXETER STREET, STRAND.
1906.
[All nights Reserved,]
;B6 6
PREFACE TO THE FOURTH EDITION.
By expansion in some directions, condensation in others, the
present edition contains more information, without material
enlargement of the bulk of the volume, than the edition which
immediately preceded it.
A large portion has been rewritten, effete processes and
unreliable reactions have been omitted. Newly discovered
poisons and injurious substances which of recent years have
come into popular use, such as sulphonal and trional, have been
added. Space has been found for a condensed account of recent
ideas as to the constitution of the vegetable poisons ; and we have
felt that no work on toxicology would be complete without some
mention of the most powerful of all modem poisons, i.e. epinephrin.
Special attention has naturally been given to araenic, and to
the delicate and reliable methods which are now available for
its separation, identification, and estimation.
The authors hope that their labours have been so far success-
ful that the new edition will retain its place as a recognised
standard work on toxicology.
3 Upper Gloucestbr Place, W.,
September 1906,
OOIfTENTS.
PART I. -INTRODUCTORY.
I. THK OLD POIRON-LORB.
SecUon Page
1. Earliest Period — Myths as to PoisoD 1
2. Egyptian Knowledge of Poison, 2
8. The use of Poison oy the Greeks and Romans — Nicander, Apollo-
donis, Dioscorides, 2-4
4. Asiatic Knowledge of Poisons, 4, 6
5. Hebrew Knowledge of Poisons, 6, 6
6. The part Poison has played in Histo^ — The Death of Britannicus —
A Commission of Murder — Royal Poisoners, .... 6-8
7. The Criminal Schools of Italy and Venice— TofTana— St Croix— The
Marchioness de Brinvilliers, 9-13
II. GROWTH AND DEVELOPMENT OF THE MODERN METHODS OF
OHBMIOALLT DETECTING POISONS.
8. The growth of Pathology 18,14
9. The Treatise of Barth^lemy d' Anglais— Portals Work— Robert Boyle
— Richard Mead — Scheele and the Chemists of the Eighteenth
Century, 14, 15
10. Proust's Discovery of Arseniuretted Hydrogen— Marsh's Test, . 16
11. Matthieu Joseph Bonaventura Orfila 15, 16
12. The Discovery of the Alkaloids 16
18. Bibliography of the Chief Works on Toxicology (Nineteenth
Century), 16-19
PART II.
I. DEFINITION OF POISON.
14. Legal Definitions of Poison, 20, 21
15. The German and French Laws as to Poison 21, 22
16. Scientific Definition of a Poison, 22, 23
II. CLASSIFICATION OF POISONS.
17. General Classification of Poisons according to Symptoms, . . 28, 24
18. Kobert's Classification 24, 25
19. Classification followed in this Work 25-29
vii
Vm CONTENTS.
III. STATISTICS.
SecUoD Page
20. Influences causing Local Variation in the Proportion of Death from
Poison, 29
21. English Statistics for the Ten Years ending 1903, .... 29-31
22. Relative Fatality of certain Poisons, 32
IV. TUK CONNKCTION BETWEEN TOXIO ACTION AND CHEMICAL COMPOSITION.
23. Advance in Knowledge of the Relationship between Chemical and
Physiological Proi>erties — The Influence of Hydroxyl—Bamberger's
Observations, 32-34
24. Physiological Effect of Replacing Hydrogen by Alkyls in Aromatic
Bodies — Overton's Researches— H. Meyer's Views on the Influence
of the Solubility of Narcotic Substances in the Fat of Living
Protoplasm, 34-39
25. The Influence of CO Groups, 39
26. Oscar Loew's Generalisations, .... .... 39-42
27. Michet's £x{)orimentB on the Comparative Toxicity of Poisonous
Metals on Fish 42
V. LIFE tests: the action of poisons on the lower forms of LIFE.
28. (1) Action of Poisons on the Red Blood Corpuscles ; (2) on Infusoria ;
(3) on CephaloiKxla ; (4) on Insects 42-45
29. The Efl'ect of Poisons on the Heart of Cold-blooded Animals—
Willliams' Apparatus — Jacobi's Apparatus, .... 45-48
30. The Eflect of Poisons on the Iris — Toxic Myosis — Toxic Mydriasis, . 48
Yi. general method of procedure in searching for poison.
31. Preliminary Examination — Distillation of Volatile Matters in a
Vacuum — Drying the Sample — Treatment by Volatile Solvents, . 48-51
32. Methods of Destroymg Organic Matter when Searching for Arsenic —
Destruction by Heat — the Methods of G. Bertrand, Verryken,
Woehler and Siebold — Basic Method — J. Ogier*s Method —
A. Villiers' Method — Process of Armand Gautier — PagcPs Process
—Subsequent Treatment of Resulting Liquid by SHg and then by
Ammonium Sulphide, 51-56
VII. THE spectroscope AS AN AID TO THE IDENTIFICATION OF
( ERTAIN POISONS.
33. Use of the Micro-Spectroscope— Oscar Braach's Observations on the
Absorption Bands produced in certain Tests, .... 56-59
ExamincUum of Blood or of Blood-Stains,
34. General Procedure — DragendoriTs Method — Solution of Blood by
Riegler's Reagent 59, 60
35. Spectroscopic Appearances of Blood — Sulphsmoglobin — Oarbon-
monoxiae Hemoglobin — Characteristics of Carbon-monoxide
Blood— Preparation of Hematin Crystals — Guaiacum Test, . . 60-65
36. Measurement of the Blood Corpuscles — Ratio of Potash to Soda in
Blood of various Animals— Biological Test for Human Blood, 65-67
CONTKNTS. ix
PART III. -POISONOUS GASES: CARBON MONOXIDE -CHLORINE-
HYDRIC SULPHIDE.
I. GABBON MONOXIDK.
flection Page
37. Properties of Carbon Monoxide, 68, 69
38. Symptoms — Acute Poisoning —Chronic Poisoning, . 69, 70
39. Action of the Gas on the Blood and Nervous System, ... 70, 71
40. Post-mortem Appearances 71,72
41. Mass Poisonings by Carbon Monoxide — The Leeds Cases — The Dar-
laston Cases, 72-74
42. Penetration of Carbon Monoxide, 74, 75
43. Detection of Carbon Monoxide — The Cuprous Chloride Reaction—
HempePs Biological Test— The Iodine Pentoxide Method, . . 75, 76
II. OHLORINE.
44. Preparation of Chlorine— Accidents in the Manufacture of Chlorine, 76, 77
45. Effects and Post-mortem Appearances, 77
46. Detection of Free Chlorine, 77,78
III. HTDRIO SULPHIDE.
47. General Properties, 78
48. Effects— the Hebbum-on-Tyne Cases— The Cleator Moor Cases, 78, 79
49. Post-mortem Appearances— Chronic Poisoning 79, 80
50. Detection, 80
PART IV.— ACIDS AND ALKALIES.
Sulphuric Acid — Hydrochloric Acid — Nitric Acid — Acetic Acid— Ammonia
— Potash — Soda— Neutral Sodium, Potassium, and Ammonium Salts.
I. SULPHURIC acid.
61. Commercial Forms of Sulphuric Acid— General Properties, . 81, 82
52. Sulphur Trioxide or Sulphuric Anhydride, 82
53. Occurrence of Free Sulphuric Acid in Nature, 82
54. Statistics, 82,83
55. Accidental, Suicidal, and Criminal Poisoning, .... 83, 84
56. Fatal Dose, 84,85
57. Local Action of Sulphuric Acid, 85, 86
58. Action of Sulphunc Acid on Vegetation, on Wood, on Paper, on
Carpets, on Clothing, and on Iron — Caution in judging of Spots, 86, 87
59. Symptoms— External Effects— Internal Effects, .... 87-89
60. 'rreatment of Acute Poisoning by the Mineral Acids, ... 89
61. Post-mortem Appearances— Oiscar Wyss* Case — Frsenkel and Reicho's
Observations on the Effects of the Acid on the Kidney, . . 90, 91
62. Pathological Preparations illustrative of Fatal Sulphuric Acid
Poisoning in the various London Museums, . . . . 91, 92
63. Chronic Poisoning by Sulphuric Acid, 92
Detection and EstiiruUion of Free Sulphuric Add.
64. Quinine Method— Solution of Free Acid by Alcohol— Hilger's Test, . 93, 94
65. Sulphates in the Urine — Changes in the Urine produced by
Sulphuric Acid 94-96
66. Effects of the Acid on the Blood, 96
67. Amount of Ordinary Sulphates in Food 96, 97
00NTENT8.
II. HYDBOGHLORIG AOID.
Section Page
68. General Properties — Uees, 97-99
69. Statistics of Poisoning by Hydrochloric Acid, 99
70. Fatal Dose, 99
71. Amount of Free Acid in the Gastric Juice — Researches of Lehmann,
Bernard, Schmidt and others 99, 100
72. Influence of Hydrochloric Acid on Vegetation, .... 100, 101
78. Action upon Cloth and Manufactured Articles, .... 101
74. Poisonous Effects of Hydrochloric Acid Gas, 101,102
75. Effects of the Liquid Acid — A. Lesser's Experiments— Illustrative
Gases, 102, 108
76. Post-mortem Appearances — Museum Preparations, . . . .103, 104
Detection and EstimcUian of Free Hydrochloric Acid.
77. (1) Detection— GUnzburg's Test— Benzo-Purpurin— The Process of
A. Villiers and Favolle ; (2) Estimation — Method of Sjokvist^
Braun's Method 106-107
78. Identification of Hydrochloric Acid Stains on Fabrics, . 108
III. NITRIC ACID.
79. General Properties and Commercial Varieties, 109
80. Use in the Arts 109
81. Statistics of Poisoning by Nitric Acid, 109
82. Fatal Dose, 109, 110
83. Action of Nitric Acid on Veeetation, 110
84. Nitric Acid Vapour — Eulenberg's and Lassar's Researches — Illustra-
tive Cases ■. 110, 111
86. Effects of Liquid Nitric Acid, 111,112
86. Local Action 112
87. Symptoms, 112, 118
88. Post-mortem Appearances — Museum Preparations, .... 113-115
89. Detection and Estimation of Nitric Acid, 115, 116
lY. ACETIC ACID.
90. statistics — Symptoms— Detection, 116
V. AMMONIA.
91. Properties, 116, 117
92. Uses— Officinal and Commercial Preparations, 117, 118
93. Statistics, 118
94. Poisoning by Ammonia Vapour, 118
95. Symptoms, 118, 119
96. Chronic Effects of the Gas, 119
97. Ammonia in Solution — Action on Plants, 119
98. Action on Human Beings and Animal Life — Effects on the Blood —
Symptoms, 119-121
99. Post-mortem Appearances — Museum Preparations, .... 121
100. Separation of Ammonia, 121, 122
101. Estimation, 122
YI. CAUSTIC POTASH AND SODA.
102. Properties of Potash 122
103. Pharmaceutical Preparations, 122, 128
104. Carbonate of Potash, 123
105. Bicarbonate of Potash, 128
106. Caustic Soda— Sodium Hydrate, 128
C0NTBNT8. XI
Sectton Page
107. Sode Carbonas — Carbonate of Soda, 12S
108. BioarbonateofSoda 128,124
109. Statistios, 124
110. Effects on Animal and Vegetable Life, 124
111. Local Effects, 124, 125
112. Symptoms, 126
118. Post-mortem Ap^rances— Musemn Preparations, .... 125, 126
114. Chemical Analysis, 126, 127
115. Estimation of the Fixed Alkalies 127
VII. NBUTRAJi SODIUM, POTASSIUM, AND AMMONIUM SALTS.
116. General Poisonous Characters of Large Doses of Salts of the Alkalies, . 127 , 128
117. Effects of Sodimn Salts, 128
118. Effects of Potassium Salts 128
119. Action on the Frog's Heart, 128
120. Action on Warm-blooded Animals, 128
121. Elimination, 128
122. Nitrate of Potash— General Properties, 129
123. Statistics of "Nitre "Poisoning 129
124. Uses of "Nitre "in the Arts 129
125. Action of Nitrates of Sodium and Potassium— Poisonous Action of
Sodic Nitrite, 129
126. Post-mortem Appearances from Potassic Nitrate, .... 130
127. Potassic Chlorate— General Properties, 130
128. Uses, 130
129. Poisonous Properties, 130
130. Experiments on Animals — Effects on Blood— Effects on the Kidney, 130, 131
131. Effects on Man— Illustrative Cases, 131
182. Nephritis from Chlorate Poisoning 131, 132
138. Elimination, 132
134. Essential Action of Potassic Chlorate 132
Detection and Estimation of Potassic Chlorate.
135. Separation from Organic Fluids— Tests— Treatment of Urine for
Chlorate 132, 133
Toxicological Detection of Alkali Salts.
136. Separation of Potassium, Sodium, and Ammonium Salts from the
Contents of the Stomach, 133,134
PART v.— MORE OR LESS VOLATILE POISONOUS SUBSTANCES CAP-
ABLE OF BEING SEPARATED BY DISTILLATION FROM NEUTRAL
OR ACID LIQUIDS.
Hydrocarbons — Camphor — Alcohol — Amtl Nitrite — Ethbr — Chloroform
AND OTHER ANJSTUKTICS — CHLORAL— CaRBON DiSULPHIDB— CaRBOLIO AoID
— Nitro-Benzbne— Prussio Acid— Phosphorus.
i. htdrooabbons.
1. Petroleum,
137. Petroleum : General Properties, 135
188. Cymofi;eno, 135
139. Biiigolene, 135
140. Gasolene, 185
XU 0ONTSNT8.
Section Page
141. Benzoline — Petroleum Spirit — Petrol — Varieties of Naphtha and dis-
tinguishing Tests, 185, 186
142. Paraffin Oil, 136
143. Effects of Petroleum 187
144. Cases of Poisoning, 137
145. Separation and Identification of Petroleum, 137
2. CoaZ'Tar— Naphtha— Benzene.
146. General Properties 138
147. Case of Poisoning by the Liquid, 138
148. Eulenberg's Exi)eriments on the Vapour, 188
149. Detection and Separation of Benzene — Purification — Conversion into
Nitro- Benzene — Conversion into Aniline, 138, 139
3. Terpcnes — Essential Oils — Oil of Turpentine,
160. Terpenes— Cedrenes — Colopheues, 139
4. Oil of Turpentine— Spirit of Turpentine— ^'^ Turps,**
151. French, English, and American Turpentines — Distinguishing Char-
acters ana Resictions, 139, 140
152. Effects of Turpentine, 140
II. CAMPHOR.
153. General Proiwrties, 141
154. Pharmaceutical Prep«u:ations, 141
155. Symptoms of Poisoning by Camphor, , . 141,142
156. Post-mortem Appearances, 142
157. Separation of Camphor from the Contents of the Stomach, 142
III. ALCOHOLS.
1. Ethylie Alcohol,
158. Statistics of Alcohol Poisoning, 142
159. Criminal or Accidental Alcoholic Poisoning, 142-144
160. Fatal Dose, 144
161. Symptoms, 144, 145
162. Post- mortem Appearances, 145, 146
163. Excretion of Alcohol, 146,147
164. Toxicological Detection of Alcohol — Conversion into the Dinitro-
benzoate Esters, 147, 148
2. Amylic Alcohol,
165. Physical Properties of the Amvlio Alcohols, 148
166. Poisonous Enects of Amylio Alcohol, 148
167. Identification of Amylic Alcohol, 148
168. Amvl Nitrite — Iso-amyl Ester Nitrate— Physiological Effects-
Post-mortem Appearances, 148, 149
IV. STHSR.
169. Ether— Ethvlic Ether, Ethyl Oxide— Chemical Properties of, . . 149
170. Ether as a Poison, 149,150
171. Fatal Dose, 150
172. Ether as an Anesthetic, 150
178. Separation of Ether from Organic Fluids— Tests, .... 150, 151
CONTENTS. xiii
Y. CHLOBOTORM.
Saotton Page
174. Physical and Chemical Properties of Chlorofonn— Tests for Purity, . 151-168
175. Method of Manufactare, 153
1. Chloroform €18 a Liquid,
176. PoiBonons Effect of liquid Chlorofonn— Statistics, .... 153
177. Local Action of Chloroform, 153, 154
178. Action on Blood, Muscle, and Nervous Tissue, .... 154
179. General Effects of the Liquid, 154,155
180. Fatal Dose of the Liquid, 155
181. Symptoms, 155, 156
182. Post-mortem Appearances 156
2. The Vapour of Chloroform,
188. Statistics of Deaths from Chloroform Vapour, 156,157
184. Suicidal and Criminal Poisoning by Chlorofonn, .... 157
186. Physiological Effects, 157, 158
186. Symptoms produced by the Vapour, 158, 159
187. Cnronic Chloroform Poisoning 159
188. Post-mortem Appearances, 159, 160
189. Detection and Estimation of Chloroform, 160
190. Estimation of Chloroform, 161
YI. CHLORAL.
191. Chemical Properties of Chloral— statistics of Chloral Poisoning, 161,162
192. Detection of Chloral Hydrate 162
198. Assay of Chloral Hydrate,- 162,163
194. Effects of Chloral Hydrate on Animals, 163,164
195. Action of Chloral on the Blood, 164
196. Effects of Chloral Hydrate on Man, 164
197. Fatal Dose 165, 166
198. Symptoms, 166
199. T^tment of Acute Chloral Poisoning, 166,167
200. Chronic Poisoning by Chloral Hydrate, 167
201. Excretion of Chloral — Separation of Uro-Chloral from the Urine, 168
202. Separation of Chloral from Organic Matters— Tests for Chloral, 169, 170
YII. MINOR AN.fi8THBTIC8 AND NARCOTICS.
203. Substitutions of the Hydrogen by Chlorine in Methane — Methane
Dichloride, 170
204. Pentane— Pentol, 170
205. Aldehyde (Acetaldehyde)—Metaldehyde, 170
206. Paraldehyde, 170
207. Somoform, 170, 171
208. Sulphones — Sulphonal, Trional, Tetronal— Cases of Poisoning by
Sulphones— Separation and Identification of the Sulphones, 171, 172
209. Veronal (Diethyl-barbaturic Acid), 172
YIIL BISITLVHIDE OF CARBON.
210. Properties of Carbon Bisulphide, 172
211. Poisoning by Carbon Bisulphide— Chronic Poisoning, . 173,174
212. Post-mortem Appearances, 174
213. Detection and Seuaration of Carbon Bisulphide 174
214. Xauthogenic Acia, 174
215. Potassic Xanthogenate and Potassic Xanthamylate, . . 174
XIV 00NTKNT8.
IX. TBB TAB AOIDS— PHXNOIr-OBBSOL.
Soclion Page
216. Carbolic Acid (Phenol)— Properties of, 174, 176
217. Commercial VarietieaH-Calyert's Carbolic Acid Powder— Carbolic
Acid Soaps, 176
218. Usee of Carbolic Acid 176
219. Statistics of Carbolic Acid Poisoning, 176-178
220. Fatal Doee, 178
221. Effects on Animals — Infusoria — Fish — Frogs, 178, 179
222. Effectson Warm-blooded Animals— Rabbits— Cats— Mice, etc., . 179
228. Symptoms in Man — External Application— Illustrative Cases, 180-182
224. Internal Administration, 182, 183
225. Symptoms of Carbolic Acid Poisoning, 183
226. Changes in the Urine from Carbolic Acid, 183-186
227. The Action of Carbolic Acid considered physiologically, 186
228. Excretion of Carbolic Acid, 185,186
229. Post-mortem Appearances— Museum Preparations, .... 186
230. Tests for Carbolic Acid — the Pinewood Test — Ammonia and Hypo-
chlorite— Ferric Chloride— Bromine, 187
231. Quantitatiye Estimation of Carbolic Acid, 187,188
232. Oresol (Cresylic Acid, Methyl-Phenol)— Ortho-, Meta-, and Para-
Cresol — Commercial Cresol, 188, 189
283. Creasote and Ereozote, 189
234. Carbolic Acid in Oreanic Fluids, 190
235. Examination of the Urine for Phenol or Cresol, .... 190-191
236. Assay of Disinfectants — Carbolic Acid Powders— Bromine Method —
Colorimetric Method of Estimation, 192
237. Analysis of Carbolic Acid Powders, 192-193
238. Analysis of Carbolic Acid Soap, 193
X. NITKO-BENZENE.
239. Properties and Commercial Varieties of Nitro- Benzene, ... 193
240. Effects of Poisoning by Nitro-Benzene, 193,194
241. Poisoning by Nitro-Benzene Vapour, 194,195
242. Poisoning by Liquid Kitro-Benzene, 195, 196
243. Fatal Dose, 196
244. Pathological Appearances, 197
246. Physiological Action of Kitro-Benzene 197
246. Detection and Separation of Nitro-Benzene from Animal Tissues, 197, 198
XI. DINITBO-BENZOL.
247. Dinitro-Benzol (Ortho-, Meta-, Para-)— Physical and Chemical
Properties, 198, 199
248. Effects of Dinitro-Benzol, 199, 200
249. The Blood in Nitro-Benzol Poisoning 200, 201
260. Detection of Dinitro-Benzol, 201, 202
XII. HYDBOOYANIO AOID.
251. General Properties of Hydrocyanic Acid, 202
252. Medicinal Preparations of Prussic Acid, 203
253. Poisoning by rrussic Acid — Use of the Acid in the Arts — Occurrence
of in the Animal and Vegetable Kingdom, 203-206
264. Laurocerasin, 206
265. Statistics of Cyanide Poisoning, 206, 207
256. Accidental and Criminal Poisoning by Prussic Acid, . 207, 208
267. Fatal Dose, 208
268. Action of Hydric and Potassic Cyanides on Living Organisms, . 208, 209
258A.Effects on Infusoria, Yeast, and Algse, 209
259. Symptoms observed in Anunals, 209, 210
CONTBNTS. XV
Section Page
260. Symptoms in Dogs, 210, 211
261. Symptoms in Man, 211, 212
262. Poisoning by the (>anide Glucosides— The Rotterdam Gases, . . 212, 218
268. Chronic Poisoning by Hydric Cyanide, 218, 214
264. Post-mortem Appearances, 214, 215
265. Tests for Hydrocyanic Acid and Cyanide of Potassiom — Sohonbein's
Test— Robert's Test, 215-217
266. Separation of Hydric Cyanide or Potassic Cyanide from Organic
Matters, 217-219
267. How long after Death can Hydric or Potassic Cyanides be Detected t 219, 220
268. Estimation of Hydric or Potassic Cyanides, 220
269. Case of Poisoning by Bitter Almonds, 220, 221
Poisonous Cyanides other than Hydric and Potassic Cyanides,
270. Sodic and Ammonic Cyanides, 221
271. Action of Potassic Perrocyanide— Silver Cyanide— Sulphooyanides
— Methyl Cyanide— Toxic Dose of the Nitriles, .... 221-224
XIII. PH0SPH0KU8.
272. Chemical and Physical Properties, 224, 225
273. Phosphuretted Hydrogen— Phospldne, 225, 226
274. Medicinal Preparations of Phosphorus, 226
275. Matches and Vermin Pastes, 226-228
276. Statistics of Poisoning by Phosphorus, 228, 229
277. FatolDose, 229
278. Effects of Phosphorus, 229
279. Varieties of Symptoms Produced, 229, 230
280. Common Form, 280, 231
281. Hsemorrhagic Form, . . \ 231
282. Nervous Form, 281, 232
283. Sequels, 232
284. Period at which the First Symptoms commence, .... 282
285. Period of Death, 282
286. Poisoning by Phosphorus Vapour, 232-234
287. Chronic Phosphorus Poisoninyg,^ 234
288. Changes in the Urinary Secretion* 234, 235
289. Changes in the Blood, 285
290. Antidote— Treatment, 285
291. Poisonous Effects of Phosphine, 235,236
292. Action of Phosphine on the Blood, 236, 237
293. Post-mortem Appearances — Museum Preparations, .... 287, 240
294. Changes produoiBa in the Kidneys, Heart, and Lungs, 240, 241
295. Diagnostic Differences between Acute Yellow Atrophy of the Liver
and Fatty Liver produced by Phosphorus, 241
296. The Detection of Phosphorus— Mitscnerlich's Process— The Produc-
tion of Phosphine— Tests dependent on the Combustion of Phos-
phine—Blondlot's Apparatus 241-248
297. Spectrum of Phosphin^—Lipowitz's Sulphur Test— Scherer's Test, . 244,245
298. Chemical Examination of the Urine 245, 246
299. Quantitative Estimation of Phosphorus, 246, 247
300. How long can Phosphorus be recognised after Death ? . . . 247
XVI CONTKNTS.
PART VI.— ALKALOIDS AND POISONOUS VEGETABLE PRINCIPLES
SEPARATED FOR THE MOST PART BY ALCOHOLIC SOLVENTS.
Division L— Veoktable Alkaloids.
l oenvral mbthods of te8tino and extbaotino alkaloids.
Section Page
301. General Tests for Alkaloids, 248
802. Group Reagents— Iodine in Hydriodic Add — Iodine and Potaasic
Iodide— Mercurio Potassic Iodide — Bismuthic Potassic Iodide-
Iodised Parethoxyphenyl Saocinimide — Chloride of Gold —
Platinic Chloride 248, 249
803. (1) Phoephomolvbdic Add as a Reagent for Alkaloids ; (2) Silico-
Tangstic Ada as a Reagent for Alkaloids ; (8) Scheibler*s Method
for Alkaloids— Phospho-Tongstic Acid, 249-251
304. Sohulze's Reagent, 251
305. DragendorfTs Reagent— Marm^*8 Reagent— Potass-Zinc Iodide, 251
306. Colour Tests— Fr5hde*s Reagent— Mandelin*B Reagent, ... 251
807. General Processes for the Separation of Alkaloidal Substances from
Organic Matters — Eippenoerger's Process, 252, 253
308. Selmrs Process, 263, 254
309. DragendorfTs Process — Kippenberger's Modification of DragendorfTs
Process, 264-256
310. Scheibler's Process, 256, 267
811. Grandval and Ln^oux's Method 267
312. Identification of the Alkaloids, 257
313. Behrens' Method of Identification of the Alkaloids 257, 258
314. Sublimation of the Alkaloids, 259-262
816. Melting-point of the Alkaloids, 262, 263
316. Identification by Organic Analysis — Methoxyl Groups — Nitrogen, . 264
817. Quantitative Estimation of the Alkaloids, 264-266
n. LIQUID VOLATILE ALKALOIDS.
THE ALKALOIDS OP HEMLOCK— NICOTINE— PITUBIE — SPARTEINE.
1. The Alkalaida of Heinlock {Conium),
318. Characters of the Hemlock Plant 266
819. Coniine— Synthesis of Coniine — Characters of Coniine — Tests, . 266-268
320. Constitution of the Coniine BasesH-Coniceines— Conhydrin- Pseudo-
couhydrine — Methylconiine, 268,269
321. Pharmaceutical Preparations, 269, 270
822. Statistics of Coniine Poisoning, 270
323. Effects on Animals, 270,271
824. Effects on Man, 271
326. Physiological Action, 271
326. Post-mortem App«irances— Fatal Dose 271,272
327. Separation of Coniine from Organic Matters or Tissues, . 272
2. Tobaeeo^Nicotine,
328. The various Spedes of Tobacco — Composition of the Fresh Leaves, . 273
329. Quantitative Estimation of Nicotine in Tobacco— Keller's Process—
The Polarimetric Method of Popoirci — Estimation by Cox of
Nicotine in various Tobaccos 273, 274
380. Chemical and Physical Characters of Nicotine — Tests for Nicotine, . 275-277
331. Effects on Animals, 277, 278
332. Effects on Man— Illustrative Cases, 278, 279
CONTENTS. xvii
Section Page
383. Cases of Tobaooo Poisoning— Tobacco Smoke— External Application
of Tobacco Leaf, 279-281
834. Physiological Action, 281,282
386. Fatal Dose, 282
336. Post-mortem Appearances, 282
337. Separation of Nicotine from Organic Matters 282, 283
337A.Antidote to Nicotine, 283
3. PUurie,
338. Chemical and Physical Characters of Piturie, 283, 284
4. Sparteine,
339. Chemical and Physical Characters of Sparteine, .... 284
5. Aniline,
340. Properties of Aniline, 284
341. Symptoms and Effects — Chronic Poisoning— Post-mortem Appear-
ances, 284, 285
342. Fatal Dose, 285
343. Detection of Aniline, 286
III. THE OPIUM GROUP OF ALKALOIDS.
344. General Composition— List of Alkaloids and other Principles —
Analysis of Samples of Opinm, 286, 287
345. Action of Solvents on Opiam, 287
346. Assay of Opinm — Process of Teschemacher and Smith— Dott's
Process— Douzard Method, 287-289
347. Medicinal and other Preparations of Opium— ( 1 ) Officinal ; (2) Patent
and other Non-Officinal Preparations of Opinm, .... 290-293
348. Statistics of Opium Poisoning, 293, 294
349. Poisoning of Children by Opmm, 294
350. Doses of Opium and Morphia, 294,295
361. General Method for the Detection of Opium, 296,296
352. Morphine : Chemical and Physical Characters of, . 297
363. Morphine Salts, 297,298
354. Constitution of Morphine and Codeine, 298, 299
355. Tests for Morphine— Robert's Test— Iodic Acid Test— Vanadic Acid
Test— Tungstic Acid Test— Titanic Acid Test and other Reactions, 300-303
356. Symptoms of Opium and Morphine Poisoning — Action on Frogs,
Dogs, Goats, Cats, and Birds, 303, 304
357. Physiological Action, 304,305
358. Physiological Effect of Morphine Derivatives, 306, 306
869. The Forms of Opium and Morphine Poisoning— Illustrative Cases, . 306-309
360. Diagnosis of Opium Poisoning, 309, 310
361. Opium-eatinff---Opium-smoking, 310-312
362. Treatmentof Opium or Morphine Poisoning 312
863. Post-mortem Appearances, 312,313
364. Separation of Morphine from Animal Tissues and Fluids, 313, 314
365. Extraction of Morphine, 314, 315
366. Narcotine : Chemical and Physical Properties— Behaviour of Nar-
ootine with Reagents — Constitution of Narcotine, . 315-317
367. Effects of Narcotine, 317
368. Codeine : Chemical and Physical Properties, 317,318
369. Effects of Codeine, . . 318, 319
370. Nareeine: Physical and Chemical Properties of Narceine and its
Salts, 319, 320
b
XVUl CONTENTS.
Seetfon Page
871. Effects of Naroeine, 820, 821
872. Papaverme : Chemical Properties and Tests^ 821
873. Effects of Papaverine, 321,822
874. Thebaine : Physical and Chemical Properties of, ... . 822
876. Effects of Thebaine, 822,828
876. Cryptopine, 823
877. Pseudomorphine, 828
378. Apomorphue 828, 824
879. Laudanine — Laudanidine — Laudanosine, 324
880. Tritopine, 824
881. Meconine, 824
882. Meconic Acid : Chemical Properties— Tests for — Se{)aration of, . 824, 325
IV. THE STRYCHNINE OK TETANUS-PRODUGINO GROUP OF ALKALOIDS.
1. Nux Vomica Group — Strychnine — Brucinc — Igasurinc.
388. General Characters of Nux Vomica Seeds 825-828
384. Chemical Constituents of Nux Vomica Seeds, 326
885. Strychnine : Chemical and Physical Characters of, . . . . 826-328
886. Strychnine Salts, 828, 829
887. Pharmaceutical and other Preparations of Nux Vomica and
Strychnine, with Suggestions for their Valuation — Separation of
the Alkaloids from Thvlx Vomica— Tests— Vermin-killers, . . 829-382
388. Statistics of Death from Strychnine— the Series of Murders by
Thomas Neill Cream— The Palmer Case, 332-834
889. Fatal Dose— Falck's Researches— Illustrative Cases, . . . 384-837
890. Action on Animals, 837, 338
391. Effects on Man — Distinction between Tetanus from Strychnine and
** Disease Tetanus," 338-340
892. Diagnosis of Strychnine Poisoning, 840
898. Physiological Action, 840, 341
894. Post-mortem Appearances, 341, 842
895. Treatment, 342
396. Separation of Strychnine from Organic Matters, .... 342-345
397. Identification of the Alkaloid, 346, 347
398. The Physiological Test for Strychnine, 847, 348
899. Hypaphorine, 848
400. Quantitative Estimation of Strychnine, .348, 349
401. Brucine — Solubility and Chemical Properties of Brucine, . . 349, 350
402. Physiological Action 850, 851
408. Tests 851, 352
2. The Quebracho Group of Alkaloids.
404. The Alkaloids obtained from Quebracho Blancko 353
405. Aspidospermine, 358
406. Quebrachine, 358
3. Pereirine.
407. Pereirine 358
4. Gelsemine,
408. Oelsemine and Gelseminine, 858, 854
409. Fatal Dose, 854
410. Effects on Animals, 854, 855
411. Effects on Man 855
412. Extraction from Organic Matters or the Tissues of the Body, . 855
OONTKNTS. XIX
5. Coca Alkaloids — Cocaine,
Section Page
413. The Alkaloids in the Leaves of BrythroxyUm coca — Cocaine, . 866
414. Cocaine Hydrochloride, 857
415. Phannaceutical Preparations, 857
416. Separation of Cocaine and Tests, ....... 357, 858
417. Symptoms, 358, 859
418. Post-mortem Appearances . . 359
419. Fatal Dose, 359
6. CorycUUim,
420. Alkaloids extracted from the Root of Corydalis cava — Corydaline, . 359, 360
V. THB AOONITB GROUP OF ALKkhOlDB,
421. Descriptioii of the Aconitum Tiapellus, 860
422. Pharmaceutical Preparations of Aconite, . . ' . . . . 860, 861
423. Dunstan's Researches— The Groups of Aconitine Alkaloids — The
Aconitine Group— The Pseudaconitines and the Atisine Group—
The Melting-points and Specific Rotations of the Alkaloids and
the Melting-point of the Gold Salts, 861,863
424. Aconitine : Extraction and Properties, ..... 368
425. Tests for Aconitine, 864
426. Benzoyl- Aconine, 864, 865
427. The Lethal Dose of Aoonitines 865,866
428. Effects of Aconitine on Animal Life : Insects, Fish, Reptiles, Frogs-
Action of Aconitine on the Heart— Effects of Indaconitine — Birds
—Mammals, 366>370
429. Statistics of Aconite Poisoning, 870
430. Effects on Man 870
481. Poisoning by the Root, 870, 371
432. Poisoning by the Alkaloid Aconitine, 372-874
433. The Lamson Case, 374
434. Poisoning by Medicinal Preparations of Aconite, .... 375
435. Physiological Action, 375
436. Post-mortem Appearances, 375, 876
437. Separation of Aconitine from the Contents of the Stomach or the
Organs, 876, 377
VI. THE MYDRIATIC OROITP OP ALKALOIDS— ATROPINR— RTOSCTAMINE—
AOLANINE— 0TTI8INR.
1. Atropine
438. Alkaloids in Plants belonging to the Solanaceoe^ .... 377, 378
439. Atropine— Alkaloidal Content of the Belladonna Plant, . . . 378,379
440. The Datura s^mTmmium- Distinction between Seeds of the Datura
and those of Capsicum 379, 380
441. Pharmaceutical Preparations of Belladonna 380
442. Properties of Atropine — Constitutional Formula, .... 380, 381
443. Tests for Atropine — Distinction between Hyoscyamine and Atropine
— Strj^chnine and Atropine — Action of Atropine on the Iris, . 381-384
444. Statistics of Atropine Poisoning, 384, 385
445. Accidental and Criminal Poisoning by Atropine, .... 385, 886
446. Fatal Dose, 886
447. Action on Animals, 386, 387
448. Action on Man, 387-889
449. Physiological Action of Atropine, 389, 390
450. Diagnosis 890
451. Post-mortem Appearances, 390
452. Treatment, 390, 891
458. Separation of Atropine from Organic Tissues, 891
XX CONTKNTB.
2. Hffoacyamine,
Section Page
454. DiBtribution and Properties of Hyosoyamine, 391-808
465. Pharmaoeutlcal and other Preparations of Henbane, 893, 894
456. Dose and Effects, 395
457. Separation of Hyosoyamine from Organic Matters, .... 895
8. Scopolamine.
458. Soopolamine, ^ 895, 896
459. Pseudo-hyoscyamine, 896
460. Atropamine, 896
460A.Belladonnine, 896
4. Solanine,
461. Distribution of Solanine, 896, 897
462. Properties of Solanine, 897
468. Solanidine, 397, 898
464. Poisoning from Solanine, 898
465. Separation of Solanine from the Tissues of the Body, 398
5. Cytisine,
466. The Oytisua Za^mum— Cytisine 398, 899
467. Reactions of Cytisine, 399, 400
468. Effects on Animals, 400
469. Effects on Man, 400,401
YII. THE ALKALOIDS OF THE YERATRUMS.
470. The Active Principles in Veratnim sahadilla, V. cUhum^ and
V,v%ride — Chemical Properties of the Alkaloids, . . 401-408
471. Veratridine— Veratric Acid — Cevadine, 408, 404
472. Jervine 404
478. Pseudo-jervine 404
474. Protoveratridine, 404, 406
475. Rubi-jervine, 406
476. Yeratralbine, 406
477. Veratroidine, 406, 406
478. Commercial Yeratrine, 406
479. Pharmaceutical Preparations 406, 407
480. Fatol Dose 407
481. Effects on Animals — Physiological Action, 407
482. Effects on Man, 407, 408
483. Symptoms, 408
484. Post-mortem Appearances, 408
486. Separation from Organic Matters, 408, 409
VIII. PHY80STIOMINB.
486. The Ordeal Bean of Calabar, 409
487. Physoatigmine or Eserine, 409, 410
488. Tests, 410, 411
489. Pharmaceutical Preparations, 411
490. Effects on Animals—Effects on Man, 411,412
491. Physiological Action, 412
492. Post-mortem Appearances, 412
493. Separation of Pnysostigmine, 412,413
494. Fatal Dose of Physostigmine, 413
OONTKNTS. XXI
IX. PILOOARPINE.
Section Page
495. The Alkaloids of the Jaborandi, 414
496. Pilocarpine, 414
497. Tests 414, 416
498. Effects of Pilocarpine— Isopilocarpine — Pilocarpidine, . . 415, 416
X. TAXINB.
499. Poisonous Properties of Taxine — Chemical Properties of Tazine, . 416
500. Poisoning by Yew, . . • 416
501. Effects on Animals— Physiological Action, 416, 417
502. Effects on Man, 417
508. Post-mortem Appearances 417
XI. CUBABE ALKALOIDS.
504. The Varieties of Curare — Isolation of the Curare Alkaloids, . 418, 419
505. Physiological Effects, 419,420
506. Separation of Curarine, 420
XII. OOLCHIOINB.
507. Content of Alkaloid in Colchicum Seeds, 421
508. Colchicine— Extraction — Chemical Composition, .... 421, 422
509. Tests, 422
510. Phaimaceutical Preparations— Quack and Patent Medicines, 422, 428
511. Fatal Dose 428
512. Effects of Colchicine on Animals, 428
518. Effects of Colchicine on Man, 424,425
514. Symptoms produced by Colchicine — Post-mortem Appearances, • 426
515. Separation of Colchicine from Organic Matters, .... 425,426
XIU. MU80ABINB AND THB AOTIYX PBIN0IPLE8 OF OEBTAIN FUNOL
516. The Amanita muscaria — Botanical Characters — Effects on the
InhabiUuts of Kamschatka, 426, 427
517. Poisoning by the Amanita, and Post-mortem Characteristics, . 427
518. Muscarine: Chemical and Physiological Properties, . . 427,428
519. Antagonistic Action of Atropine and Muscarme, .... 428,429
520. Detection of Muscarine, 429
521. The Agarieus p?ialloide8, 429,480
522. Post-mortem Appearances, 480
523. The Agaricus parUherinvs— The Agarieus rtU)er, .... 480, 481
524. The BoUtus satanas. 481
525. The Common Morelle, 481
Division II. — Glucosides.
I. DIGITALIS GROUP.
526. Description of the Foxglove 481,482
527. Chemical Composition, 482
528. Digitalein 482
529. Digitonin — Digitogenin, 432
530. Digitalin 482, 488
531. Digitaletin, 488
582. Digitoxin, 438
532A.Separation of Digitoxin from Organic Matters, .... 483, 484
538. Digitaleretin— Paradigitaletin, 434
584. Inert Derivatives— Digitin, Digitalacrin, 484
XXll CONTENTS.
Section Page
635. Beactions of the Digitalins, 484
586. Pharmaceutical Preparations of Digitaliu, 484, 485
537. Fatal Dose, 485, 486
588. Statistics 486
539. Effects on Man —Illustrative Cases, 486-489
540. Physiological Action of the Digitalins 489,440
541. Local Action, 440
542. Action on the Heart, 440-442
548. Action of the Digitalins on the Muco-intestinal Tract and other
Organs, 442
544. The Action of Digitalin on the Common Blow-Fly 442
645. Action of the Digitalins on the Frog's Heart, 442, 448
546. Post-mortem Appearances, 448, 444
547. Separation of tne Digitalins from Animal Tissues, .... 444, 445
II. OTHEB I'OIBOMOUS GLV(X)8IDE8 ACTING ON TUB UKART.
1. CryskUlisable Oluoosides,
548. Antiarin, 445
549. Effects of Antiarin, 445
550. Separation of Antiarin, 445, 446
551. The Active Principles of the Hellebores — Helleborin— Helleborein —
Helleboretin, 446
552. Cases of Poisoning by Hellebore Root, 446, 447
553. Euonymin, 447
564. Thevetin, 447
2. Stibstances partly CrysUUlisdble, but which are not Olucondes,
655. Strophantin, 447
8. Non-CrystallUable Olucosides almost Insoluble in Water.
666. Sdllain, 448
567. Adonidin, 448
668. Oleandrin, 448
559. Neriin or Oleander Digitalin, 448, 449
560. Poisoning by the Nerium oleander, 449
561. The Ma(&gascar Ordeal Poison 449
4. Substances which behave like the Digitalins,
662. Apocynin, 449
III. SAPONIN— SAPONIN 8UBSTANCKS.
668. Varieties of Saponin, 460
664. Properties of Saponin, 460, 461
666. Effects of Saponin 461,462
666. Action on Man, 462
667. Separation of Sajwnin, 462,458
668. Identification of Saponin, 463
Division III.— Vabious Veoeiablb Poisonous Principles not Rkadilt
Admitting of Classification in the Previous Division.
L santonin.
569. .Physical and Chemical Properties of Santonin 468
570. Poisoning by Santonin, 468
C0NTBNT8. xxili
Section Pige
671. FaUlDose, 454
572. Effects on Animals, 454
578. Effects on Man, 454, 455
574. Post-mortem Appearances, 455
575. Separation of Santonin from the Contents of the Stomach, . 455
IL MSZBBKOK.
576. The Daphne mezereon, 456
III. Ebgot of Rye.
577. Description of Ergotised Grain, 456
678. Chemical Constituents of Erffot—Scleromucin— Sclerotic Acid —
—Secalin-Toxin—Comutin— Inert Principles of Ergot, . . 467-460
579. Detection of Ergot in Flour 460
580. Pharmaceutical Preparations of Ergot, 460
581. Dose, 460, 461
682. Ei^otism, 461
688. Convulsive Form of Ergotism, 461, 462
684. The Gangrenous Form of Ergotism— The Wattisham Cases, . . 462, 468
586. Symptoms of Acute Poisoning by Ergot, 468
586. Physiological Action as shown by Experiments on Animals, . . 468-466
587. Separation of the Active Principles of Ergot from Animal Tissues, . 465
II. PICROTOXIN, THE AOTIVB PBINCIPLE OF THE C0CCULV8 INDICU8
(INDIAN BEBBT, LEVANT NUT).
688. Active Principles of the Menispermum coccultts, .... 466, 466
689. Picrotoxin— Picrotoxinin— Picrotin, 466, 467
690. FatolDose, 467
591. Effects on Animals, 467; 468
592. Effects on Man 468
593. Physiological Action, 468
694. Separation from Organic Matters, 468, 469
694a. III. TUTIN — COBIAMYRTIN.
IV. THE POISON OF tLUCtUM RKUGIOSVM-^A JAPANESE PLANT.
696. The Chemistry and Pharmacology of the Illicium religiosum, . . 470
v. PIGBIG AGID AND PIGBATE8.
696. Picric Acid, 470
697. Effects of Picric Acid, 470,471
698. Tests for Picric Acid, 471
VI. CICUTOXIN.
699. The Botanical Characters of CictUa nirosa, 471, 472
600. Effects on Animals, 472
601. Effects on Man 472
602. Separation of Cicutoxin from the Body, 478
VIL ^THUSA CTSAPtUM (FOOL'S PABSLEY).
608. Poisoning by Fool's Parsley 478
XXIV CONTENTS.
VIII. (ENANTUE CBOCATA.
Section Page
604. The Water Hemlock : PoieonouB Properties of, ... . 478, 474
605. Illustrative Cases, 474
606. Post-mortem Appearances, 474, 475
IZ. OIL OF SAVIN.
607. Effects of the Oil of Savin, 475
608. Post-mortem Appearances, 476
600. Separation of the Poison and Identification, 476
X. CBOTON OIL.
610. Chemical Composition of Croton Oil, 476
611. Dose and Effects, 477
612. Post-mortem Apf)earance8, 477
618. Chemical Analysis, 477
ZI. THB TOXALBUMINS 0¥ GA8T0B-01L SEEDH AVI) UF ABRV8.
614. The Toxalbumins of Castor-Oil Seeds, 478
615. Toxalbuminof^fenw, 478,479
XII. ICTBOOEN.
616. Ictrogen— Poisoning by Lupin Seeds, 479
XIII. COTTON SEEDS.
617. Poisoning by Cotton Seeds, 479, 480
XIV. LATHYRU8 SATIVUS.
618. Effects of Various Species of Zo/Ayrus, 480
XV. ARUM— BEYONY— LOCUST TREE— MALE FEEN.
619. Arum maciUcUum, 481
620. The Black Bryony, 481
621. The Locust Tree, 481
622. Male Fern, 481,482
PART VII.— POISONS DERIVED FROM LIVING OR DEAD ANIMAL
SUBSTANCES.
Division I.— Poisons Seobetbd by Living Animals.
L POISONOUS amphibia.
628. The Salamander, 483, 484
624. Poisoning by the Samandarins, 484
625. The Water Salamander, 484
626. Poisons of the Toad, 484,485
627. The Udoderma, 485, 486
CONTENTS. XXV
II. THE POISON OF THE 8G0BPI0N.
Section Page
628. Effects of Scorpion Poison, 486, 487
III. POISONOUS FISH.
629. Murceiia helena-^thQ Fugu-Poison of Japan — Tetrodonin— Tetro-
donic Acid, 487, 488
630. Other Poisonous Fish— The Toad Fish 488, 489
IV. POISONOUS SPIDEBS AND INSECTS.
6dOA.yarietiesof Spiders known to be Poisonous 489-491
681. The Katipo 491
632. Ants, 491
683. Wasps, 491
634. Gantharides, 491, 492
685. Cantharidin, 492
686. Pharmaceatical Preparations of Cantharides, 498
637. Fatol Dose, 493
638. Effects on Animals— Effects on Man, 498-495
639. Illustrative Cases, 494, 495
640. Post-mortem Appearances, 496
641. Tests for Cantharidin, and its Detection in the Tissues, . 495-497
y. POISONOUS SNAKES.
642. Classification of Poisonous Snakes, 498
643. The Poison of the Cobra 498-500
644. Fatol Dose 500
645. Effecto on Animals, 500, 501
646. Effects on Man, 501, 502
647. Cobra AntiToxin, 502, 508
647a. Other Colubrine Snakes— The Viperidae, 508
6i7B,Duboia Rtissdlii, 504
647o.The Poison of the Common Viper, 504
YL MAMMALIAN POISON.
647D.Epinephrin, 505, 506
647E. Physiological Action of Epinephrin, 506
Division II.—PtoMAiNEs— Animal Toxinbs.
648. Deianition of Ptomaine, 506, 507
Isolaiion of Animal Toxinea.
649. Gautier*s Process, 507
650. Brieger's Process, 507-509
651. Benzoyl Chloride Method, 509, 510
652. The Amines, 510-512
653. Methylamine 513
654. Dimethylamine, 518
655. Trimethylamine, 518
656. Ethylamine 518
657. Diethylamine, 513
658. Triethylamine 518
659. Propylamine, 518, 514
660. Iso-amylamine, .......... 514
XXVI CONTBNTS.
Diamines.
Section Page
661. Bate of Fonnation of Diamines, 514
662. Ethylidenediamine, 516
663. Neoridine, 515, 516
664. Gadayerine, 516-518
665. Putresdne, 518, 510
666. Metaphenylenediamine, 519
667. Paraphenylenediamine, 519
668. Hexametnylenediamine, 519
669. Diethylenediamine, 519, 520
670. Mydaleine, 520
671. Gnanidine, 520, 521
672. Methylguanidine, 521, 522
673. Saprine, 522
674. The Choline Group 522, 528
675. Neurine— Trimethyloxyammoniuni, 523
676. Betaine 523, 524
677. Peptotoxine 524
678. Pyridine Alkaloid from the Cuttle Fish, 524
679. Poisons connected with Tetanus, 525
680. Tetanotoxine, 525, 526
681. Mydatoxine, 526
682. The Poison of Mussels, 526, 527
688. Tyrotoxine, 527, 528
684. Toxines of Hog Cholera, 528
685. Other Animal Toxines, 528,529
Division III.— Food Poisonimo.
686. The Development of Toxic Principles in Food — Various Mass Poison-
ings—Statistics, 529-531
687. German Sausage Poisoning, 582
PART VIII.— THE OXALIC ACID GROUP OF POISONS.
688. Distribution of Oxalic Add, 533
689. Chemical Properties of Oxalic Acid, 533, 534
690. Oxalate of lime, 534,535
691. Use in the Arts, 535
692. Hydropotassic Oxalate Binoxalate of Potash, 535
698. Statistics of Oxalic Acid Poisoning 535
694. Fatal Dose, 535
695. Effects of Oxalic Acid and Oxalates on Animals, .... 535, 536
696. Kobert and Kiissner's Researches, 536
697. Effects of Vaporised Oxalic Acid, 537
698. Eifectsof Oxalic Acid and Hydropotassic Oxalate on Man, 537-539
699. Physiolo^cal Action, 539, 540
700. Pathological Chan^, 540
701. Specimens of Oxalic Acid Poisoning in Museums, .... 541
702. Pathological Changes produced by Hydropotassic Oxalate, . 541
703. Separation of Oxalic Acid from Ch^nic Substances, . 541-544
704. Oxalate of lime in the Urine, 544
705. Estimation of Oxalic Acid, 544-545
Certain Oxalic Bases — Oautlmethyline — Oxalpropyline,
706. Schulz and Mayer's Researches on the Oxalic Group of Poisons, . 545
CONTENTS. XXVii
PART IX.— INORGANIC POISONS.
I. Precipitated from a Hydroghlokio Acid Solution bt Uydric Sulphide
—Precipitate Yellow or Orange.
arsenic— ANTIMONY— cadmium.
1. Arsenic,
Section Page
707. Metallic Arsenic, 546
708. Areenioufl Anhydride — Areenious Acid — White Arsenic, . . 546-548
709. Arsiue-Arseniuretted Hydrogen, 548, 549
710. Arsine in the Arts, 549
711. Effects on Animals and Man of Breathing Arsine, .... 549-551
712. The Sulphides of Arsenic, 551
713. Orniment, or Arsenic Trisulphide 561
714. Haloid Arsenical Compounds— The Chloride of Arsenic— the Iodide
of Arsenic, 551
715. Arsenic in the Arts, 552
716. Pharmaceutical, Non-Officinal, and other Preparations of Arsenic, . 552-556
717. Stotistics, 556, 557
718. The Law relative to Sale of Arsenic 557
719. Dose, 557, 558
720. Effects of Arsenious Acid on Plants, 558
721. Effects on Animal Life, 558-560
722. Effects of Arsenious Acid on Man, 560, 561
723. Manner of Introduction of Arsenic, 561,562
724. Cases of Poisoning by the External Application of Arbeuic, . . 562, 568
725. Arsenic in Wall-Papers, 564
726. Forms of Arsenical Poisoning 564, 565
727. The Subacute Form, 565-567
728. The Nervous Form 567, 568
729. Absence of Symptoms 568
730. Slow Poisoning, 568, 569
781. The Maybrick Case, 569-571
781 A. Poisoning by Arsenical Beer, 571, 572
732. Post-mortem Appearances in Animals 572, 578
788. Post-mortem Appearances in Man — Museum Pre]Kirations, . . 573, 574
784. Changes in Quilet, Stomach, Liver, and Kidneys, .... 574-576
735. Physiolojjrical Action of Arsenic, 576, 577
786. Elimination of Arsenic, 577
737. Antidote and Treatment, 577
738. Detection of Arsenic, 577-585
739. Arsenic in Glycerin, 585
740. Arsenic in Organic Matters, 585-587
741. Imbibition of Arsenic after Death, 587-590
742. Analysis of Wall-Paper for Arsenic, 590, 591
743. Estimation of Arsenic, 591,592
744. Electrolytic Methods, 592-594
745. Gautier's Method, 594, 595
746. Precipitation as Tersulphido— (a) Solution of the Precipitate in
Ammonia and Estimation by Iodine ; (6) Oxidation of the
Sulphide and Precipitation as Ammonio-Magnesian Arseniatc ;
(c) Conversion of the Trisulphide into the Arseno-Molybdate of
Ammonia ; {d) Conversion of the Sulphide into Metallic Arsenic, 595-600
2. Antimony,
747. Metallic Antimony, 600
748. Antimonious Sulphide, 600, 601
749. Tartarated Antimony or TarUr Emetic, 601
750. Metantimonic Acid, 601
XXVm OOMTKNTS.
Section Page
751. Pharmaceutical, Veterinary, and Quack Preparations of Antimony
— AntimoniaJ Preparations used in Pyrotecnny, .... 602-604
762. Allocs containing Antimony, 604
758. Antimonial Pigments, 605
764. Dose, 605
755. Effects of Tartar Emetic and of Antimony Oxide on Animals, . 605, 606
756. Effects of Tartar Emetio on Man 606,607
757. Chronic Antimonial Poisoning, 607, 608
758. The Chapman Case, 608, 609
759. Poet-mortem Appearances, 609, 610
760. Elimination of Ajitimony, 610
761. Antidotes for Tartar Emetic, 610
762. Efl'ects of Chloride or Butter of Antimony, 610,611
768. Detection of Antimony in Oiganic Matters— Identification of Anti-
mony Sulphide : (a) Dir Method, (6) Wet Processes — Hyposulphite
Method--Tartaric Acid Method— ^Sodium Peroxide Method, . 611-614
768A.Stibine 614
764. Quantitative Estimation, 614, 615
8. CcLdmiuin,
765. Properties of the Metal Cadmium, 615
766. Cadmium Oxide, 615
767. Cadmium Sulphide, 615
768. Medicinal Preparations, 615
769. Cadmium in the Arts, 615
770. FatalDose of Cadmium, 615,616
771. Separation and Detection of Cadmium, 616
II. Pkbcipitated by Hydric Sulphide in Hydboguloric Acid Solution
— PiiEoiPiTATE Black.
LEAD — COPPER— BISMUTH— SILVER— MERCURY.
l.Lead.
772. Metallic Lead— Oxide of Lead— Red Lead, 616,617
778. Sulphide of Lead 617
774. Sulphate of Lead, 617
775. Acetate of Lead, 617
776. Chloride of Lead— Carbonate of Lead, 617,618
777. Prei)arations of Lead used in Medicine — Quack Nostrums containing
Lead— Lead Pigments — Salts used in the Arts — Alloys of Lead, . 618, 619
778. Statistics of Lead-Poisoning 620
779. Lead as a Poison, 620-622
780. Effects of Lead Compounds on Animals, 622, 628
781. Effects of Lead Compounds on Man— Acute Poisoning, . . 628-625
782. Chronic Poisoning by Lead, 625, 626
788. Lead Encephalopat^, 626
784. Lead-Poisoning in Wliite-lead Factories — Distribution of Lead in the
Brain, 627, 628
785. Influence of Lead on the Excretion of Uric Acid 628, 629
786. Effects of Lead- Poisoning on the Offspring, 629
786a. Lead in Drinking Water— Testing for Lead in Water 629-681
786b. The Plumstead Murder Case, 681
787. Post-mortem Appearances, 632
788. Physiological Action of Lead, 632, 688
789. Elimination of Lead 683
790. Fatal Dose— (a) Sugar of Lead ; (6) Basic Acetate ; (c) Carbonate, . 688, 684
791. Antidote and Treatment 684
792. Localisation of Lead, 684
798. Detection and Estimation of Lead, 685
CONTENTS. XXIX
Seetlon Page
798A.Tetra • methyl • diamino - phenyl • methane as a Test for Lead
Peroxide, 685, 686
798b. Electrolytic Method of Separating Lead as Dioxide, . . 686
794. Estimation of Lead, 686, 687
2. Copper.
795. Metallic Copper, 687
796. Cnpric Oxide, 687
797. Oupric Sulphide 687, 638
798. Solubility of Copper in Water and Various Fluids, .... 688-640
799. Copper in the vegetable and Animal Kingdom and in Foods, . 640, 641
800. The Coppering of Vegetables, 641-648
801. Preparations of Copper used in Medicine and the Arts, 643, 644
802. Dose— Medicinal Dose of Coiifier 644
803. Eflfects of Soluble Copper Salts on Animals, 644-646
804. Toxic Doee of Copper Salts, 6^6,647
805. Oases of Acute Poisoning, 647, 648
806. Effects of Subacetate, Subchloride, and Carbonate of Copper, . 648
807. Post-mortem Appearances 648
808. Chronic Poisoning by Copper 648-650
809. Detection and Estimation of Copper — Electrolysis of Chopper Salts-
Special Tests for Copper 650,651
810. Volumetric Processes for the Estimation of Copper, . 651,652
8. Bismuth,
811. Properties of Metallic Bismuth, 652
812. The Peroxide of Bismuth, 652
818. The Sulphide of Bismuth, 652
814. Preparations of Bismuth used in Moflicino and the Arts, . 652, 653
815. Meaicinal Doses of Bismuth, 653
816. Toxic Effects of Bismuth, 653,654
817. Extraction and Detection of Bismuth in Animal Matters, 654, 655
818. Estimation of Bismuth— Estimation of Bismuth by Potassic Dichro-
mate— Electrolytic Estimation, 655-657
4. Silver,
819. Properties of Metallic Silver 657
820. Chloride of Silver 657
821. Sulphide of Silver, 657,658
822. Preparations of Silver used in Medicine and the Arts, 658, 659
823. Meaicinal Dose of Silver Com])ounds, 659
824. Effects of Nitrate of Silver on Animals, 659,660
825. Toxic Effects of Silver Nitrate on Man — (1) Acute Poisoning;
(2) Chronic Poisoning, 660
826. Post-mortem Appearances, 660, 661
827. Detection and Estimation of Silver, 661,662
5. Mercury,
828. Properties of the Metal— Mercurous Chloride 662
829. Mercury Sulphide, 662
830. Medicinal Preparations of Mercury, 668-667
831. Mercury in the Arts, 667, 668
882. The more common Patent and Quack Medicines containing Mercury, 668
838. Mercury in Veterinary Medicine, 669
834. Medicinal and Fatal Dose, 669
835. Poisoning by Mercury —Statistics, 669, 670
836. Effects of Mercurial Vapour and of the Non-Corrosive Compounds of
Mercuiy, 670,671
XXX CONTENTS.
Baoftloii Fi«*
887. E£feot8onMui 671,672
888. Absorption of Merotuy by the Skin, 672
889. Symptoms of Poisoning by Mercury Vapour, 672, 678
840. Mercurial Tremor, 678,674
841. Mercuric Methide, 674, 676
842. Effects of the Corrosiye Salts of Merouiy, 675,676
848. Poisoning by the External Application of CJorrosiye Sublimate, 676
844. The Nitrates of Mercury 676
846. Case of Poisoning by Mercury Nitrate, 676,677
846. Mercuric Cyanide, . . . • 677
847. White Precipitate, 677
848. Treatment of Acute and Chronic Poisoning, 677
849. Post-mortem Appearances— Museum Specimens, .... 677, 678
850. Pathological Appearances after Nitrate of Mercury, 677, 678
851. Elimination of Mercury, 679, 680
852. Tests for MercuiT, 680,681
858. The Detection of Mercury in Organic Substances and Fluids, . 681-688
853a. Separation of Mercury by Hydroxylamine, 683
853B.Detectionof Mercury in the Urine, 683-685
854. Estimation of Mercury, 685
855. Volumetric Processes for the Estimation of Mercury, . 685, 686
III. Precipitated by Hydric Sulphide from a Neutral Solution.
ZINC— NICKEL— COBALT.
1. Zinc.
856. The Properties of Metallic Zinc, 686, 687
857. The Carbonate of Zinc, 687
858. The Oxide of Zinc, 687
869. The Sulphide of Zinc— The Sulphate of Zinc, 687
860. Chloride of Zinc, 687,688
861. Zinc in the Arts — Chromate of Zinc — Contamination of Liquids by
Zinc, 688,680
862. Effects of Zinc, as shown by Experiments on Animals, . 689
863. Effects of Zinc Compounds on Man— (a) Zinc Oxide, 689, 690
864. (6) Sulphate of Zinc, 690
866. \c) Zinc Chloride, 690, 691
866. Post-mortem Appearances, 691, 692
867. Detection of Zinc in Organic Liquids or Solids, .... 692, 693
868. Identification of Zinc Sulphide, 693
2. Nickel— CdbaU.
869. Poisonous Dose of Nickel Salts, 693, 694
870. Symptoms in Frogs, Pigeons, Guinea- Pigs, Rats, Rabbits, 094, 695
871. Effects on the Circulation— Nervous System, 695
872. Action on Striped Muscle, 695
873. Separation of Nickel or Cobalt from the Organic Matters or Tissues, 695, 696
874. Estimation of Cobalt and Nickel, 696
IV. Precipitated by Ammonium Sulphide.
IRON— CHROMIUM — THALLIUM— ALUMINIUM— URANIUM.
1. Iron,
875. Poisonous Properties of Iron, 696
876. Ferric Chloride— Pharmaceutical Preparations, .... 696, 697
877. Effects of Ferric Chloride on Animals, 697
CONTENTS. XXXI
S«otion P»g«
878. Effects on Man, G97, G98
879. Elimination of Iron Chloride, 698
880. Post-mortem Appearances, 698, 699
881. Ferrous Sulphate, Copperas, or Green Vitriol, .... 699, 700
882. Search for Iron Salts in the Contents of the Stomach, etc. 700, 701
2. Chromium,
883. PoisonousSaltsofChromium— Neutral Chromate of Potash, . 701
884. Potassic Bichromate 701
886. Neutral Lead Chromate, 701,702
886. Use in thp Arts, 702
887. Effects ot some of the Chromium Compounds on Animal Life, . 702
888. Effects of some of the Chromium Salts on Man— Bichromate Disease, 702, 703
889. Acute Poisoning by Potassic Bichromate — Statistics — Illustrative
Cases, 703, 704
890. Poisoning by Chromate of Lead, 704, 706
891. Post-mortem Appearances, 705
892. Detection of the Chromat^, and Senaration of the Salt-s of Chromium
from the Contents of the Stomach, 706
3. ThcUlium.
893. Thallium— General Properties, 707
894. Effects of Thallium, 707
896. Separation of Thallium from Organic Fluids or Solids, ... 707
4. Aluminium.
896. Aluminium and its Salts, 707, 708
897. Action of Alum Salts, 708,709
898. Post-mortem Appearances, 709
899. Detection of Alumina, 709,710
6. Uranium,
900. Poisonous Properties of Uranium Salts, 710
901. Detection and Estimation of Uranium 710
v. ALKALINS RA11TH8.
Barium,
902. Poisonous Salts of Barium, 710,711
903. Chloride of Barium, 711
904. Baric Carbonate, 711
906. Sulphate of Barium, 711
906. Effects of the Soluble Salts of Barium on Animals, . 711,712
907. Effects of the Salts of Barium on Man— Fatal Dose, ... 713
908. SjTuptoms, 713, 714
909. Distribution of Barium in the Body, 714, 715
910. Post-mortem Appearances, 715
911. The Senaration of Barium Salts from Organic Solids or Fluids, and
their Identification, 715, 716
XXXU G0NTBNT8.
APPENDIX.
Treatment by Antidotes or otherwise of Gases of Poisoning.
Section Page
912. Instraments— Emetics— Antidotes,
913. Alphabetical List of the Chief Poisons, with Antidotes and Treatment, 719, 738
Domestic Readv Remedies for Poisoning.
914. The Multiple Antidote and Simple Remedies 733, 734
Index, 736-772
LIST OF ILLUSTRATIONS.
Williams' Apparatus for Investigating the Action of Poisons on the Frog's Heart, 46
Jaoobi's Apparatus, 47
MercuiT Ihunp, 60
Ether Keoovery Apparatus, 61
Micro-Spectroscope, 67
Diagram showing Absorption Bands pnxlucod from Colour Reactions, 68
Spectroscopic Appearances of Blood 61
Haematin Crystals, 64
Deaths per Million Living from Alcohol, 1876-1903, 143
Tube for Treatment of Liquids by Ethereal Solvents, 163
Diagram of Visual Field in Nitro-Benzol Poisoning, 200
BlondloVs Apparatus for Production of Phosphine, 244
Subliming Cell, 260
Crystals of Methyl- Brucine Iodide 362
Diagram Indicatmg Action of Atropine on the Heart 390
Curves showing Changes in the Pulse, and Arterial Tension produced by an
Infusion of i>i^iito/i5, 441
Bocklisch's Flask for Distillation in a Vacuum, 608
BerzeliuH* Tube for Reduction of Arsenic, 578
Thorpe's Electrolytic Apparatus for Determination of Arsenic, . . 692
Gabriel Bertrand's Apparatus for same, 695
Bent Tube for Assay of Mercury, 686
POISONS:
THEIR EFFECTS AND DETECTION,
PART K— INTRODUCTORY.
L— The Old Poison-Lore.
§ 1. It is significant that tlie root ^Uox*' of the modera word tojda^^y
can be traced back to a very ancioiit word meaning " bow " or '* arrow,'*
or, in it"! broadest senae, sorae " tool " used for slaying \ henoe it is no
far-fetched supposition that the first poison knowledge was that of the
septic poisons, Perchance the savage found that weapons soiled with
the blood of former victims made svounda fatal ; from this observation
the nert step naturally would be that of experiment — the arrow or
spear would bo steeped in all mauner of ofTensive pastes^ and smeared
with the vogetable juices of those plants which were deemed noxious ;
and as the effecta were mysterious, they would be ascribed to the
supernatural powers, and covered with a veil of superstition*
The history of the poimn-lehre^ like all history, begiua in the region
of the myths j there was a dark saga prevailing in Greece, that in the
far north existed a land ruled by sorcerers — all children of the snn —
and named Aeetee, Perses, Hecate, Medea, and Circe* Later on, the
enchanted land was localised at Colchis, and Aeetes and Peraes were
aaid to be brothers. Hecate was the daughter of Perses; she was
married to Aeetes, and their daughters were Medea and Circe, Hecate
was the discoverer of poisonous herbs, and learned in remedies both evil
and good. Her knowledge passed to Medea, w^ho narcotised the dragon,
the guardian of the golden fleece, and incited Jason to great undertakings.
In the expedition of the Argooauts, the poets loved to describe
Hecate's garden, with ita lofty walls. Thrice-folding doors of ebony
barred the entmnee, which was guarded by terrible forms : only the
initiated few, only they who bore the leavened rod of expiation, and the
concealed conciliatory offering of the Medea, could enter into the
sanctuary. Towering above all was the temple of the dread Hecate,
whose prieste^eB offered to the gods ghastly sacrifices.
I
2 POISONS : THEIR EFFECTS AND DETECTION. [§ 2, 3.
§ 2. The oldest Egyptian king, Menes, and Attains Phjlometer, the
last king of Pergamus, were both famous for their knowledge of plants.
Attains Phjlometer was acquainted with hyoscyamus, aconite, conium,
veratrum, and others; he experimented on the preparation of poisons,
and occupied himself in compounding medicines. Mithradetes Eupator
stood yet higher : the receipt for the famous theriacct, prepared in later
years at an enormous price, and composed of fifty-four different ingredi-
ents, is ascribed to him. The wonderful skill shown by the Egyptians
in embalming and technical works is sufficient to render it fairly certain
that their chemical knowledge was considerable ; and the frequent opera-
tions of one caste upon the dead must have laid the foundations of a
pathological and anatomical culture, of which only traces remain.
The Egyptians knew pnissic acid as extracted in a dilute state from
certain plants, among the chief of which was certainly the peach ; on a
papyrus preserved at the Louvre, M. Duteil read, " Pronounce not the
name of I. A. 0. under the penalty of the peach ! " in which dark threat,
without doubt, lurks the meaning that those who revealed the religious
mysteries of the priests were put to death by waters distilled from the
peach. That the priests actually distilled the peach-leaves has been
doubted by those who consider the art of distillation a modern inven-
tion ; but this process was well known to adepts of the third and fourth
centuries, and there is no inherent improbability in the supposition that
the Egyptians practised it.*
§ 3. From the Egyptians the knowledge of the deadly drink appears
to have passed to the Romans. At the trial of Antipater,t Yerus brought
a potion derived from Egypt, which had been intended to destroy Herod ;
this was essayed on a criminal, he died at once. In the reign of Tiberius,
a Eoman knight, accused of high treason, swallowed a poison, and fell
dead at the feet of the senators : in both cases the rapidity of action
appears to point to prussic acid.
The use of poison by the Greeks, as a means of capital punishment,
without doubt favoured suicide by the same means ; the easy, painless
death of the state prisoner would be often preferred to the sword by one
tired of life. The ancients looked indeed upon suicide, in certain in-
stances, as something noble, and it was occasionally formally sanctioned.
Thus, Valerius Maximus tells us that he saw a woman of quality, in the
island of Ceos, who, having lived happily for ninety years, obtained
leave to take a poisonous draught, lest, by living longer, she should
happen to have a change in her good fortune ; and, curiously enough,
* Zosemus of Alexandria gives a drawing of a still which he states is copied from
the ancient temple of Memphis in Egypt Analyst, xxx. 295, 1906, and Hoeflfer,
Histcire de Ch,emi€y vol. i. p. 262.
t Jos., AtU,, b. xvii. c. 5.
%3]
TUB OLD POtSON-LORE.
this sanctioiring of self (J est ruction seems to bave been copied in Europe.
Msad relates that the people of Matiieilles of old bad a poison, kept by
the public authoritieSi in which oictita was an ingredient : a dose was
allowed to any one who eould show why he should desire death. What-
ever use or abuse might be matie of a few violent poisons, Greek and
Roman knowledge of poi^ons^ tbeir etl'eeta and methoda of detection,
was Btationarjf primitiye, and incomplete,
Nicander of Colophon (204-138 rx.) wrote two treatises, the mo8t
ancient works on this subject extjint, the one describing the effects of
snake venora ; the other, the properties of opium, henbane, certain
fungi, colchicum, aconite, and conitnu. He divided poisons into tbose
wbich kill quickly, and those which act slowly. As antidotes, those
medicines are recommended which excite vomiting — e.^.t bikewarm oil,
warm water, mallow, linseed tea, etc.
A^mllodi^rwi lived at the commencement of the third century B.C. :
he wrote a work on poisonous animals, and one on deleterious medicines ;
tbese works of Apollodorus were the sources from which Pliny, HeraclituSj
and tie vera! of the later writers derived most of their knowledge of poiaous,
lHQ&*ondes (40-90 a.d.) well detailed the effects of cautbaride% sul*
phate of copper, mercury, lead, and arsenic. By arsenic he would
appear sometimes to mean the sulphides, sometimes the white ox:jde.
Btoscorides divided poisons, according to their origin, into three classes,
?iK. : —
L Animal Poisons. — Under this bead were classed ciintharides and
allied lieetlett, toads, salamanders, poisonous snakes, a particular variety
of honey, and the blood of the oi, probably the latter in a putrid state.
He also speaks of the ** »fa-hare.'* The sea-hare wfts considered by the
ancients very poisonous, and Domitian is said to have murdered Titus
witb it. It is supposed by naturalists to have been one of the genua
Apljjma, among the fjmteropt-HU. Bf»th Pliny and Dioscorides depict the
atiimal as something very formidable : it was not to Ik? looked at, far
teas touched. The aplysise exhale a very nauseous and fcctid odour
when I hey are approached : the beat known of the species resembles,
when in a state of repose, a mass of unformed flesh ; when in motion, it
is like a common slug ; its colour is reddish-brown ; it has four boma
on its head; and the eyes, wbicli are very small, are situated between
the two hinder ones. This aplysia has an ink re^rvoir, like the sepia^
and ejects it in or;Ijr to escape from its enemies ; it inhabits the muddy
bottom of the water, and lives on small crabs, mollusea, etc*
2, PoiBona from PUutB.^-^Dioscorides enumerates opium^ black
and white hjoscyamus (especially recognising the activity of the seeds),
niandragora, which was probably a mixture of various solanacea?, conium
(used to poison the condemned by the people of Athens aud the dwelletn
i^J
4 POISONS : THEIR KFFBCTS AND DETECTION. [§ 4.
of ancient Massilia), elaterin, and the juices of species of euphorbia and
apocynesB. He also makes a special mention of aconite, the name of
which is derived from Akon, a small city in Heraclea. The Greeks were
well aware of the deadly nature of aconite, and gave to it a mythical
origin, from the foam of the dog Cerberus. Colchicum was also known
to Dioscorides ; its first use was ascribed to Medea. Veratrum album
and nigrum were famous medicines of the Romans, and a constituent of
their "rat and mice powders"; they were also used as insecticides.
According to Pliny, the Gauls dipped their arrows in a preparation of
veratrum.* Daphne mezereon, called by the Romans also smilax and
taxus, appears to have been used by Cativolcus, the king of the Eburones,
for the purpose of suicide; or possibly by "taxus" the yew-tree is
meant, t
The poisonous properties of certain fungi were also known. Nicander
calls the venomous mushrooms the " evil fermentation of the earth," and
prescribes the identical antidotes which we would perhaps give at the
present time — viz., vinegar and alkaline carbonates.
3. Mineral Poisons. — Arsenic has been already alluded to. The
ancients used it as a caustic and depilatory. Copper was known as
sulphate and oxide ; mercury only as cinnabar : lead oxides were used,
and milk and olive-oil prescribed as an antidote for their poisonous
properties. The poiaon-lehre for many ages was cousidered as something
forbidden. Galen, in his treatise "On Antidotes," remarks that the
only authors who dared to treat of poisons were Orpheus, Theologus
Morus, Mendesius the younger, Heliodorus of Athens, Aratus, and a
few others ; but none of these treatises have come down to us. From
the close similarity of the amount of information in the treatises of
Nicander, Dioscorides, Pliny, Gkilen, and Paulus iEgineta, it is probable
that all were derived from a common source.
§ 4. If we turn our attention to early Asiatic history, a very cursory
glance at the sacred writings of the East will prove how soon the art of
poisoning, especially in India, was used for the purpose of suicide, revenge,
or robbery.
The ancient practice of the Hindoo widow — self-immolation on the
burning pile of her husband — is ascribed to the necessity which the
Brahmins were under of putting a stop to the crime of domestic poison-
ing. Every little conjugal quarrel was liable to be settled by this form
of secret assassination, but such a law, as might be expected, checked
the practice.
Poison was not used to remove human beings alone, for there has
been from time immemorial in India much cattle-poisoning. In the
Institutes of Menu, it is ordained that when cattle die the herdsman
• Pliny, XXV. 6. f De Bello Gallico, vi. 31.
TH« OLD P0I80N-L0R1.
s
shall uarry to his master tlietr ears, tlioir hideg^ their tailsi, the akin
below their uavele, their tendons, and the liquor oozing from their
foroheads. Without doubt these regitlatious were directed against
cattle-poison era,
The poiBOiis ktiown to the At^iattos were arsenic, riconilei i>piuiii, and
various Bolanaceoua plants. There has been a mytli floatiug through
the ages that a potsou exists which will slay a long time after its intro*
duetion. All uiodeni authors have treated the matter as an oxiiggerated
legend^ but, for my own part, I see no reason why it should not, In
reality, be founded on fact» There is little doubt that the Asia tie
poisoners were well acquainted with the infectious qualities of nerUin
fevers and malignant diseases. Now, these very maligu&ut disc&BGtt
answer precisely to the deseriptiou of a poison whi(!h lum no irn mediate
effects. Plant smallpox in the body of a man, and for a wlioh; fortnight
he walks about, weU and hearty. Clothe a pemon with a gartneiit
soaked in typhus, and the same thing occurs — for many day a there will
be no sign of failure, Agaiui the gipsies, speaking a tongue which is
essentially a deformed prakriii ^^^ therefore Indian in origin, have long
posBessed a knowledge of the properties of the curious **mumr
ph^d&myem" This was considered an alga by Agaron, but Berkeloy
referred it to the fungi* The gipsies are said to have administered the
spores of this fungi in warm water* In this way they rajiidly attauh
themselves to the mucous membrane of the thrt»it^ all the symptoms of
a phthisis follow, and death takes place in from two tii thrt*e weeks.
Mr, Berkeley informed me that he hiis seen specimens growing on hrt^th
which had been rejeeted from the stomach, and that i( develops in
enornious quantities on oil-easks and walls impregnattMl with groaj«e.
The filaments are long, from 12 to 18 inches, and it is capable of very
rapid development.
There is also a modern poison, which, in certain doses^ doomn the
unfortunate indivi<lual to a terrible malady, simulating, to a eouaiderablo
extent, natural disease --that is phosphorus. This poison wa% bow«veri
unknown until some time in the eleventh century, when Alchid ]k*ciier,
blindly ei|>enmenting on the distillation of urine and carbon, obtained
his ^* esearhQurh,** and passed away without knowing the importance of
his diseovery, which, like so many olbers, had to be rediieovered at a
later period*
g 5. The Hebrews were aequaint^d with certain poisiotut, th«i exact
nature of which is not quite clear. The worda "rapeft" and "ehmna'*
teem to be used oocasioually as a generic term for polaoil, and •ODMtllsef
to mean a specific thing ; ** nmeh" especially, in uied to nigiiify toQid
poisonous parasitic plant. Tbij knew yellow araenjo under ibf jaaoM of
'' wf/«," aeonlte under the nmmo id '' boHhlm^^ and poMibly ^' mm *'
6 POISONS : THEIR EFFECTS AND DETECTION. [§ 6.
ergot.* Id the later period of their history, when they were dispersed
through various nations, they would naturally acquire the knowledge of
those nations, without losing their own.
§ 6. The part that poison has played in history is considerable.
The pharmaceutical knowledge of the ancients is more graphically and
terribly shown in the deaths of Socrates, Demosthenes, Hannibal, and
Cleopatra, than in the pages of the older writers on poisons.
In the reign of Artaxerxes II. (Memnon), (b.o. 405-359), Phrysa
poisoned the queen Statira by cutting food with a knife poisoned on one
side only. Although this has been treated as an idle tale, yet two
poisons, aconite and arsenic, were at least well known ; either of these
could have been in the way mentioned introduced in sufficient quantity
into food to destroy life.
In the early part of the Christian era professional poisoners arose,
and for a long time exercised their trade with impunity. t Poisoning
was so much in use as a political engine that Agrippina (a.d. 26)
refused to eat of some apples offered to her at table by her father-in-
law, Tiberius.
It was at this time that the infamous Locusta flourished. She is said
to have supplied, with suitable directions, the poison by which Agrippina
got rid of Claudius ; and the same woman was the principal agent in the
preparation of the poison that was administered to Britannicus, by order
of his brother Nero. The details of this interesting case have been
recorded with some minuteness.
It was the custom of the Romans to drink hot water, a draught
nauseous enough to us, but, from fashion or habit, considered by them a
luxury ; and, as no two men's tastes are alike, great skill was shown by
the slaves in bringing the water to exactly that degree of heat which
their respective masters found agreeable. I
The children of the Imperijil house, with others of the great Roman
families, sat at the banquets at a smaller side table, while their parents
reclined at the larger. A slave brings hot water to Britannicus ; it is too
hot ; Britannicus refuses it. The slave adds cold water ; and it is this
cold water that is supposed to have been poisoned ; in any case,
Britannicus had no sooner drunk of it than he lost voice and respiration.
Agrippina, his mother, was struck with terror, as well as Octavia, his
sister. Nero, the author of the crime, looks coldly on, saying that such
fits often happened to him in infancy without evil result ; and after a
few moments' silence the banquet goes on as before. If this were not
* R. J. Wunderbar, Bihlisch-talmudische Medicin, Leipzig, 1860-60.
t Tacitus, lib. xii. , xiii. Mentioned also by JuTenal and Suetonius.
t The death of Anus (a.d. 325) is ascribed by Gibbon either to a miracle or to
poison — *' his bowels suddenly burst out in a privy."
§6.]
THK OLD POIS0N*L0RK.
sudden death from heart or brain diaease^ the poison muet hav6 been
either a cyanide or prussitj acid.
In thoge times no autopsy was possible : although the Alexandrian
school, some 300 ymts before Chriet, had dissected both the living and
the dead, the work of Herophilus and Eraai stratus had not been pureiied,
and the great Roman and Greek writers knew only the rudicnents of
human anatomy, while as to pathological changes and their true inter-
pretJfctioii, their knowledge may be said to have been absolutely nil It
was not, indeed, until the ftfteenth century that the Popes^ silenciug
ancient scruples, authorised disgections ; and it was not until the
sixteenth century that Vesalius, the first worthy of being considered a
great anatomist, arose. In default of pathological knowledge^ the
ancients attached great importance to mere outward marks and discolorar
tions. They noted with special attention spots and lividitj, and supposed
that poisons mingled out the heart for some quite peculiar action, altering
its substance in such a manner that it resisted the action of the funeral
pyre^ and remained uuconiunied. It may, then, fairly be presumed that
many people must have died from poison without suspicion, and still
more from the sudden e fleets of latent diseat^e, iiserlbed wrongfully to
poiBOD. For example, the death of Alexander was generally at that time
ascribed to poiHon ; but Littri^ has fairly proved thut the great emperor,
debilitated by his drinkitig habits, caught a malarioui^ fever in the
marshes around Babylon, and died after eleven days' illness. If, added
to sudden death, the body, from any cause, entered into rapid putrefac-
tion, such signs were considered by the people absolutely conclusive of
paisoning: this belief, indeed, prevailed up to the middle of the
seventeenth century^ and lingers still among the uneducated at the
present day. Thus, when Bntannicua died, an extraordinary lividity
spread over the face of the corpse, which they attempted to conceal by
painting the face. When Pope Alexander VI. died, probably enough
from poison, his body {according to Guieciardini) became a frightful
spectacle^ — it was lividf bloated^ and deformed ; the gorged tongue
entirely filled the mouth ; from the nose flowed putrid pus, and the
stench was horrible in the extreme.
All these effects of decomposition, we know, are apt to arise in coarse,
obese bodies, and accompany both natural and im natural deaths ; indeed,
if we look strictly at the matter, putting on one side the preservative
ejects of certain metallic poisons, It may be laid down tliat generally the
eorj^ses of those dying from poison are less apt to decompose rapidly than
those dying from disease — this for the simple reason that a majority of
diseases cause changes in the lluidsand tissues, which render putrefactive
changes more active, while, as a rule, these who take poieon are suddenly
killed^ with their fluids and tissues fairly healthy.
8 POISONS : THEIR EFFECTS AND DETECTION. [§ 6
When the Duke of Burgundy desired to raise a report that John,
Dauphin of France, was poisoned (1457), he described the imaginary
event as follows : —
" One evening our most redoubtable lord and nephew fell so grievously
sick that he died forthwith. His lips, tongue, and face were swollen ;
his eyes started out of his head. It was a horrible sight to see — for so
look people that are poisoned."
The favourite powder of the professional poisoner, arsenic, was known
to crowned heads in the fourteenth century , and there has come down
to us a curious document, drawn out by Charles le Mauvais, King of
Navarre. It is a commission of murder, given to a certain Woudreton,
to poison Charles VI., the Duke of Yalois, brother of the king, and his
uncles, the Dukes of Berry, Burgundy, and Bourbon : —
" Go thou to Paris ; thou canst do great service if thou wilt : do what
I tell thee ; I will reward thee well. Thou shalt do thus : There is a
thing which is called sublimed arsenic ; if a man eat a bit the size of a
pea he will never survive. Thou wilt find it in Pampeluna, Bordeaux,
Bayonne, and in all the good towns through which thou wilt pass, at
the apothecaries' shops. Take it and powder it ; and when thou shalt
be iu the house of the king, of the Count de Valois, his brother, the
Dukes of Berry, Burgundy, and Bourbon, draw near, and betake thyself
to the kitchen, to the larder, to the cellar, or any other place where thy
point can be best gained, and put the powder in the soups, meats, or
wines, provided that thou canst do it secretly. Otherwise, do it not."
Woudreton was detected, and executed in 1384.*
A chapter might be written entitled ** royal poisoners."! King
Charles IX. even figures as an experimentalist. J An unfortunate cook
has stolen two silver spoons, and, since there was a question whether
** Bezoar " was an antidote or not, the king administers to the cook a
lethal dose of corrosive sublimate, and follows it up with the antidote ;
but the man dies in seven hours, although Par6 also gives him oil.
Truly a grim business !
The subtle method of removing troublesome subjects has been more
often practised on the Continent than in England, yet the English throne
in olden time is not quite free from this stain.§ The use of poison is
* Tr69or de Ckartes. Charles de Navarre. P. Mortonval, vol. ii. p. 384.
t Napoleon Bonaparte poisoned at Jaffa (1799) those of his soldiers who had
plague and were too ill to be moved. — Memoirs of Napoleon Bonaparte, by F. de
Bourrienne.
t (Euvres de Pari, 2nd ed., liv. xx. Des Venines, chap. xliv. p. 507.
§ For example, King John is believed to have poisoned Maud Fitzwalter by *'a
poisoned egg."
**In the reign of King John, the White Tower received one of the first and
fairest of a long line of female victims in that Maud Fitzwalter who was known to
THE OLD POIfiON-LOHE,
wholly opposed to the Anglo-Sa^cou luethod of thought. To what auger
the people were wrought on tletecting poieonere ie seen in the fact tbst,
in 1542, a joung womnn was boiled alive in Smithfield for poisoning
three households,*
I 7. Two great criminal schools an>B6 from the fifteenth to the
seventeenth centuries in Venice and Italy, The Venetian poisoners are
of earlier date than the Italian, and flourished cliiefly in the fifteenth
century. Here we have the strange spectacle, not of the depravity of
indivitiaals, but of the government of the tState formally recognising
secret aasagsinatiou by poison, and proposals to remove this or that
prince, duke, or emperor, as a routine part of their deliberations. Still
more curious and unique, the dark communings of ** the council of im$ *'
were recorded in writings and the number of those who voted for and
who voted against the proposed crime, the reason for the assasainatjon,
and the sum to be paid, still exist in shameless b!ack and white. Those
who desire to study this branch of secret history may be referred to a
small work l>y Carl Hoti', whicL gives a brief account of what is known
of the proceedings of the council One example will here su^ce. On
the 15th of December 1513 a Fiunciscan brother, John of Ragnbo,
offered a selection of poison a, and declared himself ready to remove any
objectionable person out of the way. For the first sucoesaful case he
required a pension of 1500 ducats yearly, which waa to be increased on
the execution of future serviced. The presidents, Girolando Duoda and
Pietro Guiarina, placed the matter before the "ten^* on the 4tb of
January 1514, and on a division (10 against 5) it was resolved to accept
the singirfi of lier time ab Maud tho F&ir, The father of tliia beautiful girl wm
Robert* Lord FifcEwalttr, of Castle Buyjiard^ ou th(? Thames, one of Joku'a greatest
barons^ Yet the king, durkig li tit of viuleuce \i'ith tlie queen, fell madly in love
with tliia youog girl As neither the My lierself n«r her powerful aire would listen
to his disgraceful suit^ the king is &aid la hiive siuzed her by force at Duumow^ and
brought bcr to tbii Tower. Ftti^walWr ribLieU an otatery, oa wMoh the king sent
troops into Castle Bay nurd and his} other houses] ; and when the baron prottisUid
•gaiiuit these wfongi, Im maater battiahod him from the rcNhlm. Fitzwalter fled to
France with his wife and hiB other chddren, leaving his d&ughter Maud in the
Tower, where she suffered a daily iuBidt m the king's unlawful stut. On ht^r pr^md
and scornful answer to hia pa^ion being heard^ John eiirried her up to thf roof, and
lacked her in the njund turrn^t, standing on the north-east angle of the keep*
Ifaud'a eage was the highest, chill test den in the Tower ; but neither cold, nor
solitude, tior hunger could bre^k her striength. In the rage of his di^ppointed
bve^ the king sent one of hU miniona ttJ h«r room with a pcjisoned egg, of which the
brave girl ate and died."^^«r M^ut^^i Tm€>et, by Hepworth Dixon, Loud., 180i> j
i p. 46.
* "This yeare, the 17 th of Mareh, waa boy led inSmithfield one Margaret Davie,
a tn»yden, which had ponysoned 3 hoUBeholdes that she dwelled in. One bein^ her
miatre^js, wliidi dy^ of the same, and one Daringtoo and hia wyfe, which ahe also
dwelled with In Coleman i^treet, which dyed of the aame, and also one Tinleya,
which dyed also of the same,'* — Wriolht?rley*s Chr<inidf, A.u. 1512,
to POISONS : THBIB EFFECTS AND DETlCCTION. [§ 7.
80 patriotic an offer, and to experiment first on the Emperor Maximilian.
The bond laid before the " ten " contained a regular tariff— for the great
Sultan 500 ducats, for the King of Spain 150 ducats, but the journey
and other expenses were in each case to be defrayed ; the Duke of Milan
was rated at 60, the Marquis of Mantua at 50, the Pope could be removed
at 100 ducats. The curious offer thus concludes : — ** The farther the
journey, the more eminent the man, the more it is necessary to reward
the toil and hardships undertaken, and the heavier must be the pay-
ment.'* The council appear to have quietly arranged thus to take away
the lives of many public men, but their efforts were only in a few cases
successful. When the deed was done, it was registered by a single
marginal note, **factuni"
What drugs the Venetian poisoners used is uncei'tain. The Italians
became notorious in the sixteenth and seventeenth centuries for their
knowledge of poisons, partly from the deeds of Toffana and others, and
partly from the works of J. Baptista Porta, who wrote a very comprehen-
sive treatise, under the title of Natural Magic,* and managed to slide
into the text, in the sections on cooking {Be Re Goquinaria, lib. xiv.), a
mass of knowledge as to the preparation of poisons. There are prescrip-
tions that little accord with the title, unless indeed the trades of cook
and poisoner were the same. He gives a method of drugging wine with
belladonna root, for the purpose of making the loaded guest loathe drink ;
he also gives a list of solanaceous plants, and makes special mention of
nux vomica, aconite, veratrum, and mezereon. Again, in the section {De
Ancu2)io, lib. xv.) he gives a recipe for a very strong poison which he calls
^'venenum lupinum*' ; it is to be made of the powdered leaves of Aconi-
turn lycoctonum, Taxus baccata, powdered glass, caustic lime, sulphide
of arsenic, and bitter almonds, the whole to be mixed with honey, and
made into pills the size of a hazel- nut.
In the section De Medicis Experiinentis he gives a process to poison
a sleeping person : the recipe is curious, and would certainly not have
the intended effect. A mixture of hemlock juice, bruised datura,
stramonium, belladonna, and opium is placed in a leaden box with a
perfectly fitting cover, and fermented for several days ; it is then opened
under the nose of the sleeper. Possibly Porta had experimented on
small animals, and had found that such matters, when fermented, exhaled
enough carbonic acid gas to kill them, and imagined, therefore, that the
same thing would happen if applied to the human subject. However
this may be, the account which Porta gives of the effects of the solana-
ceous plants, and the general tone of the work, amply prove that he
was no theorist, but had studied practically the actions of poisons.
• J. Bapt. Porta, bom 1637, died 1616. NeapolUani Jlagice NaturcUis. Neapoli,
1689.
§ 7j THE OLD POISOK-LORK,
The miqiittous Toifana (or Tophaaa) made fiolutioiia of arsenbua acid
of varying strength, aud sold these solutions in phials under the name of
" Acquetta di NapAi*' for many years* She is supposed to have poisoned
more than 600 persons, among whom were two Popes — viz,, Pius TIL
and Clement XIV, The composition of the Naples water was long a
profound secret, but it is said to have been known by the reigning Pope
and by the Emperor Charles VI. The latter told the secret to Dr
(larelli, his physician, w^ho, again^ imjiarted the knowledge to the famous
Fried rich Hoffman in a letter still extant. Totfana was brought to justice
in 1709, but, availing herself of the imm unity afforded by con vents,
e«caped puuishmeut, and continued to sell her wares for twenty years
afterwHrds. When Kepfer * was in Italy he found her in a prison at
Naples, and many people visited her, as a sort of lion (1730). With
the Acq tin Toffajia, the ^* Acquetta di Perugia** played at the same
time il:s part. It is said to have been prepared by killing a hog, dis-
jointing the same^ strewing the pieces with white arsenic, which was
well rubbed hi, and then collecting the juice which dropped from
the meat^ this juice was considered far more poison ous than an
ordinary solution of art^etiic. The researciies of Selmi on compounds
conUiiuing arsenic, produced when animal bodies decompose in arsenical
fluids, lend re-ason and supjiort to this vicw^ ; and probably the juice
would not only be very poisonous, but act in a different manner,
aud exhibit symptoms ditfereut from those of ordinary arsenical
poisoning. Toffanu had diaoiples; she taught the art to Hieronytna
Spara, who formed an association of young married women during
the popedom of Alexander VII, ; these were detected on their own
confession.t
Contemporaneously with Tofiana, another Italian, Exili or Egide or
Gilles, attached to the service of Queen Christiana of Sweden, devoted
himself t-o similar crimes » He made the acquaintance of M, de St*
Croix or (jodin, a captain of horse in the Tra^cy regiment, when both
were imprisoned in the Bastille. It is popularly supposed that he it
Wifcs who iustnicted St. Croix in the use of poisons, and St. Croix, in his
turn, imparted the secret to bis partner Madame (or Marchioness) de
Briuvilliers, a little woman with very soft blue eyes, and said to be of
marvellous beauty. Frant^ Funck Brentauo % denies this account, saying
that the true version is that St, Croix and Madame de Briuvilliers got
their knowledge from Christopher G laser, a Swiss chemist, author of
a treatise on chemistry, and discoverer of potassium sulphate. The
• Kepfer 8 Trarei*. Load., 1758.
t Le Bret*s Mmjatuv lit Gcbraiiche der SUmi tu Kirchf^tt-UeschiMty TLcil 4,
FimukfoTt Jiad Leipzig, 1774*
t Princes and PoMOWiT*; Simdk^ ofiM Ctmri o/Zouis XI F.
12 POISONS: THEIR EFFECTS AND DETECTION. [§ 7-
lovers, at all events, wrote of their poisons as " Glaser's recipes," the
chief ingredient of which was without doubt arsenic.
Madame de Brinvilliers poisoned her father, her brothers, and other
members of her family ; she is also said to have experimented on the
patients at the Hotel Dieu, in order to test the strength of the powders
prepared for her by St. Croix. These powders were afterwards called
" Les poudres de succession," from a joking remark made by Madame
in her cups. St. Croix robbed the executioner by dying a natural death,
and Madame de Brinvilliers, after a sensational trial, at the end of which
the first president wept bitterly and all the judges shed tears, was
sentenced to torture * and death. The tale that St. Croix was suffocated
through the breaking of a glass mask while he was preparing some
poisonous substances, and that Madame de Brinvilliers was courted and
arrested by a police officer disguised as an abb^ according to Funck
Brentano, has no foimdation in fact.f
The numerous attempts of the Italian and Venetian poisoners on the
lives of mouarchs and eminent persons cast for a long time a cloud over
regal domestic peace. Bullets and daggers were not feared, but in their
place the dish of meat, the savoury pasty, and the red wine were re-
garded as possible carriers of death. No better example of this dread
can be found than, at so late a period as the reign of Henry VIII., J the
extraordinary precaution thought necessary for preserving the infant
Prince of Wales.
* The Marchioness was imprisoned in the Conciergerie and tortured. Victor
Hugo, describing the rack in that prison, says, **The Marchioness de Brinvilliers
was stretched upon it stark naked, fastened down, so to speak, quartered by four
chains attached to the four limbs, and there suffered the frightful extraordinary
torture by water," which caused her to ask, ** How are you going to contrive to put
that great barrel of water in this little body 1 **— Things seen by Victor ffugo, vol. i.
The water torture was this :—a huge funnel-like vessel was fitted on to the neck,
the edge of the funnel coming up to the eyes ; on now pouring water into the
funnel so that the fluid rises above the nose and mouth, the poor wretch is bound to
swallow the fluid or die of suffocation ; if indeed the sufferer resolve to be choked,
in the first few moments of unconsciousness the fluid is swallowed automatically,
and air again admitted to the lungs ; it is therefore obvious that in this way pro-
digious quantities of fluid might be taken.
t For the court of poisoners {chambre ardeiUc) and the histories of St. Croix, De
Brinvilliers, the priest Le Sage, the women La Voisin, and La Vigoureux, the reader
may be referred to Voltaire's SUcle de Louis XIV,, Madame de S^vignd*s Lettres,
Martinifere's HisL de la Rkfne de Louis XIV., Strutzel, De Veneni^, etc.
t Henry VIIL, at one time of his life, was (or pretended to be) apprehensive of
being iwisoned ; it was, indeed, a common belief of his court that Anne Boleyn
attempted to dose him. ** The king, in an interview with the young Prince Henry,
burst into tears, saying that he and his sister (meaning the Princess Mary) might
thank God for having escaped from the hands of that accursed and venomous harlot,
who had intended to poison them." — A Chronicle of England during the Reign of the
Tudorsy by W. J. Hamilton. Introduction, p. xxl
§ 8.] MODERN METHODS OF CHEMICALLY DETECTING POISONS. 1 3
*' Jfo person, of whatsoever rank, except the regular afetendanta in the
nursery, should apprtwvch the cradle, except with an order from the king's
hand. The food supplied to the child was to be largely * a^^^aijed^' and
h'lB clothes were t<> be washed by his own servanta, and no other hand
might touch them. The material was to be Bubmitted to all tests. The
chamberlain and vice-chamberlain must be present, morning and evening,
when the prince was washed and dressed, and nothing of any kind
bought for the use of the nursery might be introduced until it was
washed and perfumed* No person, not even the domestics of the palace,
might have access to the prince's rooms except those who were specially
appointed to them, nor might any member of the household approach
London, for fear of their catching and conveying infection," *
However brief and ini perfect the foregoing historical sketch of the
part that poison has played may be, it is useful in showing the absolute
necessity of a toxicological science— a science embracing many branches
of knowledge. If it is impossible now for ToflTanas, LocustaM, and other
specimens of a depraved humanity to carry on their crimes without
detection ; if poison is the very last form of death feared by eminent
political persons; it is not so much owing to a different state of society,
as to the more exact scientific knowledge which is appilied during life to
the discrimination of symptoms, diBtinguisbing hatweeu those resutting
from disease and those due to injurlouB substances, and after death to a
highly developed pathology, which has learned, by multiplied observa-
tions, all the normal and abnormal signs in tissues and organs; and,
finally, to an ever-advancing chemiatryj which is able in many instances
tiD separate and detect the hurtful and noxious thing, althougli hid for
Uionths deep in the ground.
'Growtb and Development of the Modern Methods of
Chemically Detecting Poisons.
§ 8. The history of the detection of poisons has gone through several
phases. The first phase has already been incidentally touched upon —
{.«,, detection by antecedent and ?nrruunding ci re tmi stances, aided some-
times by experiments on animals. If the death was sudden, if the post-
mortem decomposition was rapid^ poison was indicated : sometimes a
portion of the food last eaten, or the suspected things would be given
to an animal ; if the animal also died, such accumulation of proof won Id
render the matter beyond doubt. The modern toxicologists are more
sceptical, for even the last test is not of itself satisfactory. It is now
• Ftoude's Sistirrji qf England, vol. iii. p. 202-
14 POISONS : THKIR EFFECTS AND DETECTION. [§ 9.
known that meat may become filled with bacilli and produce rapid death,
and yet no poison, as such, has been added.
In the next phase, the doctors were permitted to dissect, and to
familiarise themselves with pathological appearances. This was a great
step gained : the apoplexies, heart diseases, perforations of the stomach,
and fatal internal haemorrhages could no longer be ascribed to poison.
If popular clamour made a false accusation, there was more chance of
a correct judgment. It was not until the end of the eighteenth and
the beginning of the last century, however, that chemistry was far
enough advanced to test for the more common mineral poisons ; the
modern phase was then entered on, and toxicology took a new departure.
§ 9. From the treatise of Barth^l^my d' Anglais * in the thirteenth
century (in which he noticed the poisonous properties of quicksilver
vapour), up to the end of the fifteenth century, there are numerous
treatises upon poison, most of which are mere learned compilations, and
scarcely repay perusal. In the sixteenth century, there area few works,
such, for example, as Porta, which partook of the general advancement of
science, and left behind the stereotyped doctrine of the old classical
schools.!
In the seventeenth century the Honourable Robert Boyle made some
shrewd observations, bearing on toxicology, in his work on Tlie Useful-
ness of Natural Philosophy ^ etc. : Oxford, 1654. Nicolas L'Emery also
wrote a Cours de Chimie — quite an epitome of the chemical science of
the time. I
In the eighteenth century still further advances were made. Richard
Mead published his ingenious Mechanical Theory of Poisons, Great
chemists arose — Stahl, Marggraf, Brandt, Bergmann, Scheele, Berthollet,
Priestley, and lastly, Lavoisier — and chemistry, as a science, was bom.
Of the chemists quoted, Scheele, in relation to toxicology, stands chief.
It was Scheele who discovered prussic acid,§ without, however, noting
its poisonous properties ; the same chemist separated oxalic acid from
sorrel, 1 1 and made the important discovery that arsenic united with
hydrogen, forming a foetid gas, and, moreover, that this gas could be
• De Berum Proprietaribus.
t In the sixteenth century it was not considered proper to write upon poisons.
Jerome Cardan declared a poisoner worse than a brigand, " and that is why I have
refused not only to teach or experiment on such things, but even to know them." —
/. Garden : De Subtilitate, Basel, 1558.
X Co^irs de Chimie^ contenant la manicre de faire le$ op^aiions qui sont en usage
dans la M^icine, Paris, 1675.
§ OpusctUa Chemica, vol. ii. pp. 148-174.
II De Terra Bhuharhi et Acido Acetosellm, Nova Acta Acad. Veg, Sued. Anni,
1784. Opuscula Chemica^ vol. ii. pp. 187-195.
Bergmann first described oxalic acid as obtained by the oxidation of saccharine
bodies ; but Scheele recognised its identity with the acid contained in sorrel.
I lO, II.] MODEBN METHODS OF CHEMICALLY DETECTING POISONS. 1$
decomposed by lieat.* From this obeervatiou, a delicate t^t for arsenic
was afterwards elaborated, which for the first time rendered the most
tasteless and easily administered poison in the whole world at once the
easiest of detection. The further history of what is now called ** Marsh's
Test 'Ms aii follows : —
jj 10* Proust t observed that a very foetid hydrogen gas was disengaged
when arsenical tin wm dissolved in hydrochloric acid» and that arsenic
was deposited from the inflamed gas on cold surfaces which the flame
touched, TroramsdorflT next announced, in 1803, that when ai^enical
ino was io trod need into an ordinary flask with water and sulphunc
dd, an arsenical hydrogen was disengaged ; and if the tube was
sufficiently long, arsenic was deposited on its walls.J Stromeyer, Gay-
Lussac, Thenardj Gehlen, and Davy later studied this gas, and Serullas
in 1821 proposed this reaction as a toxicological test^ Lastly, in 1636,
Marsh published his Mmmr.^ He conatrncted a special apparatus
of great simplicity^ developed hydrogen by means of zinc and sulphuric
acid, inflamed the issuing gas, and obtained any arsenic present as a
metal, which could be afterwards converted into at^senious acid^ etc.
This brief history of the so-called ** Marsh's Test " amply shows
that Marsh wa^ not the discoverer of the test Like many other useful
processes, it seems to have been evolved by a combiuRtiou of many
minds. It may, however, be truly said that Marsh was the first who
perfected the test and brought it prominently forward.
§ IL Matthien Joseph Bonaventura Orfila must be considered the
father of modem toiicology, His great work, Traite tie Toxif^logie,
was first published in 1814, and went through many editions. Orflla's
chief merit was the discovery that poisons were absorbed and accumu*
lated in certain tissues — a discovery wliich bore immediate fruit, and
greatly eiteuded the means of seeking poisons* Before the time of
Orfila, a chemist not finding anything in the stomach would not have
troubled to eJiamine the liver, the kidney, the brain, or the blood. The
immense number of experiments which Orfila undertook is simply
marvellous. Some are of little value, and teach nothing accurately
as to the action of poisons— as, for example, many of those in which he
tied the gullet in order to prevent vomiting, for such are experiments
under entirely unnatural conditions ; but there are still a large number
which form the very basis of our pathological knowledge.
Orfila's method of experimeTit was usually to take weighed or
• Mim(4re$ de Schfdf^, L I, 1775.
t Proust, Annates dt Ohimkf t, utviii., 1798*
+ Mkfutl^n*i Journal^ vol. vL
I "Deecriptioii of & N^fw Process of Sepamting Small Qii»jititie8 of Artieiiic rrom
Subtttanoes with whicli it is mlxud" £d, N«w. PkU. Jtmmal, 18S6.
l6 POISONS: THEIR EFFECTS AND DETECTION. [§ 12, 1 3.
measured quantities of poison, to administer them to animals, and then
after death — first carefully noting the changes in the tissues and organs
— to attempt to recover by chemical means the poison administered.
In this way he detected and recovered nearly all the organic and
inorganic poisons then known ; and most of his processes are, with
modifications and improvements, in use at the present time.'^
§ 12. The discovery of the alkaloids at the commencement of the
nineteenth century certainly gave the poisoner new weapons ; yet the
same processes (slightly modified) which separated the alkaloids from
plants also served to separate them from the human body. In 1803
Derosne discovered narcotine and morphine, but he neither recognised
the difference between these two substances, nor their basic properties.
SertUmer from 1805 devoted himself to the study of opium, and made
a series of discoveries. Robiquet, in 1807, recognised the basic characters
of narcotine. In 1818 Pelletier and Caventou separated strychnine;
in 1819, brucine; and in the same year delphinine was discovered
simultaneously by Brande, Lassaigne, and Feneuille. Coniine was
recognised by Giesecke in 1827, and in the following year, 1828,
nicotine was separated by Keiraann and Posselt. In 1832 Robiquet
discovered codeine ; and in 1833 atropine, aconitine, and hyoscyamine
were distinguished by Geiger and Hesse. Since then, every year has
been marked by the separation of some new alkaloid, from either
animal or vegetable substances. So many workers in different coimtries
now began to study and improve toxicology, that it would exceed the
limits and be foreign to the scope of this treatise to give even a brief
rSsume of their labours. It may, notwithstanding, be useful to append
a short bibliography of the chief works on toxicology of the last
century.
§ 13.— BIBLIOGRAPHY OF THE CHIEF WORKS ON TOXICOLOGY
(NINETEENTH CENTURY).
Anolada, Jos. — * * Traits de Toxicologic G^n^rale, ** etc. Montpellier et Paris, 1 835.
Atttenrieth. — *' Kurze AnleituDg zur AuflBndung der Gifte." Freiburg, 1892.
Bandlin, 0. — " Die Gifte." Basel, 1869-1873
Baumert, G. — **Lehrbuch dergerichtl. Chemie." Braunschweig, 1889-92.
Bayard, Henri.—** Manuel Pratique de M^ecine L%ale." Paris, 1843.
• Orfila^s chief works are as follows : —
TraiUdes Poisons, 2 vols., 8vo. Paris, 1814.
Lemons de ChimUf appliqv^es d la Mid. Pratique, 16mo. Brussels, 1836.
M&moire sur la Nicotine et la Conieine, Paris, 1851.
Lemons de lu Mid, lAgale, 8vo. Paris, 1821.
TraiU des Eichumations Juridiques^ et Considiraiio7is sur les ChangemerUs
Physiques que les Cadavres eprouvent en se pourrissant, 2 torn. Paris, 1831.
§13-]
BIBLIOGRAPHY.
I?
BblwKi, BANiKRL"'*Mftiiuel de Toadcologifl/' Pisa, 1878.
BiftLiN, Ni J. — * ' Najchriclit J die gBwohnliehBn Gifte chejmBob zu entdecken/^
Stockholm, 1846.
BfiftKABP, C. — ** Le^^na sur lee ERets dea Subaiatices Taziquea et Medicajnenteu^^"
Paris, 18&7*
BRETitAKD, C. A. K. A. — *' Manuel Medico* L^le dca Poisous mtrtiduita dans
TEatomaCj et lea Moyens Tli^ra|>eutiquefl qui leur convienneiit : mivi d*un
Plan d'Organisfttion M/'dico-Judicmrai ©t d*nT> Tableati de la Claasifi cation
G^iif^i'ale dea Empoison DemenH/^ Paris, 181S,
BiNK, C,^ — 'Mntoxicatioaetj" in Cerlmrdt*!* *' H4ndbuch der Kinderkmnklieiten/'
iii. HefL Tubingen, 1878,
BLTTag A. Wtntke.— *' A iiamml oj' Practical Chemistry; The Analjaia or Foods
and the Detection 4>fPtnsonj*.^* London^ 1679»
Bo€EKK» FRiKT>Ea. WiLHELBi,— '* Die Yergiftiingen hi fomuaisoher u. kliniscber
BeJiiehting/' Iserlohn^ 1867.
B5liM| E>, Najjnyk^ B., and iroN Boecjk, H. — " Haudbucb dei* Intoxicaticjnen/-
(Bd. 15 of tha German edition of 2iemflsen*s Cyelop^dia.)
Bbani>t, pHrtBDSj and Ratzeburo, — "* Deutachlanda Giftg^wiichBe." Berlin,
183i-3S (2 Tok.p with 50 coloiir«d platea),
BfttAND, J., fttid Chaudk, Erit. — " Matiuel Complet dc MMecine L^galis," (The
Utett edition, 1679.) Thf] chomi<iaI portion U by J. Bonis.
BtTOHJTEB, E. — "Lehrbuch der geriobtlichen Medicin fiir Acrzte u, Jnriateii." 3fd
ed* Miincben, 1872.
OAfiPKR, J. L.— '* Haiidbuch der gerichtlioh^n Medicin**' 7tb ed. Berlin, 1881.
Cbb? ALLiEKt A, — "Traits de Toxicologie et de Cbbiie JndiciairBw^' Pms, 1868*
GbujK| Step. — "Eutihiridis di TossiooIogiA teorico-pnitica." 3rd ed. N*i)oli,
1868.
CHEiaTiaONj ]RoBEttT.— '* A Treatiae on Poisona." Edinburgh, 1830, (A thii-d
edition appeared in 1SS@.)
CofiMETiK, C— ** Dea Plantes V^nt^neuse/' Paris, 1887p
DktkroIX, Alfhoi^be, — "MMecine legale ^ Th^riqne^ et Pratique*'* 3rd ed.
Park, 18i^2.
Dbaiiijjborff, Jean Qiob«i8. — **Dio gedobllich-cbemiacho Ermittolung rou
Giften In Nahrungamittelu, Luftgemiachen, Speiseratsten, Kotpertbeikn/*
eU5, St Peteraburg, 1868. 3rd ed. Cnjttingeti, 1888.
— - — ** UnterauchuBgen aus dem Pharmaceutiscben Iniititute in Dorf^at Btiitriige
zur gerichtlicbeu Chfimie einaeloer orgitiiaober Gifte.'* Erstes Hefl. 3L
Petflrabargi 1871.
— • — ** .Tahreabericht iiber die Fortachrittu der Pharmacognooie, Fhanoactei und
Toiicologie." Hamnsgegeben von Dr. Dfagendorlt 1870*
DuFLoa, A. — *' Handbuch der angewandlou gericbtlich-chemischen ADaty&e der
chemischen Qifte, ihre Erkenuung la reluem Zustande u, in Gemengen
lietrelTi^nd,'* Bretdau u. Leipzig, 1873,
EutENUKRtfj, Dr* HiRHAWW.-^** Handbtiob der Gewerbe-Hygieiie." Berlin, 1876.
FalcK| C, Ph, — **Die KlinUcbwiohtigeu Intoiicationen.'* (Handbuch der apeo.
Pathologie u, Therapie red, ron R. VirchoWj Bd. 2.) Erlangen^ 1854*
fAlJCKt Febb. Aug. — ** Lebrbuch dor praktiachen Todcologie* *' Stuttgart, 1880*
FtAKDiw, C. — ^^ Traits des Poiaona, ou Toiicologie appliqnee h la Miklecine I/^le,
k U Pbysiologiej et a la Tbtrapeutique.** Paiia, 1847, 1853,
FidHNSR, Euo.— " Lehrbuch der Toadcologie Air Thienirzte." Stuttgart, 1890.
GAtnim, C. P. — ^'TraibS de Toiieologie Medico* li'gale et de la Falsification des
A}unoiita/' etc Paris, 1815.
** Traits de Toadoologio M4diD*le, Chiimque efc lig^te/' ete. Paria, 1855. A
later edition of the same work.
Z
1 8 POISONS : THEIR KFPECTS AND DETECTION. [§ 1 3.
Gbeenb, Will. H.— ''A Practical Handbook of Medical Chemistry, applied to
Clinical Research and the Detection of Poiaons." Philadelphia, 1880.
GuEBiN, G. — ** Traits Pratique d' Analyse Ohimique et de Recherches Toxicologiques.'
Paris, 1893.
Guy, W. a., and Ferrisb, David. — "Principles of Forensic Medicine." London,
1874.
Harnaok, Ebioh. — '' Lehrbuch der Arzneimittellehre," etc. Hamburg, 1883.
Hasselt, yak, a. W. M. — ''Handbuch der Gifdehre fiir Chemiker, Aerzte,
Apotheker, n. Richtspersonen." (A German translation of the original
Dutch edition, edited by J. B. Henkel. Braunschweig, 1862. Supplemental
vol. by N. Husemann, Berlin, 1867.)
HsLWio, A. — **Das Mikroskop in der Toxicologic." 64 photographs, roy. 8vo.
Mainz, 1865.
Hemming, W. D. — ** Aids to Forensic Medicine and Toxicology." Loudon, 1877.
Hermann, L. — "Lehrbuch der experimentellen Toxicologic." 8vo. Berlin,
1874.
Hoffmann, K R.— "Lehrbuch der gerichtlichen Medicin." 5th ed. Wien,
1890-91.
Husemann and A. Hiloer. — "Die Pflanzeustoffe in chemischer, pharmakolog-
ischer, u. toxicologischer Hinsicht" 2nd ed. Berlin, 1882.
Husemann, Th., and Husemann, A. — "Handbuch der Toxicologic." Berlin,
1862. (Suppl. Berlin, 1867.)
Robert, Rud.— " Lehrbuch der Intoxicationeu." Stuttgart, 1893.
EoEHLER, R. — "Handbuch der speciellen Therapie, einschliesslich der Behandlung
der Vergiftungen." Srd ed. 2 vols., roy. 8vo. Tubingen, 1869.
Lesser, Adolf.— " Atlas der gerichtlichen Medicin." Berlin, 1883.
LoEW, Oscar. — " Ein natiirliches System der Giftwirkungen." Miinchen, 1893.
LuDWio, £. — " Medioinische Chemie in Anwendung auf gerichtliche Untersuch-
ungen."
Mahon, a.— " M^ecine L^le et Police M^dicale." Paris, 1807.
Marx, K. F. H.—" Die Lehre von den Giften." Gottingen, 1827-29.
Maschka, J.—" Handbuch der gerichtlichen Medicin." Tubingen, 1881-82. This
work is under the editorship of Dr. Maschka, and contains separate articles
on medico-legal and toxicological questions by various eminent toxicologists,
somewhat after the manner of Ziemssen*s Clyclop»dia.
Mende, Lud. Jul. Casp.— "Ausfuhrliches Handbuch der gerichtlichen Medicin."
1819-32.
MoHR, Fried. — * * Chemische Toxicologic. " Braunschweig, 1874.
MoNTOARNY, H. DE. — " Essai de Toxicologic, et specialement avec la Jurisprudence
M^icale.»' Paris, 1878.
MoNTMAHON, E. S. DE.— " Mauucl M^dico- Legale des Poisons," etc. Paris, 1824.
MuTEL, D. Ph. — " Des Poisons, consider^ sous le rapport de la M^ecine Pratique,"
etc. Montpellier et Paris, 1835.
Nacquet, a. — " Legal Chemistry : A Guide to the detection of Poisons, Examina-
tion of Stains, etc., as applied to Chemical Jurisprudence." New York,
1876.
A translation from the French.
NicoLAi, JoH. Ant. Heinr.— " Handbuch der gerichtlichen Medicin." Berlin, 1841.
The chemical portion is by F. R. Simon.
OosTON, F.— " Lectures on Medical Jurisprudence." London, 1878.
Orfila, Matthieu Jos. Bon a ventura.— "Traits des Poisons, ou Toxicologic
Gen^rale." Paris, Ist. ed., 1814 ; 5th ed., 1862.
Orfila et Lesueur.— " Traits de M^ecine Legale." Paris, 1821 ; 4th ed., Paris,
48.
§ 13.] BIBLIOGRAPHY. IQ
Otto, F. G.--**Anleituiig znr Ausmittelung der Gifte." Braunschweig, 1856 ; 5th
ed., 1875. 6th ed. by Robert Otto, Braunschweig, 1884.
Pbaao, van, Lbokidbs, and Opwybda, R. J. — ** Leerboek voor practische giftleer."
In Zwee Theilen. Utrecht, 1871.
Rabutbau, a. — "^^mens de Toxicologic et de M^ecine L^le, appliqu^es k
rEmpoisonnement" Paris, 1873. 2nd ed. by Ed. Bourgoing. Paris, 1888.
Reess, John J. — " Manual of Toxicology, including tiie Consideration of the Nature,
Properties, Effects, and Means of Detection of Poisons, more especially in
their Medico-legal relations." Philadelphia, 1874.
Rkmeb, W. H. G.— ''Lehrbuch der polizeilich-gerichtlichen Chemie." Bd. 1 u. 2.
8. Auflage, Helmstadt, 1824.
ScHNEiDKB, F. C. — "Die gerichtliche Chemie filr Gerichtsarzte u. Juristen."
Wien, 1852.
ScHNSiDKE, P. J.—'' Ueber die Gifte in medicinisch-gerichtlicher u. gerichtlich-
polizeilicher Riicksicht/' 2nd ed., 1821.
Selmi, F.— *' Studi di Tossicologio Chimica." Bologna, 1871.
SoBBBNHBiM, Jos. Fr., and Simon, J. F.— " Handbuch der praktischen Toxicologic,"
etc. Berlin, 1838.
SoNNBNSOHEiN, L. — '' Handbuch der gerichtlichen Medicin." Berlin, 1860. A
new edition by Dr. A. Classen. Berlin, 1881.
Tardieu, a. — ** ^tude M^dico-L^gale et Cliuique sur I'Empoisonnemont, avec la
Collaboration de M. T. Roussin pour la partie de ^expertise relative k la
Recherche Chimique des Potsons." Paris, 1867.
Tatlob, Alfred Swain e. — " On Poisons in relation to Medical Jurisprudence and
Medicine.'* 3rd ed. 1875. Manual, 1879.
"Principles and Practice of Medical Jurisprudence." 3 vols. London,
1873.
ViBBRT, Ch.— " Pr^is de Toxicologic." Paris, 1900.
Webber, Ant. — ** Lehrbuch der praktischen Toxicologie." Erlangen, 1869.
Wood, Horatio C— "Therapeutics, Materia Medica, and Toxicology." Phila-
delphia, 1874.
WooDMANN, W. Bathdrst, and Tidy, Ch.— *' A Handy-Book of Forensic Medicine
and Toxicology." London, 1877.
WoRMLBY, Theodore G.— "Micro-Chemistry of Poisons, including their Physio-
logical, Pathological, and Legal Relations." New York, 1857.
Wurtz, a. — "Traits El^mentaire de Chimie M^dicale, comprcnant quolques notiouH
de Toxicologic," etc. 2nd ed. Paris, 1875.
PART 11.
L— Definition of Poison.
§ 14. The term ^* Poieon" may be considered first in its legal, as
distinct from its scientific, aspect.
The legal definition of " poison " is to be gathered from the various
statute-books of civilised nations.
The English law enacts that : " Whoever shall administer, or cause to
be administered to, or taken by any person, any poison or other destruc-
tive thing, with intent to commit murder, shall be guilty of felony."
Further, by the Criminal Consolidation Act, 1861: ** Whosoever
shall^ by any other means other than those specified in any of the
preceding sections of this Act^ attempt to commit murder, shall be
guilty of felony."
It is therefore evident that, by implication, the English law defines
a poison to be a destructive thing administered to, or taken by, a person,
and it must necessarily include, not only poisons which act on account
of their inherent chemical and other properties after absorption into the
blood, but mechanical irritants, and also specifically-tainted fluids.
Should, for example, a person give to another milk, or other fluid,
knowing, at the same time, that such fluid is contaminated by the
specific poison of scarlet fever, typhoid, or any serious malady capable
of being thus conveyed, we believe that such an offence could be brought
under the first of the sections quoted. In fine, the words " dedructive
thing " are widely applicable, and may be extended to any substance,
gaseous, liquid, or solid, living or dead, which, if capable at all of being
taken within the body, may injure or destroy life. According to this
view, the legal idea of " poison " would include such matters as boiling
water, molten lead, specifically-infected fluids, the flesh of animals dying
of diseases which may be communicable to man, powdered glass, diamond
dust, etc. Evidence must, however, be given of guilty intent.
The words, "administered to or taken by," imply obviously that the
framers of the older statute considered the mouth as the only portal of
entrance for criminal poisoning, but the present law effectually guards
§ 'SO
DSFINITIDN OF POISON.
21
agnhist &aj ttttempt to commit murder, no matter by what means.
There is thus :impk provision for all Ihe strange ways by which poieou
has beeu introduced into tba system, whether it be by the ear, nos6»
brain, rectum, vagina, or any other coiiceivable way, so that, to borrow
the words of Mr, Graves (Notes mi Vrimifml Law CofisolviaHmt), "the
uialicious may rest satiafied that every attempt to murder which their
pei*verted ingenuity may devise, or their fiendish malignity suggest,
will fall within gome clause of this Act, and may be visited with peual
servitude for life/'
Since poison i^ often ejthibited, not for the purpose of taking life,
but from various motives, and to accomplish various ends — as, for
eiample, to narcotise the robber's victim (this especially in the East),
to quiet children, to create love in the opposite sex (love philters), to
detect the secret sipper by sititably preparing the wine, to expel the
inconvenient fruit of illicit affection, to cure inebriety by polluting the
drunkard's drink with antimony, and, finally, to satissfy an aimless spirit
of mere wantonness and wickednesSj the English law enacts " that whom-
ever shall unlawfully or maliciously administer to, or cause to be taken
by, any other person, any poison or other destructive or noxious thing, so
as thereby to endanger the life of such person, or so as thereby to inflict
upon such person any |^ievo\is bodily harm, shall be guilty of felony,"
There is also a special provision, framed, evidently, with reference to
volatile and stupefying poisons, such as chloroform, tetrachloride of
carbon, etc. : —
" Whoever sliall utUaw fully apply, or administer to, or cause to be
taken by any person, any chloroform, laudanum, or other stupefying or
overpowering drug, matter, or thing, with intent, in any such case,
thereby to enable himself or any other person to commit, or with intent,
eto., to assist any other person in committing, any indictable of!ence,
shall be guilty of felony."
j^ 15. The Oemmn statute, as with successive amendments it now
stands, enaeta as follows : * —
" Whoever wilfully administers (Imbrtwjt) to a person, for the
* • * Wt?r vomitzlich etnem Audenij cm doaaen Gesutidheit zn be««haedigien, Gift
odiranderw Stollu beibringt, welch© die Gestmdheit eu zerstureu geeigii^^t ttind, wird
mit Zuclithans von zwei Ma ku zelui Jaliron bestraft.
**lHtdmt!h die Handluiig eim schwerc Koi-j>BrverletKung venirsacht wortleO| w
ist auf Zuchthaus nioht unter fiinf JAhren, uud wenii dun^h dm Hiitjdiuug der Tod
verursKcht worden, Auf Zuchtbaus niclit ixtit&T zehn Jalirisik oder atif lebenftldngUch^s
Znchthaus zu erkenuen.
" Iflt die voraatzliolie reelit^widrige Haudlung dm Gift — etc.,— Beibringfns aur
das ' Tc>dt^« * gerichtet, soil alao dupcli dies«lbe gewollter Weiso derTod exam Atidevtu
herlwigefidirt werden, so kommt in bettmcht : WeT vomitzlich eiBen Mt^uschen todtst,
wird, WGUTi er die Tddtmig tnit Ueberlegung ausgefuhrt hmt, wegeii Mordes mit deiu
Tade buatralL"
22 POISONS : THEIR EFFECTS AND DETECTION. [§ 1 6.
purpose of injuring health, poison, or any other substance having the
property of injuring health, will be punished by from two to ten years'
imprisonment.
" If by such act a serious bodily injury is caused, the imprisonment
is not to be less than five years ; if death is the result, the imprisonment
is to be not under ten years or for life.
"If the death is wilfully caused by poison, it comes under the
general law : ' Whoever wilfully kills a man, and if the killing is pre-
meditated, is on account of murder punishable with death.' "
The French law runs thus (Art. 301, Penal Code) : — " Every attempt
on the life of a person, by the effect of substances which may cause
death, more or less suddenly, in whatever manner these substances may
have been employed or administered, and whatever may have been the
results, is called poisoning. " *
There is also a penalty provided against any one who " shall have
occasioned the illness or incapacity for personal work of another, by the
voluntary administration, in any manner whatever, of substances which,
without being of a nature to cause death, are injurious to health." t
§16. Scientific Befinition of a Poison. — A true scientific definition
of a poison must exclude all those substances which act mechanically
— the physical influences of heat, light, and electricity ; and parasitic
diseases, whether caused by the growth of fungus, or the invasion of an
organism by animal parasites, as, for example, " trichinosis," which are
not, so far as we know, associated with any poisonous product excreted
by the parasite; — on the other hand, it is now recognised that
pathogenic micro-organisms develop poisons, and the symptoms of all
true infections are but the effects of "toxines." The definition of
poison, in a scientific sense, should be broad enough to comprehend not
only the human race, but the dual world of life, both animal and
vegetable.
Husemann and Robert are almost the only writers on poisons who
have attempted, with more or less success, to define poison by a
generalisation^ keeping in view the exclusion of the matters enumerated.
Husemann says: — "We define poisons as such inorganic, or organic
substances as are in part capable of artificial preparation, in part existing,
ready-formed, in the animal or vegetable kingdom, which, without being
• ** Est qualify empoisonnenunit — tout attentat k lavied'une personne par Teffet
de substances qui peuvent douner la mort plus on moins promptement, de quelque
mani6re que ces substances aient ^t^ employees ou administr^es, et quelles qu'en
aient ^U les suites."— Art. 301, PencU Code,
t "Celui qui aura occasionne k autrui une maladie ou incapacity de travail
personnel en lui administrant volontairement, de quelque mani^re que ce soit, des
substances qui, sans etrc de nature k donner la mort, sont nuisibles h, la sant^.*' —
Art 317, Penal Code,
§'7-1
CLASSIFICATION 07 POISONS,
23
able to reproduce themselves^ through the chemical nature of their
mo] ecu 1 OB uiulcr certaio couditioti^ change in the healthy organism the
form and general relationship of the organic parts, and, through amii-
hilation of organs, or destruction of their functions, injure health, or,
under certain oonditions, destroy life." Kohert says : — " Poisons are
organic or inorganic utiorgani^ed snbBtauces orlgiuating in the organism
itself, or introduced into the organism, either artificially prepared, or
ready formed in nature, which through their chemical properties,
under certain conditions, so influence the organs of living beings,
that the health of these beings is seriously influenced ten>porarily or
peramueotly,"
In the first edition of this work an attempt was made to define a
poison : the delinition slightly abbreviated is thus : — A mibdance may
h& miled a ptmon if U u capable of hmng tak^i into any Imng
organism f and causeft^ '^'/ its mm inhere/it chemical nature ^ impairment or
d^iruciiofi of f unction. We prefer this delinition to Robert's, and
believe that it fairly agrees with what we know of poiBonfi,
IL— Claasifieation of Poisons.
§17, At some future time, with a more intimate knowledge of the
way in which each poison actti upon the various forms of animal and
vegetable life, it may be possiblu to give a truly scientific and philoso-
phimd classification of poisons— one based neither upon wymptomsj upon
local effects, nor upon chemical structure, but upon a collation and com-
parisoa of all the properties of a poison, whether chemical, physical, or
physiological No perfect systematic arrangement U at present attain*
able : we are either compelled to omit M classification, or else to arrange
poisons with a view to practical utility merely.
From the latter point of view, an arrangement simply aocording to
the most prominent symptoms is a good one, and, without doubt, an
aaaistance to the medical man summoned in haste to a case of real or
suspected poisoning. Indeed, under such circumstances^ a scheme some-
what similar to the following probably occurs to every one versed in
toxicology :^
A. Poisons caubimo Death imiibdiately, or ik a fsw minutes.
There are but few poisons which destroy life in a few miuutefi.
Omitting the strong mineral acids, carbon monoxide, carbon dioiide,
with the irreapirabie gases— iVtt^r add^ the cijanideif^ oxalk acid, and
ooeaaionally drythnimy are the chief poisons ooming under this bead.
24 POISONS: THEIR EFFECTS AND DETECTION. [§ 1 8.
B. Irritant Poisons (symptoms mainly pain, vomiting, and purging).
Arsenic, antimony^ phosphoruSy cantharides, savin, ergot, digitalis^
colchicum, zinc, mercury, lead, copper, silver, iron, baryta, chrome, yew,
laburnum, and putrid animal substances,
C. Irritant and Narcotic Poisons (symptoms those of an irritant
nature, with the addition of more or less pronounced cerebral
indications).
To this class more especially belong oxalic acid and ths oxalates,
with several poisons belonging to the purely narcotic class, but which
produce occasionally irritant effects.
D. Poisons morb especially affecting the Nervous System.
1. Narcotics (chief symptom insensibility, which may be preceded
by more or less cerebral excitement) : Opium, Ghloraly Chloroform,
2. Dbliriants (delirium for the most part a prominent symptom) :
Belladonna, hyoscyamus, stramonium, with others of the Solanacece,
to which may be added — poisonous fungi, Indian hemp, Lolium temulen-
turn, CEnanthe crocata, and camphor,
3. CoNVULSiVES. — Almost every poison has been known to produce
convulsive effects, but the only true convulsive poisons are the alkaloids
of the strycJinos class,
4. Complex Nervous Phenomena: Aconite, digitalis, liernlock,
calabar bean, tobacco. Lobelia injlata, and curara,
§ 18. Kobbrt's Classification. — Robert has classified poisons
according to the following scheme : —
I. POISONS WHICH CAUSE COARSE ANATOMICAL CHANGES OF THE
ORGANS.
A. Those which specially irritate the part to which they are applied.
1. Aeids,
2. Caustic alkalies.
3. Caustic sails, especially those of the heavy metals.
4. Locally irritating organic substances which neither can be classified as
corrosive acids nor alkalies, nor as corrosive salts ; such are i—eanlhari-
dine, phrynine, and others in the animal kingdom, croton oil and savin
in the vegetable kingdom. Locally irritating colours, such as the aniline
dyes,
5. Gases and vapours which cause local irritation when breathed, such as
ammonia, chlorine, iodine, bromine, and sulphur dioxide,
B. Those which have but little effect locally, but change anatomically other
])art8 of the body ; such as lead, phosphorus, and others.
S ■9.)
CLA8SIPICATI0N OF POISOMS.
2S
IL BLOOD PoiaoNa
1. Blood poisotu inlerfaiing with the eircuUtioti in & piiroly [ibysicil mmnet^
sticli A&pero^iU q/ hydrogen^ rietne^ a^riju,
2. Fomoua which have the piniperty of diasolving tho wd blood coi'pusali^
iUch as the safMnin^.
3. Poisons which, with or without primufy soltttion of Ihc; rod blood oor-
jmat^lbs, produc« In the bloud m^thtemoglobin ; snch urn peiam^ MmaUf
i. Poutoiis having a. p>oouliftr action ojj th« colounng matter of the blowi, or on
its deGomp(;«]tion prciducts, ffuch iis hydric sulphide, hydric c^fanide, and
ths ci/(tnidi:M and tftrbon wtono.cid4^
IIL POISONS WHICH KILL WITHOUT THE PRODUCTION OF COAESE
ANATOMICAL CHANOE.
1, Poisons a^ectitig the oercbro- spinal aystem ; sjuch aa ehlor&fgrtn,, dhctj
niirous oxMc, ale&fwi, thhtrfif^ coeainCj tMtropiji^, morphittSt nieeiinSf
eimiintf f^Qnitin^^ strychnine, curmrinef and others*
2, Heart Poisona ; euch asj digikxlU^ kelle^rm, ftiUiearintM
IV, POISONOUS PRODUCTS OF TISSUE CHANGE.
L Pgisonqua album ill.
2. Poisons develofted in food.
3. Auta-jniaomng, <\g., urmim&t glyoosuria, oxahirii,
4. Tht more imjKtrtant (iroduiita of tissue change ; auoh m, faU^ aeidSf o^-
aeids, amido-faUij aeidat avtines^ diamhiest and tttonminAi,
S 19, 111 this work the armngemeiit is one which, as far aa
poBsiblSj follows the order in which a cheaiical expert would search for
an unki^own poi&on — hence an arniug:ement partly cbemical and partly
Bymptomatic. First the chief gases which figvjre in the mortalitj
fitatistics are treated, and then follow in order other poisons.
A chemistf giren a liquid to exaniinef would naturally t^st first its
reaction, and, if strongly alkaline or strongly acid, would at once direct
his attention to the mine nil acidB or to the alkalies, In other cases^ he
would proceed to separate yolatile matters from those that were fixed,
leet substances such as prussic auid^ chloroform, alcohol, and phosphorus
be dissipated or destroyed by his subsequent operations.
Distillation over, the alkaloids, glueosides» and their allies would
next be naturally sought, since they can be extracted by alcoholic and
utUereal solvents in such a manner as in no way to interfere with au
ei^ffiT^earch for metals.
The metals are last in the list, because by suitable treatment, after
a!l organic substances are destroyed, ei titer by actual lire or powerful
chemical agencies, even the volatile metals may be recovered. The
metals are arranged very nearly in the same order as that in which they
would be separated from a solution — viz», according to their behaviour
to hydric and ammonium sulphides.
26 POISONS: THKIR EFFECTS AND DETECTION. [§ 1 9.
There are a few poisons, of course, such as the oxalates of the
alkalies, which might be overlooked, unless sought for specially ; but it
is hoped that this is no valid objection to the arrangement suggested,
which, in greater detail, is as follows : —
A.— POISONOUS GASES.
Carbon monoxide.
Chlorine.
Hydric sulphide.
B.-ACIDS AND ALKALIES.
1. Sulphuric acid.
2. Hydrochloric acid.
3. Nitric acid.
4. Potash.
5. Soda.
6. Ammonia.
7. Neutral sodium, potassium, and ammonium salts.
In nearly all cases of death from any of the above, the analyst, from
the symptoms observed during life, from the surrounding circumstances,
and from the pathological appearances and evident chemical reactions
of the fluids submitted, is put at once on the right track, and has no
difficulty in obtaining decided results.
C— POISONOUS SUBSTANCES CAPABLE OF BEING SEPAR-
ATED BY DISTILLATION FROM EITHER NEUTRAL OR
ACID LIQUIDS.
1. Hydrocarbons.
2. Camphor.
3. Alcohols.
4. Amyl-nitrite.
5. Chloroform and other anaesthetics.
6. Carbon disulphide.
7. Carbolic acid.
8. Nitro-benzene.
9. Prussic acid.
10. Phosphorus.
The volatile alkaloids, which may also be readily distilled by strongly
alkalising the fluid, because they admit of a rather diflerent mode of
treatment, are not included in this class.
§ ig.] CLASSIFICATION OF POISONS. 27
D.-ALKALOIDS AND POISONOUS VEGETABLE PRINCIPLES
SEPARATED FOR THE MOST PART BY ALCOHOLIC
SOLVENTS.
DIVISION I. — Vbgetablb Alkaloids.
1. Liquid volatile alkaloids, alkaloids of hemlock, nicotine,
piturie, sparteine, aniline.
2. The opium group of alkaloids.
3. The strychnine or tetanic group of alkaloids — strychnine,
brucine, igasurine.
4. The aconite group of alkaloids.
5. The mydriatic group of alkaloids — atropine, hyoscyamine,
solanin, cytisine.
6. The alkaloids of the veratrines.
7. Physostigmine.
8. Pilocarpine.
9. Taxine.
10. Curarine.
11. Colchicin.
12. Muscarine and the active principles of certain fungi.
There would, perhaps, have been an advantage in arranging several
of the individual members somewhat differently — e.^., a group might
be made of poisons which, like pilocarpine and muscarine, are antago-
nistic to atropine ; and another group suggests itself, the {)hysiological
action of which is the opposite of the strychnos class ; solanin (although
classed as a mydriatic, and put near to atropine) has much of the
nature of a glucoside, and the same may be said of colchicin ; so that,
if the classification were made solely on chemical grounds, solanin
would have followed colchicin, and thus have marked the transition
from the alkaloids to the glucosides.
DIVISION II.— Glucosides.
1. The digitalis group.
2. Other poisonous glucosides acting on the heart.
3. Saponin.
The glucosides, when fairly pure, are easily recognised; they are
destitute of nitrogen, neutral in reaction, and split up into sugar and
other compounds when submitted to the action of saponifying agents,
such as boiling with dilute mineral acids.
28 POISONS: THEIR EFFECTS AND DETECTION. [§ I9.
DIVISION III. — Various Vbgbtablk Poisonous Principles not
readily admitting of classification in the previous
Divisions.
1. Santonin. 2. Mezerein.
It is probable that this class will in a few years be extended, for
several other organic anitrogenous poisons exist, which, when better
known, will most likelj prove to be anhydrides.
Ergot, picrotoxin, Tutin, the poison of lUicium rdtgiosum^ picric acid,
cicutoxin, jEthtLsa cynapiuni^ (Enanthe crocata^ croton oil, savin oil, the
toxalbumins of castor oil and AhruSy Ictrogen, Lathyrus satictis, arum,
and others.
The above division groups together various miscellaneous toxic
principles, none of which can at present be satisfactorily classified.
E.-POISONS DERIVED FROM LIVING OR DEAD
ANIMAL SUBSTANCES.
DIVISION I. — Poisons Secreted by the Living.
1. Poisonous amphibia.
2. Poison of the scorpion.
3. Poisonous fish.
4. Poisonous insects — spiders, wasps, bees, beetles, etc.
5. Snake poison.
6. Mammalian poison. Epinephrin.
DIVISION II. — Poisons Formed in Dead Animal Matters.
1. Ptomaines.
2. Poisoning by putrid or changed foods — sausage poisoning.
F.-THE OXALIC ACID GROOP.
6.-IN0R6ANIC POISONS.
DIVISION I. — Precipitated from a Hydrochloric Acid Solution
BY Hydric Sulphide — Precipitate, Yellow or Orange.
Arsenic, antimony, cadmium.
DIVISION II. — Precipitated by Hydric Sulphide in Hydro-
chloric Acid Solution — Black.
Lead, copper, bismuth, silver, mercury.
§ 20, 21.]
STATISTICS.
29
DIVISION in> — pREGiPITATSn PROM A I^HUTRAL Soi^UTION UV
Hydrio Sulphidk.
Zinc, nickel, cobalt,
DIVISION IV.^Frecipitatbd by Ammonium Bulfhidsi
Iron, clironiiam^ thallium, alufniniuin.
DIVISION v.— Alkaj^ink Earths.
Barium.
Ill,— Statisties.
§ 20, The n amber of deaths from poison (whether accidetitat,
suicidal, or homicidal )j as compared with other forms of violentj as
well as natural deaths, poesesses no small interest; and this t^ more
especial 1 J tnie when the statistics are studied in a comparative manner,
and town m compared with town, country with count rj.
The greater the development of commercial industries (especially
thofi€ neeeflsi toting the use or manuractUFe of powerful chemical
agencies), the more likely are accidents from poisons to occur. It may
alao be stated, further, that the higher the mentnl development of a
nation, the more likely are its homicides to be caused by subtle potsoE
— its suicides by the euthanasia of chloral, morphine, or hemlock.
Other hifluences causing local diversity in the kind and frequency
of poisoning are those of race, of religion, of age and sei, and the
mental stress concomitant with sudden political and social changes.
I 21. During the ten years ending December 1903 there have died
from poisons and poisonous vapours 1 1,035 persona. The following list
deals only with those poisons which are definite and fairly common, and
accounts for 8544, or over 77 per cent, of the whole. The balance is
made up of deaths from the folio vving among others : coal gas, sul-
phuretted hydrogen, sewer gas, carbon dioxide, carbon monoiide>
arseniuretted hydrogen, varions so-called " fumes from kilns/^ ** from
coke," etc. ; there are also a few deaths recorded under each of the
following heads : tobacco, yew leaves or berries, poisonous berries,
ei^otj castor-oil seeda, oil of cloves, parsnip wine, eantharidea^ bryony^
opodeldoc, sheep dip, weed killer, fungus, water hemlock, coiclncmn
wine, quinine, Gregory ^s powder, antifebrin, buttercup, sulpholine, and
vague things such as overdose of medicine, liniment, ptomaines,
poisonous iish, and, generally, bad or changed food.
30
POISONS: THEIR EFFECTS AND DETECTION.
[§2I.
DEATHS FROM POISON IN ENGLAND AND WALES DURING THE TEN
YEARS ENDING DECEMBER 1903.
Aoddulor
8iildd«.
Muid«r,
T<rt»l,
Metal».
M.
F.
IL
F.
H.
F.
KL
F.
ArsMiio
Antimouj,
Sr*. : ; : : ;
Silver Nitrate, ....
Zinc CHoride or Sulphate, .
Mercuiy, Salt* of^ . . ,
Chromic Acid or Preparations qfl
Chromiuui, . * . /
Iron Pcrobloridc,
2
2
754
1
7
U
8
107
3
m
"2
17
e
!
3S
2
2
6
1
2
48
1
14
S
1
1
1
9
18
1
,..
1
t*4
90
4
4
760
2
9
62
9
121
6
1
186
I
11
35
7
1
Alkalikk Eaetsh.
Barium Chloride, ....
Linie,
1
i
...
...
.,.
**W
1
'1
Thk AtKAi^rss AKi> THBiR Sxim
(jftiifltic Potash, ....
Potasmum Ctilorat«|
», Nitrate,
Bromidis,
,, Bichromate,.
Ammonia,
1
"i
7
6
SO
4
"i
4
7
63
22
59
64
"i
...
ti
"2
20
6
100
4
7
117
AciDa.
(a) Mineral
Acidp Sulphuric
i. Nitric
,» Hydrochloric,
„ Hydrofluoric^
34
13
ei
1
9
8
33
30
46
204
22
23
165
2
...
ir*
66
69
205
1
31
81
198
(b) OnjraRfe
Acid, Carbolic
,, Acotic, ....
M O^lic
184
1
27
153
6
28
796
2
85
828
€
4»
2
2
3
982
3
94
982
n
77
EtieuiKTi.
Pho&phoruB,
Iodine
Carry forward ^
2d
2
38
21
1
60
1
1267
7
4
60
3
98
1310
665
1320
2637
1916
§21-]
STATISTICS.
31
DEATHS FROM POISON IN ENGLAND AND WALES DURING THE TEN
YEARS ENDING DECEMBER 190Z--€(mHnued.
Brought forward,
Vol ATI Li! LiQUirmp
Pamffio (Petmleum), .
BenxoHne, . , . ,
Nitrubtinz4>Ir
Ether, » * » . .
Clilopoform, . , * »
Chloroform add Etlmr, .
Alcohol J Chloroform, and Ether,
TarpeiitiEe, .
SwiMst Nitre,
Methyl Alcohol,
Nitrous Oxide,
Alcohol,
Fusel Oil, .
Spii'it of Oamphor,
Bmndy,
Paraldeivjde,
Coal Naphtha,
AntfiBthetic (kbd not stated).
OMATas OR Nabcotiob.
Opium, Lanclanum,
Morphine, ,
SooUxing Synip,
Ghlor^idyue, .
Chloral,
Sulphonyl, .
Cocaine,
„ and Ether,
,, Atropine,
Belladonna and Opium,
Belladonna, .
Atropine,
Hen bane.
Narcotic (kind not stated),
Ctanidib.
P rustic Acid and Oil of Almonds, .
PotAflaic Cyanide, . . . .
Ammommn Snlpho-Cjanide,
stk7chnine and bom% otuf^h
Organic Poisons.
Strychnine and Nux Yomiea,
Aeotiit«, , , , . .
Digitalia, . . , , .
Aceittgtit or
M.
1310
19
4
1
38
520
6
6
1
9
56
1
117
536
e
66
66
2
3
1
I
S3
16
SO
IT
Toul,
Total poisonous aubstancaa, includ-
ing glhs^ and Tarious other poidon^a.
^d3S
3880
F.
656
33
292
6
4
4
1
1
6
3
4
1
346
3
36
16
&
6
33
1
IS
24
M.
1320
Suicide.
F.
1257
432
36
12
12
"3
272
166
2
70
14
1686 2364
2078
2923
189
3
2
I
1
17
22
21
n
6
Mttrder.
M.
1634
2128
Total,
11
14
M.
2637
10
i
1
38
529
6
e
4
9
69
117
063
6
102
73
2
6
3
1
1
45
19
302
138
2
126
36
3
1016
4
1
33
301
6
4
5
1
1
6
28
1
"3
4
2
69
537
3
39
13
Q
6
1
50
1
18
34
lis
9
6313 3231
6817 421 S
11,035
32 POISONS : THEIR EFFECTS AND DETECTION. [§ 22, 23.
§ 22. Although BO large a number of Bubstances destroy life by accident
or design, yet there are in the list only about 26 which kill about 2 persons
or above each year. It must at the same time be confessed that several
of the 26 are not simple substances, so that the statement underrates
the actual facts. The 26 substances arranged in the inverse order of
their fatality are as follows : —
Namber of deaths
in ten yean.
Antimony, 10
Potash, 10
Soda, 18
Acetic add, 14
Nitrous oxide, 16
Cocaine, either alone or with other substances, ... 16
Zinc salts (chloride and sulphate), 20
Paraflan, 28
Aconite, 45
Chromic acid and preparations of bichromate of potash, 53
Ether, 71
Alcohol, 87
Belladonna preparations, including atropine, ... 95
Chloral, 96
Mercuric salts, 97
Phosphorus, 148
Oxalic acid, 171
Arsenic, 211
Ammonia, 217
Strychnine 244
Pmssic acid and cyanides, 535
Mineral acids, 680
Chloroform, 852
Lead, 926
Opiates, including laudanum, soothing syrup, morphine, . 1655
Carbolic acid, 1964
IV.— The Connection between Toxic Action and Chemical
Composition.
§ 23. Considerable advance has been made of late years in the study
of the connection which exists between the chemical structure of the
molecule of organic substances and physiological effect. The results
obtained, though important, are as yet too fragmentary to justify any
great generalisation ; the problem is a complicated one, and as Lauder
Brunton justly observes : —
** The physiological action of a drug does not depend entirely on its
chemical composition, nor yet on its chemical structure, so far as that
can be indicated even by graphic formula, but upon conditions of solu-
bility, instability, and molecular relations, which we may hope to discover
in the future, but with which we are as yet imperfectly acquainted." *
• iTUroductum to Modem Therapeutics, Lond., 1892. 136.
§23-]
TOXIC ACTION AND CHEMICAL COMPOSITION,
33
The occurrence of hjdroiyl, whether the substance belong to the
simpler chain carbon series or to the aromatic carbon compoundaj appears
to usually endow the substance with more or leas active and frequently
poisououa properties, aSj for example^ in the alcohols, and aa in hydro-
xylamine. It is also found that among the aromatic bodies the toxic
action is likely to increaie with the number of hydroxy Is : thus phenol
has one hydroxy 1, resorcin two, and phloroglucin three ; and the toxic
power is strictly in the same order ; for, of the three, phenol is least and
phloroglucin most poisonous.
Replacing hydrogen by a halogen, especially by ohlorine, in the fatty
aeids mostly produces Bubstances of oarootio properties, as, for instance,
monochloracetic acid* In the sulphur compounds, the entrance of
chlorine modifies the physiological action and intensifies toxicity : thus
ethyl sulphide {C^^^),Js is a weak poison, monochlorethyl sulphide
C^HgO^HjClS a strong poison, and dichlorethyl sulpbide C^HgClgfei
a very strong poisoti : the vapour kills rabbits within a short time^ and
a trace of the oil applied to the ear prodnees intense inflammation of
both the eyes and the ear**
The weight of the molecule has an influence in the alcohols and aeida
of the fatty series ; for instance, ethyls propyl, butyl, and amyl alcohols
show as they increase in carl>on a regular increase in toxic power ; the
nareotic actions of sodium propionate, butyrate, and valerianate also
iuoreaae with the rising carbon. Nitrogen iu the triad condition in
the amines is far less poisonous than in the pentad condition*
Bamberger t distinguishes two classes of hydrogenised bases derived
from a and jS naphthylamiiic, by the terms ^^acylic" and "aromatic."
The acylic contains the four added hydrogens iu the amidogen nucleus,
the aromatic iu the other nucleus, thus —
a NaphthyUnune.
CH
OH CH
CNHu
CH^CH
^ N&plithylamtnt}.
OH
CH CHa
CNHi
CH,
CH^ CH
OH^OHj
Acylic tetiahy tiro-
es N&phtliykmine*
V. >reyer, Bir, <i chcm^ 9m, , ix* 17S6.
CTfHs
CH
CHa
cfl;^CH
Aronmtic t*ftrahydro-
^ Naphthy limine.
t Bm, xxii. 7/7-778.
5
34 POISONS : THEIR BPFECTS AND DETECTION. [§ 24.
The acylic^tetrahydro-naphthylamine, the)3 tetrahydroethylnaphthj-
lamine, and the p tetrahydromethjluaphthylamine all cause dilatation of
the pupil and produce symptoms of excitation of the cervical sympa-
thetic nerve ; the other members of the group are inactive.
§ 24. The result of replacing hydrogen by alkyls in aromatic bodies
has been studied by Schmiedeberg and others ; replacing the hydrogen of
the amidogen by ethyl or methyl, usually results in a body having a
more or less pronounced narcotic action. The rule is that methyl is
stronger than ethyl, but it does not always hold good ; ortho-amido-
phenol is not in itself poisonous, but when two hydrogens of the
amidogen group are replaced by two methyls thus —
HO HO
/\
\/
NH.J
/\
\/
N(CH,X,
the resulting body has a weak narcotic action.
It would naturally be inferred that the replacement of the H in the
hydroxyl by a third methyl would increase this narcotic action, but this
is not so : on the other hand, if there are three ethyl groups in the same
situation a decidedly narcotic body is produced.
The influence of position of an alkyl in the aromatic bodies is well
shown in ortho-, para-, and meta-derivatives. Thus the senior author
proved some years ago that with regard to germicidal properties, ortho-
cresol was more powerful than meta- ; meta-cresol more powerful than
para- ; so again ortho-aceto-toluid is poisonous, causing acute nephritis ;
meta-aceto-toluid has but feeble toxic actions but is useful as an
antipyretic ; and para-aceto-toluid is inactive.
In the trioxy benzenes, in which there are three hydroxyls, the toxic
action is greater when the hydroxyls are consecutive, as in pyrogallol,
than when they are symmetrical, as in phloroglucin.
OH OH
/NOH /\
OH HO
OH
Pyrogallol. Phloroglucin.
The introduction of methyl into the complicated molecule of an
alkaloid often gives curious results : thus methyl strychnine and methyl
brucine instead of producing tetanus have an action on voluntary muscle
like curare.
Benzoyl-ecgonine has no local anaesthetic action, but the introduction
of methyl into the molecule endows it with a power of deadening the
§24]
TOXtC ACTION AND CElMIOAL COMPOSITION,
55
sensation c»f the skin locally ; on the othef baEd^ oocefctiyl produces no
effeet of this kind.
Drs. Crum Brown and Fmser * ha^e wuggested that there is jsonie
relation between toxicity titid the sat n rated and nmi-aiitti ruled condition
of the molecule.
Hiiial>erg nnd Trenpul Imve studied the physiological ctfect of sub-
atitnting various alkyk for the hydrogen of the hydroxy 1 group in ijara-
aoeto-am id o- phenol, ^
Para-aceto-amido- phenol when given to dogs in doses of 0*5 grm. for
every kilogr. of body weight causes slight iiarrotie symptoms, with slight
paralysis ; there is cyanosis and in the blood mnch meth^emc^lohin.
In men doses of half a graratne <7'7 grains) act as an antipyretic,
relieve neuralgia, and have weak narcotic eflecta.
The following is the result of substituting certain alkyls for H in
the HO group.
{!) MethyL—The narcotic aotion is strengthened and the antipyretic
action uuaffected. The meth^enioglobiu in the blood is somewhat leas,
(2) Ethyl, — Action very siniilar, but ranch less met hemoglobin is
produced,
(3) Propyl. — Antipyretic action a little weaker, Methiemoglobin
in the blood smaller than in para-ace to- am ido-pheuol^ but more than
when the methyl or ethyl compound is administered.
(4) AxnyL — Antipyretic action decreased,
The smallest amount of toxicity is in the ethyl substitution ; while
the maximum antipyretic and an ti neuralgic action belongs to the methyl
substitution.
Next substitution was tried in the Imid group. It waa found that
substituting ethyl for H in the imid group annihilated the narcoiic and
antipyretic properties, No methiemoglobin could be recogtiised in the
blood.
I^atly, simultaneous aubstitution of the H of the HO group by ethyl
and the substitution of an alkyl far the H in the NH group gave the
following results: —
Methyl, — In dogs the narcotic action was strengthened^ the methse-
mogiohin iu the blood diminished. In men the narcotic action wus also
more marked as welt as the auti-ueural action* The stomach and kid-
neys were also stimulated,
Etbyl, — In dogB the narcotic action was much strengthened^ while
the me th hemoglobin wtis diminished. In men the antipyretic and anti-
neural actions were nnaffocted,
Propyl, — In dogs the narcotic action was feebler than with methyl
or ethyl, and in men there was diminished antipyretic action.
** J^^nu AnMn und Phys^y vol. ij, 224«
36 POISONS : THEIR EFFECTS AND DETECTION. [§ 24.
Amyl. — In dogs the narcotic action was much smaller.
From this latter series the conclusion is drawn that the maximum
of narcotic action is obtained by the introduction of methyl, and the
maximum antipyretic action by the introduction of methyl or ethyl.
The ethyl substitution is, as before, the less toxia *
The effect of the entrance of an alkyl into the molecule of a substance
is not constant ; sometimes the action of the poison is weakened, some-
times strengthened. Thus, according to Stolnikow, dimethyl resorcin,
CjjH^(0CHg)2, is more poisonous than resorcin, GflH^(0H)2. Anisol
CgHgOCHg, according to Loew, is more poisonous to algsB, bacteria, and
infusoria than phenol, C^HjOH. On the other hand, the replacement
by methyl of an atom of hydrogen in the aromatic oxyacids weakens
OH
their action ; methyl salicylic acid CJi^\ is weaker than
X^OOH.
salicylic acid C^jH.c^
XIOOH.
Arsen-methyl chloride, A8(CH3)C1.2, is strongly poisonous, but the
introduction of a second methyl As (CHg)^ CI makes a comparatively
weak poison.
These results admit, however, of a different interpretation, for
Overton's t researches show that the effect of narcotic substances depends
on their greater or smaller power of penetrating into the nerve or other
cells, and that this penetrating power has a direct relationship to the
solubility of the substance in oil : those substances that are not soluble
in oil do not enter into the nerve cells, those that are soluble easily
penetrate. In the living cells there are not only oily matters^ but
also lecithin and cholesterin and their derivatives. The brain cells
are especially rich in such ; to the fatty mixtures in the brain cells the
name of brain lipoids has been given (Xittos = fat). Alcohol or chloroform,
after absorption by the blood, are practically in aqueous solution ; and
when this aqueous solution is carried to the brain lipoids there is a
partition of the alcohol between the lipoids and the serum, the value of
which is capable of being expressed by the coefficient — — , the degree
water
of penetration being dependent on the magnitude of the resulting figure,
which is obviously the larger the more soluble the substance is in oil.
* Ueber die physiologisclic Wirkuiig des p-amido-phcnol u, einiger DcrivaU
desselben, 0. Hinsberg u. G. Treujtel, Archivf. exp. PaUiol. u, Pharm,^ xxxiii. 216.
t Overton, Sludien iiber die Narkosc^ Jena, 1901.
H. Meyer, "Zur theorie der Alcohol Narkoso," Arch, f, exptr, Pharmac,^ xlii.
H. Meyer, Der Einfluaa icccfutclnder Temperature auf Wxrkungstarke u, Teiiungs-
coejffieietU, op, cU. xlvi.
§ 24.] TOXIC ACTION AND CHEMICAL COMPOSITION. 37
Limit of oonoentntion
necessary to produce Partition coefficient
narcosis in A-moIecules olive oil.
per litre.
Trional, 0*0018 4 46
Tetronal 0-0018 4*04
Butyl chloral hydrate 0*002 1*69
Triacetin, 0*010 0*80
Diacetin, 0*016 0 28
Chloral hydrate, 0*02 0*22
Aethyl-urethane, .... 0*026 0*14
Monacetin, 0*0126 0*06
Methyl urethane 0*40 0*04
With a trifling exception, which future research may explain, the
greater the solubility in oil of the above substances, the greater the
narcotic effect; thus trional, with a coefficient of 4*46, is active in a
concentration of 1*8 mgrm. (molecules) per litre, while methyl urethane
with a coefficient of only 0*04 must be dissolved in the proportion of
400 mgrms. per litre.
By the same process Meyer has shown that in the alkyl substitutions
it is not, as formerly held, the ethyl group which is the specific carrier
of narcotic properties, but that the activity is strictly parallel to the
partition coefficient.
Coefficient.
Dimethyl-sulphon dimethyl -methane (CH.,)2 - C - (SO2CH3X,
very weak, 0*106
Diethyl-sulphon-methane CHs(SOaC.jHB)o very weak, , . 0*1514
Tertiary butylal (CH3)3COH weak, . " . 0*176
„ amylal {CU.^)^
^COH strong, 10
C2H5/
Sulphonal(CH3)2-C-(S0aCaH3)2 8tning, . . . . 1*115
Tetronal (CaHnXj-C- (80262118)2 much stronger than
sulphonal, 4*039
Trional Cfl^
\C(S02C2H6)2 much stronger than sulphonal, . 4*458
CjH,
H. Meyer lays down the following deductions from the various
experiments on narcotics : —
(1) All chemical indifferent matters which are soluble in fat and
fatty bodies must act as narcotics on living protoplasm so far as they
enter into the same.
(2) The action will be the stronger and the earlier on those cells
in which the fatty components' are essential to the function of the cell.
(3) The proportionate activity of such narcotic must be dependent,
on the one hand, to the chemical activity of the fat-like substance ; on
the other, to the remaining constituents of the body, especially water.
The activity has, therefore, a direct relation to the partition coefficient
38 POISONS : THEIR EFFECTS AND DETECTION. [§ 24.
which determines the distribution of the substance between water and
the fatty substance.
The action of a pure narcotic is, therefore, not chemical ; it forms no
definite chemical compound with the cell, nor does it alter its structure ;
it simply interferes for the time being with its function. If the amount
of narcotic in the serum diminishes, the partition coefficient alters its
value ; and if ever new narcotic free serum leaves the brain cells, the
narcotic dialjses out and the cell resumes its function : e,g, ethyl-alcohol
is soluble in oil and in water, and 2 per cent, narcotises tadpoles in water
in a few minutes ; but if the tadpoles are now transferred to 1 per cent,
alcohol, within five minutes their vivacity is restored, as the alcohol has
dialysed out of the nerve cells.
The partition coefficient can be estimated chemically or physiologically
by the following simple methods.
(a) Non-volatile solid substances soluble in water, — Dissolve 1 grm. in
50 C.C. of water ; add an equal bulk of olive oil ; shake ; then allow the
oil to separate, and take of the aqueous solution a known volume, say
10 c.c, and evaporate to dryness ; weigh the residue.
If the original strength of the aqueous solution be designated as
a, and after shaking with oil the concentration be represented as b^
then the partition coefficient is equal to -^ •
Example. — A solution had a strength of 2 per cent, before shaking
1*8
and of 0*2 per cent, after shaking ; partition coefficient equals — - = 9.
(b) Solid substances more soluhie in oil than in water, — In this case
only 1 volume of oil is taken to 10, 50, or 100 of water, the ultimate
result being multiplied accordingly.
(c) Fluid substances soluble in oil and in water, and not too volatile. —
10 c.c. of the fluid are shaken with 50 c.c. of oil and water in a
graduated burette and the increase in volume of the oil noted. The
volume of the water is noted ; the increase of volume of the oil divided
by that of the water gives the coefficient — - —
water
(d) Physiological method, — Tadpoles as compared with leeches or
species of worms belonging to the genus Nais are used. As a rule, a
leech requires double the dose necessary to narcotise a tadpole. An
aqueous solution of the substance is made of such strength that it will
just narcotise tadpoles = ^ ; another which will narcotise leeches, say
2/3. If the original concentration of the liquid equals a, and after
shaking with oil = 5 ; if this b solution narcotises tadpoles but does
not narcotise leeches, the concentration evidently lies between fi and 2j8 ;
the solution is now diluted with a measured quantity of distilled water
I 2S, 26,] TOXIC ACTION AND CHEMICAL COMFOSITJON,
39
until the tadpoles show signs of recovery. From the a 01 omit of added
water the concentration b m cHh.'ultttedj and the partition eoefticient
obtained. That the nareotiL^ action to a great extent is parallel with
the solubility in oil is well ^hown by a r^aaarcfa of H. Meyer ou tadpoles^
in which the coefficient of each of the subBtances experimented with
waa alao ascertained.
§ 25. In gome cases the increase of CO groups weakens the action
of a poison; thus, in allantoiu there are three carbonyl (CO) groups;
thLs Hubstance does not produeo excitation of the spinal cord, but it
heightens muscular irritability mid causeSj like xanthin, muscular
rigidttj; alloxautiui with a similar structure but containing six car*
bonjl groups, does not possess this action*
FH-CH— NH NH-^CO CO-HN
io
1
AliautOLQ^
lo-^
HK
AUox&ntin.
I 26. A theory of general api>licatioti hm been put forward and
supported with great ability by Oscar Loew * which explains the action
of poisons by presuming that living has a different composition to dead
albumin ; the albumin of the chemist is a dead body of a definite
composition and has a stable character ; liYing albumin, such as circu-
lates in the blood or forma the protoplasm of the tissues, h not " stable "
but "labile*" Loew says: — ** If the old idea is acceptefl that living
albumin ii^ cheniically the same substance as that which i» dead,
numerous toxic phenomena are inexplicable. It is impossible, for
instance, to explain how it is that diamide N^H^ and hydroxy la mine
^H^.OH are toxic, even with great dilutiou, on all living animals j whilst
neither of those sul>3tances have the smallest action on dead plasma or
the onlinary dissolved passive albumin, there must tijerefore be present
in the albumin of the living plasma a grouping of atoms in a * labile*
condition {Aimngruppimjigen lahiler Ati) which are capable of entering
into reactions; audi, according to our present knowledge^ can only
be the aldehyde and the ketone groupa. The first mentioned groups
are more labile and react in far greater dilution than the Intter
groups/*
Loew oonsiders that all substances which enter into combination
with aldehyde or ketone groups must be poisonous to life generally.
For instance, hydroxy lamine, diamide and its derivatives, phenylhy-
draKine, free ammonia, phenol, pruasic acid, hydric sulphidci sulphur
dioxide and the acid sulphites all enter into combination with
aldehyde.
* ^in niUnrlicheM System dtt &i/i-mrk%Tt^m^ Munchen, 1E03,
40 POISONS : THKIR EFFECTS AND DETECTION. [§ 26.
So again the formation of imide groups in the aromatic ring increases
any poisonous properties the original substance possesses, because the
imide group easily enters into combination with aldehyde : thus piperi-
dine (CH2)5NH is more poisonous than pyridine (CH)5N; coniine NH
(CH2)4CH - CH2 - CHgCHg is more poisonous than collidine N(CH)4
C - CH - (GH^a ; pyrrol (CH)4NH than pyridine (CH)5N ;
C^Hfi-CH— NHv
and amarin* | ^CH-C^Hj than hydrobenzamide
aH,-CH=N,
>CH-C«H,
D,H,-CH=N/
If the theory is true, then substances with "labile" amido groups,
on the one hand, must increase in toxic activity if a second amido group
is introduced ; and, on the other, their toxic qualities must be diminished
if the amido group is changed into an imido group by the substitution
of an atom of hydrogen for an alkyl.
Observation has shown that both of these requirements are satisfied ;
phenylenediamine is more poisonous than aniline ; toluylenediamine
more poisonous than toluidine. Again, if an atom of hydrogen in the
amido (NHg) group in aniline be replaced by an alkyl, e.g. methyl or
ethyl, the resulting substance does not produce muscular spasm ; but if
the same alkyl is substituted for an atom of hydrogen in the benzene
nucleus, the convulsive action remains unaffected.
If an acidyl, as for example the radical of acetic acid, enter into the
amido group, then the toxic action is notably weakened ; thus, acetani-
lide is weaker than aniline, and acetylphenylhydrazine is weaker than
phenylhydrazine. If the hydrogen of the imido group be replaced by
an alkyl or an acid radical, and therefore tertiary bound nitrogen
restored, the poisonous action is also weakened.
In xanthin there are three imido groups ; the hydrogen of two of
these groups is replaced by methyl in theobromine ; and in caffeine the
three hydrogens of the three imido groups are replaced by three methyls,
thus : —
NH— CH N . CHs— CH N . CH^r-CH
I II I II I II
CO C-NH CO C— N . CHs CO C— N . CH,
I I y^ I I y^ I I y^^
NH— C=N NH C=N N . CH,-C=N
Xanthine. Theobromine. Caffeine.
* Th. Weyl (Lehrhuch der organixhen Chemie) states (p. 885) that amarin is not
poisonous, but Baccheti {Jahr. d. Chemie, 1855) has shown that 250 mgrms. of the
acetate will kill a dog, 80 mgrms. a guinea-pig ; and that it is poisonous to fishes,
bjrds, and frogs : h^drobenzan^de in the same 4o8e8 has no effect.
I 26,] TOXIC AOTIOK AKD CHRMICAL COMPOSITION, 4 1
— and experiment has shown that theobromine 11 weaker than xanthine,
and caiFeine still weaker than theobroinine.*
Loew t makes the following generalisations : —
1. Entrance of tlje carboxjl or sulpho groups weakens toxic
action,
2. Entrance of a chlorine atom exalts the toxic character of tlie
catalytic poisons (Loew's catalytic poisons are alcohols, ether ^ chloroform,
chloral, tsarbon tetrachloride, methylal, carbon disuiphide and volatile
hydrocarbons).
3. Entrance of hydroxyl groups in the cataljttc poisons of the
fatty series wenkena toxic character; on the other hand, it exalts the
toxicity of the anbstituting pojaooa. (Examples of Locw'a class of
" subfcstitntiog " poisons are hydrosylamine, phenyl hydrazine, hjdric
cyanide, hydric sulphide^ aldehyde, and the phenols.)
4. A substance increases in poiBonous character through every
influence which increases its power of reaction with aldehyde or amido
griiups. If, for example, ati amido or inddo group in the poison
molecule be made more ^* labile/' or if thrice linked nitrogen is converted
into nitrogen connected by two bands, whether through addition of
water or transposition {umhKjerurig)^ or if a second amido group enterstj
the poisonous quality ia increased. Presence of a negatii^e group may
modify the action,
5. Entrance of a nitro group strengthens the poisonous character.
If a carboxyl or a Bulpho group is present in the molecule, or if» in
passing through the animal body* negative groups combine with the
poison molecule^ or carlmxyl groups are formed In the said molecule ; in
such cases the poisonous character of the nitro group may not be
apparent,
6* Substances with double carbon linkitigs are more poiaonoua than
the corresponding saturated sul>Btances* Thus neurine witli the double
linking of the oarhon of CH^* is more poisonous than choline ;
vinylamine than ethylamine.
* V, Luaim (UorsoHt lSt8» xxl 2&7)givDi th« following leth»l doses for frog^ per
too gmiA, body weight ;-^
M on 0111 e thy Ixftn thine, 0*03
Theobrommi*, .,.*.,.. 0-02
CafTeine • . . . • 0012
^-■aooeanTe mlrodujatioti of methyl groti|ifi beiitg nooompaaied by on i'neremtd tovie
icMoii,
J. T. Ciwh nnd W» R Ihinatan {/V^c. Ho\f. Sot.^ xviii 384, l&Ol) have akown
th&t witlidrnwal of tbo aie^tyl pfroup both in pyraoonitiue and in lnnizaconine almost
dwttoys their toxioity ; by aubBtitatlng methyl for ftOftyl in aoonitiiit there ia alto a
rediiotiou of toxieity.
42 POISONS : THKIR EFFECTS AND DETECTION. [§ 2/, 28.
<CH=CHo /CHa-CHjOH
(CH,)3N<;
OH \0H
Neurine. Choline.
CH, CH,
II I
CH.NH2 CH^NH,
Vinylamine. Ethylamiue.
§ 27. M. Ch. Michet * has investigated the compamtive toxicity of
the metals by experiments on fish, using species of Serranufi, Grenfdabrus,
and Julius, The chloride of the metal was dissolved in water and
diluted until just that strength was attained in which the fish would
live 48 hours; this, when expressed in grammes per litre, he called
* * the limit of toxicity, "
The following is the main result of the inquiry, by which it will be
seen that no relation was found between " the limit of toxicity " and the
atomic weight.
TABLE SHOWING THE RESULTS OF EXPERIMENTS ON FISH.
No. of limit of
Bxperimentfl. Metal. Toxicity.
20. Mercury, '00029
7. Copper, -0038
20. Zinc, . . 0084
10. Iron, -014
7. Cadmium '017
6. Ammonium, '064
7. Potassium, '10
10. Nickel, '126
9. Cobalt, -126
11. Lithium, -3
20. Manganese, *30
6. Barium, '78
4. Magnesium, 1*6
20. Strontium, 2*2
6. Calcium, 2*4
6. Sodium, 24-17
v.— Life-Tests : The Action of Poisons on the Lower
Forms of Life.
§ 28. The progress of synthetic chemistry places annually a large
number of more or less toxic substances in commerce, and it may often
be necessary to ascertain whether a given extract is poisonous at all, and
if so, what is its action. Similarly, the action of poison on life forms
generally will assist the toxicological chemist in the identification of a
substance.
• "DelaToxicit^S compar^e des diff^rents M^taux." Note de M. Ch. Michet
Compl, Eend.^ t. xciii. p. 649, 1881.
§28]
LTFK-TISTS.
43
The chief methods of experiment are the following ; —
(1) Aofcion on the red blood corpuacles* ,
(2) Action on unicellular organisDis.
(3) Cephalopoda,
(4) Insects*
(5) Effect of poisons on the heart of cold-blooded animals,
(1) Action on the red blood corpufioles (erythrocytes).
Any hlood may be U8ed| but Heiusi * hm proposed that rabbit's blood
bould be taken as a standard.
The blood is defibrinated and severivl test tubes are charged, each with
10 drops of the defibriuated Wood. A solution of the substance in
various strengths is now abided to the bloody adding also common salt to
ejich solution so as to bring the concentration equal to 0*9 jier cent, of
common salt; such a solution j with regard to rabbit's blood, is osmotic*
If the red blood corpusitcles dissolve^ it shows the substance has a
hiBmolytrc poisonous action on the red blood corpuscles.
Examples of poisons which dissolve the red blood corpuscles are —
arseniurctt^Kl hydrogen, the poison of the bee, snake poison generally,
saponin, phallin.
(2) Action on Infnsoria.— The infusoria are extremely sensitive to
the poisonous alkaloids and other chemical agents. Strong doaes of the
alkaloids cause a contraction of the cell contents, and somewhat rapid
disintegration of the whole body ; moderate doses at first quicken tlie
movements, then the body gets perceptibly larger, and finally, as in the
first case, there is disintegration of the animal substance.
The most suitable for the research are the larger kinds, such as
parama*cia: these are easily obtained by steeping hay in water and
iucnhat ing at blood heat for about 2i hours. Among a number of species
will be observed several paramaecia^ such i\s Paramecium caudtdupi
and others. Still more suitable organisms are, however, the opalina,
Opalina ranarum. — The ojmliniB are ciliated organisms which are
found ill the rectum of almost every frog at all times of the year*
They are oval, can just be seen with unaided siglit as white points, con-
tain a number of clear nuclei, and are capable of active movement by
reason of the numbers of cilia which clothe the surface.
They are usually obtained from the frog by first paralysing the
brain so as to destroy sensibility to pain, cutting out the intestine and
the lower part of the ctecum, and slitting it up while immersed in a 0*6
per cent, solution of common salt.
The inner lining m?iy now be stroked by means of a cameVs hair
brush and the opalinm thus detached. Two drops of water containing
44 POISONS : THEIR EFFECTS AND DETECTION. [§ 28.
opalinse substances are added in aqueous solution of known but varying
strength, and the behaviour of the organisms observed as compared with
one br more " controls " contained in watch-glasses or shallow dishes. A
weak magnifying power is alone required. The chief changes are either
swelling or shrinking, alterations in form, and often the appearance of
several vacuoles ; sometimes, again, the contents become granular.
Rossbach * gives the following intimations of the proportion of the
toxic principle necessary to cause death : — Strychnine 1 part dissolved
in 1500 of water; veratrine 1 in 8000; quinine 1 in 5000; atropine 1
in 1000 ; the mineral acids 1 in 400-600 ; salts 1 in 200-300.
(3) Cephalopoda. — The action of a few poisons on the cephalopoda
has been investigated by M. E. Yung.t Curara placed on the skin had
no effect, but on the branchisB led to general paralysis. If given in even
fifteen times a greater dose than necessary to kill a rabbit, it was not
always fatal. Strychnine, dissolved in sea-water, in the proportion of
1 to 30,000, causes most marked symptoms. The first sign is relaxation
of the chromataphorc muscle and the closing of the chromataphores ;
the animal pales, the respiratory movements become more powerful,
and at the end of a notable augmentation in their number, they fall
rapidly from the normal number of 25 to 5 a minute. Then tetanus
commences after a time, varying with the dose of the poison ; the arm
stiffens and extends in fan-like form, the entire body is convulsed, the
respiration is in jerks, the animal empties his pouch, and at the end of
a few minutes is dead, in a state of great muscular rigidity. If at this
moment it is opened, the venous heart is found still beating. Nicotine
and other poisons were experimented with, and the cephalopoda were
found to be generally sensitive to the active alkaloids, and to exhibit
more or less marked symptoms.
(4) Insects. — The symptoms which may be distinguished in poisoned
flies are dulness or vivacity of movement, loss of power of progression,
paralysis of legs or wings or both, protrusion of the fleshy proboscis,
disorderly movements, and so forth.
Flies are caught without injury by swiftly placing over them a
watch- glass on the window-pane ; a card is then inserted under the watch-
glass and the fly or flies transferred to a table in a good light. Powders,
extracts, liquids can now be easily introduced into the watch-glass, or
the flrst watch-glass may be placed on another ; in either case, owing to
the confined space, the insect becomes soiled with the substances placed
under the watch-glass, and also usually sucks some up in the efforts to
cleanse itself.
As controls may be used a fly untreated and one submitted to a
* N. J. Rossbach, Pharm, ZeUschr. fUr Russland, xix. 628.
t Compt. Rend,, t xci. p. 806.
§29i]
LIFE-TESTS.
4$
N
little of the powder of the Pgre&hrum r«>*e«, one of the most powerful of
the insecticides-
In tbe presetice of pyrethnini powder, within four minutes there is
much excite men tj m from two to three minutes longer, disordered move-
in en ts, loss of balancing power, paraljsis of the wings occur, and the fly
generally lies on it8 back, death taking place in from two to three houi-s.
In poisoning by sausages, bad meat, curanne^ aud in obscure amies
Eierally, in the present state of sctetice, experimetita on living animals
are absolutely neces^sury. In this^ and in tins way oidyi in very many
instances, can the expert prove the presence of 2)motic, or show the
absence of chemical poison*
The Vivmection Act, however, effectually precludes the use of life-
test« in England save in liceosed institutions. Hence the *' methods ''of
applying life-tests described in former editions will be omitted.
§ 29. Effect of polaonB on the heart of Cold-blooded Aaimalf, — ^TIii' Vi visits tioti
Act doL^s not, liowovtjf^ itiUrfere with
tlie use of certAin living tusU, sueb,
for iiistakiicti^ as tliti teatitig of tlje
action i>f i>oiflon3 upon the recently
cxtirjiated hetiitH of oold - blooded
The hc*4vrt of th« frog^ uf (he
tuTtU", of the toitoiiie, (ind of the
jsliArk will iKJiit I'pgidarly for u long
tltije aft*r rt3moVttl fmiii the body, if
supplied with a rttgiilar silrc^Hin of
nutrient fluid* The fluids UHed fur
thiH ptirjjose aiti tbe Mootl of tlie
herbivom diUltod with Ltoninmii saU
iK)lutionT or a serum ulbnniin i^t^utioii,
or a 2 [ler cent solution of |Tiim iimhic
in ^'hich red blood cor|iusclfS are bub^
[lendod. The Bimpl«i&t apparatus to
use is tliat known an ** WilliAms',**
Willianifl* jipparatns consist* of two
glass bulba (sae dii»gmni), the one, P,
containing nutrient fluid to which a
known quuntity of the poison has b«en
added ; tht^ other, N, containing tb(^
eamo fiuid but to which no poison bos
been added i these bulbs are connected
by caoutchouc tubing to 9 three-way
tubs, T, and e4ch pieee of caoutchotie
tubtpg ha& a pressing ecrew clip, V*
iiud V ; the three- w»y tube ia eon-
nect«d with a wider- tube oonUitiiug a
valve float, F, which gives free pa^Bago
of fluid in one direction ouly^ that is,
la the directioo of tUe arrow ; tbiJ! last wide tube ia comiwcted with a Y pi^'o
of tubing, which ^aiu is cotinocted with the ttorU of the Heiart uoder o£&munitioii|
WillianiH' A])[jttnitUK
46 POISONS : THEIR EFFECTS AND DETECTION. [§ 29.
the other leg of the Y tube is connected with another wide tube, X, having a float
valve, F^ : the float containing a drop of mercury and |)ennitting (like the float valve
F) passage in one direction only of fluid, it is obvious that if the clip communicating
with N is opened and the clip communicating with P is closed, the normal fluid
will circulate alone through the heart ; if, on the other hand, the P clip is 0})en
and the N clip closed, the poisoned blood will alone feed the heart It is also clear
that by raising or depressing the bulbs, the circulating fluid can be delivered at any
pressure, high or low. Should a bubble of air get into the tubes, it can be got rid of
by removing the cork at S and bringing the fluid up to the level of the top of the
aperture. The observation is made by first ascertaining the number and character of
the beats when the normal fluid is circulating, and then afterwards when the normal
is replaced by the poisoned fluid. A simpler but less accurate process is to pith two
frogs, excise their respective hearts, and place the hearts in watch-glasses contain-
ing either serum or a solution of common salt (strength 0*75 per cent) ; to the one
heart is now added a solution of the poison under examination, and the difierence in
the behaviour and character of the beats noted.
The phenomena to be specially looked for are the following : —
1. The heart at the height of the poisoning is arrested in diastole.
2. The heart at the height of the poisoning is arrested in systole.
Arrest in diastole.— The arrest may be preceded by the contractions becoming
weaker and weaker, or after the so-called heart peristalsis ; or it may be preceded by
a condition in which the auricle shows a different frequency to the ventricle.
The final diastole may be the diastole of paralysis or the diastole of irritation.
The diastole of irritation is produced by a stimulus of the inhibitory ganglia, and
only occurs after poisoning by the muscarine group of poisons. This condition may
be recognised by the fact that contraction may be excited by mechanical and electrical
stimuli or by the application of atropine solution ; the latter paralyses the inhibitory
nervous centres, and therefore sets the mechanism going again. The diastole of para-
lysis is the most frequent form of death. It may readily be distinguished from the
muscarine diastole ; for in muscarine diastole the heart is full of blood and larger
than normal, but in the paralytic form the heart is not fully extended, besides which,
although, if normal blood replace that which is poisoned, the beats may be restored
for a short time, the response is incomplete, and the end is the same ; besides which
atropine does not restore the beats. The diastole of paralysis may depend on para-
lysis of the so-called excito-motor ganglia (as with iodal), or from jiaralysis of the
muscular structure (as with copper).
Tlie heart at the height of the poisoning stops in systole.
2. Arrest in systole.— The systole preceding the arrest is far stronger than
noimal, the ventricle often contracting up into a little lump. Contraction of this
kind is 8i)ecially to be seen in poisoning by digitalis. In poboning by digitalis the
ventricle is arrested before the auricle ; in muscarine poisoning the auricle stops
before the ventricle. If the reservoir of Williams' apparatus is raised so as to
increase the pressure within the ventricle the beat may be restored for a time, to
again cease.
A frog's heart under the influence of any poison may be finally divided into
pieces so as to ascertain if any parts still contract ; the significance of this is, that
the particular ganglion supplying that portion of the heart has not been affected : the
chief ganglia to be looked for are Remak's, on the boundary of the sinus and auricle ;
Ludwig's, on the auricle and the septum of the auricle ; Bidder's, on the atrioventri-
cular border, especially in the valves ; and Dogiel's ganglion, between the muscular
fibres. According to Dogiel, ]K>isons acting like muscarine aff'ect every portion of the
heart, and atropine restores the contractile power of every portion.
Jacobi's apparatus.— Glass canulas are introduced into the left vena cava and
aorta i-espectively, the other big vessels being ligatured ; the arrangement is as in the
I 290
UFE-TiSTS.
47
tigtirc. Th« on^ e^nuU U conttcctrd wtlB nn induirtibber tube n^ atl«;h«d to Mar^
riott'fl flasks by meiiiis of si Y -piece ; the other t4> a T^pieee T, eoDnecti^d un the ou@
side to » j^umlt nietcur^ m&iiometer ; tlie limb of t\w mutomnter Dearest the T-pince
itf connected with a pnewnfe take 8 ; tbe other limb of the m&nometer is, as shown,
providod with a. recording Ap(jar&tiii wUieb drmwa & curve iu th« revolving cyliuder C ;
the other side of the T-piece cousistJi of a tube, connected with a wider tub<* W ; into
this tits a g]&s& rodf wLieh can be pushed in ami out ; thu i;Ia^ rod is no armxii^ an
to leave a Irne capillary slit ; the farther tbi^ rod h pulled out ihc ea-^ier the fluid
dropA iuto V, the farther it is pushed iu tlie slower the Uquid drops, and therefore
tbi' gri^ter the pn^^ure. The tube with the glass rod i^ horizon tal» and a few mms^
liigher than the level of tbe fluid in R ; tbe zero imnt of the mauocueUr i* carefully
adjujcled to thiA kveJ. If, iu tlie manner stated^ the pressure is raised ^ the pref^san^
tmbe 8 begins to fill with the nutria t fluid, and the heart is comiiollf>d to work at a
gndually Ibcrcaaing pre^j^ure^ and Ihi^ pressure nmy be registered on the kyuiograpb
hf ocRDpanson of tbe tracing with tbai i>f the ^' time curve -^ Z.
Jacobi*s Apparatus,
Jaeobi has experinieuted with tbe prei^ures in the aorta and the auncle of luge
frogs, and has been able to nearly imitate the natui-al pressure in tbe isolated beiart.
If the latter works with a difl'erence in level of 10-20 mm. the ventricle drives the
fluid into the pressure tub* 50-66 cm, and tbe fluid droika into the little syphon V
regidarly with each systole^ two or thiii^e drops escapirig, that is. with Urn pialfiatious
from 1*0*1*5 (Jfrma., which with a height of 50 cm* corresponds to work of 50-7rt
grnis.
Jacobi ingeniously registers graphically the amount of fluid flowing in relation
to time^ pre^sTire, and pulse as follows : — Around the little glass rod is wound a uioiat
slired of wool, leading the liquid into a ismaU glass vessel syphon shaped^ V, which is
bakneed at oi»e i?nd of a slender rod g, equilibrinm being obtaiiml by a eouuterjioise ]
the little vei^sel when full rapidly empties itself by ^ypbon aettott, and hence is in
intermittent vibration ; these vibrntiona are recorded graphically by breaking and
middng contact at p with a galvanic battery arrangement, arid by means of the
niagiiet. at M the attached marker draws a line on the revolving cylinder C, at the
aanie moment lines are drawn by the markers A and Z. By means of this instrument
either normal or pmaoaied flmd may be put into the iaolateil heart, and tbe etfedtti
thus graphically registered.
48 poisons: theib effects and detection. [§ 30, 31.
§ 80. The effect of polBons on the iris. —Several poisons affect the pnpil, causing
either contraction or dictation. The most suitable animal is the cat, the pupil of
the cat readily showing either state.
Toxic myoeifl, or toxic contraction of the pnpil.— There are two forms of toxic
myosis, one of which is central in its origin. In this form, should the poison be
applied to the eye itself, no marked contraction follows ; the poison must be swallowed
or iigected Rubcutaneously to produce an effect The contraction remains until
death.
The contraction in such a case is considered to be due to a paralysis of the dilata-
tion centre; it is a *' myosis paralytica centralis -y the best example of this is the
contraction of the pupil caused by morphine.
In the second case the poison, whether applied direct to the eye or entering the
circulation by subcutaneous injection, contracts the pupil ; the contraction persists if
the eye is extirpated, but in all cases the contraction may be changed into dilatation
by the use of atropine. An example of this kind of myosis is the action of muscarine.
It is dependent on the stimulation of the ends of the nerves which contract the pupil,
especially the ends of the nervus oeulomolariua supplying the sphincter iridis ; this
form of myosis is called myosis spastica periphera. A variety of this form is the myosis
spastica musctUaris, depending on stimulation of the muse, sphincter iridis, seen in
poisoning by physostigmine. This causes strong contraction of the pupil when locally
applied ; the contraction is not influenced by small local applications of atropine, but
it may be changed to dilatation by high doses. Subcutaneous injection of small doses
of physostigmine does not alter the pupil, but large poisonous doses contract the pupil
in a marked manner.
Toxic mydriasis, or toxic dilatation of the pnpil.— The following varieties are
to be noticed:—
1. Toxic doses taken by the mouth or given by subcutaneous injection give rise
to strong dilatation ; this vanishes before death, giving place to moderate contraction.
This form is due to stimulation of the dilatation centre, later passing into ])aralysis.
An example is found in the action of aconite.
2. After subcutaneous or local application, a dilatation neutralised by physostig-
mine in moderate doses. This is characteristic of )3-tetrahydronaphthylamine.
3. After subcutaneous injection, or if applied locally in very small doses, dilatation
occurs persisting to death. Large doses of physostigmine neuti-alise the dilatation, but
it is not influenced by muscarine or pilocarpine : this form is characteristic of atropine,
and it has been called mydriasis paralytica periphera.
VL— General Method of Procedure in Searching*
for Poison.
§ 31. Mineral substances, or liquids containing only inorganic
matters, can cause no possible difficulty to any one who is practised
in analytical investigation; but it is otherwise with organic fluids or
solids.
The first thing to be done is to note accurately the manner in which
the samples have been packed^ whether the seals have been tampered
with, whether the vessels or wrappers themselves are likely to have
contaminated the article sent ; and then to make a very careful observa-
\
§3«-l
PROCSDURE IN 8EABCHINQ FOR t>OISON,
49
tion of the appearance^ bid ell, colour^ and reaction of the matters^ not
forgetting to take the weight, if solid — the volume, if liquid. All these
are obvious precautions, requiring no particular directions.
If the abject of research is^ the stomach and its coateuts, the con ten is
should be carefully transferred to a tall conical glaae ; the organ cut
opeti^ spread out on a sheet of gla^s^ and examined minutely by a len8,
picking out any suspicious- looking substance for closer observation.
The mucous membniue should now be well cleansed by the aid of a
wash-bottle, and if there is any necesaity for destroying the stomach, it
may be essential in important cases to have it photographed , The
washings bavmg been added to the couteut« of the stomach, the sedi-
ment m separated and submitted to inspection^ for it must be remembered
that, irrespective of the discovery of pobon» a knowledge of the nature
of the food last eaten by the deceased may he of extreme value.
If the death has really taken place from disease, and not from
poiBon, or if it haa been caused by poison, and yet no definite hint of the
partioular poison can be obtained either by the sympteius or by the
' attendant circumstances, the analyst has the difficult task of endeavour-
ing to initiate a process of analysis which will be likely to discover any
poison in the animal, vegetable, or mineral kingdom. For this purpose
the following process has been devised, which differs from those published
at an earlier date mainly in the prominence given to operations iu a
high vacuum, and the utilisation of biological experiment as a matter of
routine. Taking one of the most difficult cases that can occur — viz.,
one in which a small quantity only of an organic solid or fluid is available
— the best method of procedure is the following : —
1. Distillation in a vacuum at a low temperature*
2. Collecting the volatile products.
3. Dehydrating the organic substances.
4. Dissolving out from the dry mass fatty matters and alkaloids,
glucosidea, etc., by ethereal and alcohol ic solvents.
5. Destroying organic matter and searching for metals.
A small ixjrtion is reserved and examined microscopically, and, if
thought desirable, submitted to various '* cultivation " experiuients*
The greater portion is at once examined for volatile matters, and having
been placed iu a strong flask, and, if neutral or alkaline, feebly acidulated
with tartaric acid, connected with a second or receiving flask by glass
tubing and caoutchouc corks. The caoutchouc cork of the receiving-
flask has a double perforation, so as to be able, by a second bit of angle
tubings to be connected with the mercury purap described in theauthor*a
work on ** Foods," the figure of which is here repeated (see the
accompanying figure). With a good water-pump having a sutUeient
length of fall-tuhei a vaeitum may be also obtained that for practical
4
31.]
PROCSD0KE IN SEARCHING fOR POrSON.
51
action of s^uy ejEternal heat; but tf this is too slow, the faak uontaiDing
Ihe aubBtaDces or liquid under examination may be gently heatad bj a
water-bath : water, volatile oils, a variety of volatile aabstances, such as
prusaic acid, hydrochloric acid, phosphoms, etc., if present, will distil
over. It will be well to free in this way the substance^ as much as
possible^ from volatile matters and water. When no more will come
over, the distillate may be carefully examined by redistillation and the
various appropriate tests,
Tiie next step ia to dry the Btimple thoroughly* This is best effected
also in a vacuimi by the use of tlie same apparatus, only this time the
receiviug-flask is to be imlf filled with Btrong sulphuric acid. By now
applying very gentle heat to the fij-st flask, and cooling the sulphuric
acid receiver, even such substances as the liver in twenty-four hours
may be obtained dry enough to powder.
Having by these means obtained a nearly dry
friable mELsa, it is reduced to a coarse powder, and
extracted with petroleum ether, and triaated as under
the special section for Alkaloids and Glucosides (see
Index),
It mu^t also be remembered that there are a few
metallic compounds (as, for example, corrosive sub-
limate) which are soluble in alcohol and ethereal
solvents, aiid must not be overlooked,
The residue, after being thus acted upon succes-
sively by petroleum, by alcohol, and by ether, is both
water-free and fat-free, and also devoid of all organic nmucrBed in mer-
I J ' ' 1 J J. 1 ' cury, whicb tlio deep
poisonous bases and principles, and it only remains rrroovo recoivca,
to treat it for metals, various processes for which are
as follows^ These proceisB6fi have been devised chiefly for the detection
of arsenic and antimony^ but evidently may be used, with obvious
limitations, for most mineral matters*
A very fair and complete analysis may he made from a small amount
of material. The process is, however, somewhat faulty in reference to
phosphorus, and also to oxalic acid and the oxalates ; these poison^ if
suspected, should be specially searched for in the manner to be more
particularly described in tlie sections treating of them* In most cases
there is sufticient material to allow of division into three part^ — one for
organic poisons generaliy, one for inorganic, and a third for reserve in
case of accident. When such is the case, altliough, for organic principteB,
the process of vacuum distilhition just described still hold a good, it will
be very much the most convenient way not to nse that portion for
metals, hut to operate on the portion reserved for the inorganic poisous
as follows, by destruction of the organic matter.
Thb figure islrotn
**Foc«k^ B is a
h^ll^ar^ whi(:h eau
he aaai'ted by a cork
to u coudensev ; E is
made of ii-on ; the
[iiD of the belKjar is
52 POISONS: THEIR EFFECTS AND DETECTION. [§ 32.
METHODS OF DESTROYING ORGANIC MATTER WHEN
SEARCHING FOR MINERAL POISONS (ESPECIALLY
ARSENIC).
§ 32. (A) Destruction by heat. — Of all methods, destroying by heat
alone or in a current of oxygen is the most perfect ; always provided
that the apparatus is so arranged that volatile metallic vapours can be
condensed or otherwise recovered.
G. Bertrand,* in researches on the presence of arsenic in the animal
tissues, burns the organic matter by means of compressed oxygen in
Berthelot's calorimetric bomb. From 1-2 grms. of the substance,
previously dried, is placed in the bomb ; and the combustion is initiated
by a very small shred of fulminating cotton in a platinum loop, through
which is passed an electric current.
Where necessary, the product of several combustions is acciimulated
in the same bomb. The bomb is then washed out with water. The
water contains traces of nitric acid produced in the combustion, which
it is usually best to evaporate off.
The objection to the process is the expense of the apparatus, the
cheaper enamelled bombs in commerce, according to Bertrand, always
containing traces of arsenic ; besides which, only a very small quantity
of the substance can be dealt with at one operation. On the other hand,
the advantages are obvious. The combustion is complete, and a solution
can be readily obtained suitable for treatment by hydric sulphide or by
Marsh's apparatus.
Verryken t places 5-10 grms. of the previously dried organic matter
in a combustion tube, into which is led dry oxygen by three small tubes
of different length, in order to distribute the gas equally ; the tube is
connected with a series of bulbs charged with water. The tube is very
carefully heated to a dull red heat on each side of the substance ; then
the substance itself is heated very carefully, in such a way as to
avoid brisk inflammation of the mass ; on cooling, the tube is washed
out with hot nitric acid, the water in the bulbs added, and thus a nitric
acid solution obtained.
In the method of Woehler and Siebold, the matters, suitably divided,
are heated in a porcelain dish with their weight of nitric acid until
an homogeneous mass has been obtained, then the acid is neutralised,
by soda, potash, ammonia, or lime, and evaporated to dryness. The
product is now cast in small portions at a time into a porcelain crucible
brought to a dull red heat. The ultimate mass, which should be of a
* G. Bertrand, * ' Emploi de la bombe calorimetrique pour demontrer I'existence
de Tarsenic dans Torganisme," Camptes Bend., 1903.
+ Journ. depharm, iVAnvers, 1872.
§ 32-1 PROCKOURB IN SKARCHING FOR MINERAL POISONS.
S3
pure white colour, is then di^olved in boiling water and a HolutioD
obtained absolutely free from organic matter. According to A. Gautier,
this method should not be used in reaearches on arsenic, the loss of
arsenic being considerable.
Sfimc method,— In this method the organic matters^ iutimately mixed
with half their weight of pure lime or pure magneflia, are burned up in
a niutHef and the proihiet treated with nitric or hjdrochlorie acid until
dissolved. The process has been used in researches on malt and on
coal, and it is titated no arsenic is lost; but it haa not been used in
other toxioologioal investigations.
X Ogim^s met hod.* — The organic matter (viscera, ejj>) is finely
dividcfl and made into a soupy mass by the addition of water, and
introduced into a large Hask ; about j\y of the weight of the organic
substance of potaasie chlorate is added. Hydruchlorie acid gas produced
by the action oF pure sulphuric acid on pure hydrochloric acid is passed
through the liquid, the gas finally escaping being led through a little
water t^ arr^t possible traces of arsenic chloride. As soon as yellow
vapours are seen above the lii|uid the current of gas is stopped, the
process of destruction going on now without farther assistance. The
end of the reaction is indicated by the yellow colour of the liquid. The
insoluble matters are filtered ofT, and, if desired, may he treated by one
or other of the dry methods ; but it can be shown that, as a rule, thej
are destitute of poisonous metals. The destruction is rapid, 500 to
1000 grms, of organic matter being destroyed within the hour,
A, lV//»Vrff*t Tfiethod. — Villiers uses the salts of mangimese. The
substances^ made into the consistence of porridge by the addition of
hydrochloric acid diluted with from 2-3 times its volume of water, are
hitroduced into a suitable Sask, which has a cork carrying a funnel
provided with ii stopcock and a tube, the end of which dips into water.
Through the funnel is gradually intro<iuced a solution of a manganese
salt and a little nitric acid, a regulated heat being nt the same time
applied ; the gases evolved are nitrogen and carlwn dioxide, hence the
products are without odour ; the process is even more rapid than that
of Ogier, In researches for arsenic it is obviously nec^sary to take
accurately weighed or measured i| nan ti ties of the refigenl*(, aud, if arsenic
is found, to make with equal quantities of the reagents a blank
experiment for the purpose of ascertaining their freedom from arsenic,
Procem </ Armafid GauHen *—G9,uihr has revived the old process
of destruction of organic matter by sulphuric and nitric acids, with
improvements in detail.
*' Tt'mit* dp thimie tojnmditff^itfti.et Paris, ISftO,
t A* Oftutifir, Bull, Spe, chim,, 190S.
54 POISONS : THEIR EFFECTS AND DETECTION. [§ 32
Four grms. of pure sulphuric acid and 40 grms. of nitric acid
(1*42 sp. gr.) are added to 100 grms. of the organic matter in a
porcelain dish. This is carefully heated until the entire mass assumes
a chocolate colour ; 30 additional grms. of nitric acid are added little
by little, taking care that before the addition of a fresh quantity the
matters have a brown tint; after the addition of the final quantity,
the heat is continued until the contents are almost black, with
commencing carbonisation.
Next, 12 more grms. of nitric acid, three successive times are added,
after each addition pushing the carbonisation still farther. The operation
is finished when no more fumes are evolved and the carbon detaches itself
from the dish. The mass is now rubbed to a powder in the dish itself
by means of a pestle, and exhausted with from 250 to 300 c.c. of boiling
water. This, after being filtered, contains the metals ; some sulphurous
acid is added, and the whole is submitted to a current of SHg for 3
hours, first at a temperature of lOO^C. and then at ordinary temperatures.
100 grms. of muscle leave from 2*5 to 3 grms. of carbon. The quantity
of acid used in ordinary cases is therefore 4 grms. of sulphuric acid
and 106 of nitric acid ; but should the matters be very fatty, more
nitric acid is recommended.
According to Gautier, the nitric acid acts on the chlorides,
forming a nitro-hydrochloric acid, very poor in the latter (hydro-
chloric) acid, so that the chlorine is expelled with the nitrous
products without a trace of arsenic chloride being formed. The
excess of nitric acid also effectually prevents the formation of
arsenic sulphide.
PagePs process, — The older processes in which arsenic is distilled
over as chloride of arsenic, according to the researches of Gautier, do
not yield good results. Schlagdenkaufen and Pagel have, however,
elaborated a process in which they state that in all cases the total
amount of arsenic may be recovered in the form of chloride.
The suspected organic matters are placed in a tubulated retort
with a mixture of two parts of pure sodium chloride and one part of
potassium bichromate ; by means of a funnel tube provided with stopcock,
pure sulphuric acid is allowed to drop little by little on to the mixture.
A violent reaction occurs, chromous chloride (CrOgClg) gas being pro-
duced ; the vapours are caused to pass first into a flask cooled with
water, then through bulbs or other apparatus, the final portion of which
is charged with a weak solution of potash. The action is aided by
heat ; the addition of sulphuric acid is continued until no more yellow
vapours are produced and the carbon disappears. The gas is decom-
posed by the first washing of water into hydrochloric acid and chromic
acid, CrOgClj + HjO = CrOg + 2HC1. The heat being continued, sulphur
§ 32.] PEOCEDURE IN SEARGHIHG FOR MINERAL POISONS.
55
dioxide is produced, which, in its tum^ reduces the chromic acid. The
final green Bolution, with the various washing waters, are freed from
sulphur dioxide and submitted to hydric fiiilphiile, while the non-
volatile metalt are tested for in the residue remaining in the fiask,
the residue for this purpose being exhausted with hot water, and the
solution filtered.
In all cases the amount of acid it j of the solution of the inorganic
salts should be ascertained by titrating with normal soda an aliquot
part of the same.
The liquid is now satumted with a current of gaseous sulphuretted
hydrogen until it smells strongly of the gas. The flask should now be
corked and set aside for at least twelve hours, any precipitate is Altered
off, the liquid is ishakeri and warmed to expel the excess of Bulpbiiretted
hydrogen, Bodic acetate is now added in slight excess of the acidity,
as determined by the titration above mentioned, so as to replace the
mineral acid by acetic acid. For every 10 c.c, of normal soda 1*36
grra. of sodic acetate in theory would exactly replace the mineral acid.
For example, supposing that the original liquid measured 510 c.c,
10 c,c. of which was neutralised by 5 c.e, of normal soda, then the
proper quantity to add of sodic acetate to the 500 c.c, would be 34
gnaas. to exactly replace the acid, and an extra couple of grms. so as to
ensure an excess ; in all 36 grms* The liquid is now again saturated
with sulphuretted hydrogen in order to throw down any zinc as
sulphide.
Should a precipitate occur, this is filtered off, and the filtrate
saturated with aramonium sulphide.
(a) Frectpilate from acid H,^ soluHoih — From the acid solution,
the sulphide of a large number of substances may theoretically be
present in the precipitate, ejj, amenic, antimony, tin^ germauiimi,
molybdenum, selenium, tellurium, gold, platinum^ iridium, silrer,
mercury, lead, bismuth, copper, cadmium, palladium, osmium, rhodium^
and ruthenium ; but it is obvious that many of the above substances
are not likely to occur in a routine toxicological investigation. These
snip hid e& are treated with ammonium sulphide, which dissolves the
members of the above group up to and includiDg iridium, and leaves
insoluble the remainder, which may be searched for in the ordinary
manner (see ^eoJ, Merem-yt etc.).
With regard to the sulphides soluble in ammonium sulphide, we
nted only here consider tin, antimony, and arsenic, and these are best
Beparated by Carnot's method.* The ammonium sulphide solution is
made acid by means of HCl, and the dissolved sulphides {with sulphur)
sre thrown down j these are collected on a filter, and dissolved by
56
POISONS: THDR KFFECTS AMD DETECTIOM.
[§ 33-
means of either HCl and potasaic chlorate or HCl with a little uttric
acid; to the solution m added ammonium oxalate and ammonia^ but
not in sufficient quantity to form a precipitote Tlie cle^r solution is
neated to ebullition and a solntion of sodic hyposulphite added ; this
throws down {with sulphur) the red sulphide of uutimony, should
antimony be present On separating the precipitate by filtration the
filtrate is made a«id by hydrochloric acid, and a current of hydric
sulphide passed through^ and well boiled to get rid of sulphur dioxide;
auy arsenic is precipitated as yellow sulphide, and any tin remains in
solution ; the latter may be separated as bisulphide by saturating the
filtrate with ammonia, then adding ammonium sulphide, and after a few
minutes, acetic acid.
(b) PreHpitate/rtmi acetie H^S mitdum. See Zine.
(c) Precipitate from ammomum mdphide. See Uhrommm^ Nickel,
Cobalt, etc,
(d) Examine the filtmte for alkalies and alkaline earths. Any
residue remaining after destroying organic matter and dissolving in
acids may be specially treated for the detection of silver and barium
salts, should th^e be present in an insoluble form.
The residue is dried and intimately mixed with three times ita
weight of a mixture containiug two partfl of sodio nitrate and one part
of sodium hydrate* This is placed, little by little, m a red-hot porcelain
crucible and melted. The melted mass is cooled, dissolved in a little
water, a current of CO^ passed through the solution to convert
any caustic soda into carbonate, and the solution boiled* The
insoluble portion cousista of carbonates of lead and baryta, and
of nietallic silver The mixture is filtered ; the insoluble residue on
the filter is wiirmed for some time with dilute nitric acid; the solution
of nitrates of silver, lead and barium are concentrated on the water-
bath nearly to dtyness so as to get rid of any excess of acid, and the
nitrates dissolved in water ; then the silver is precipitated by hydro-
ohloric acid, the lead by SH^, and the barium by sulphuric acid.
VIL— The Spectroscope as an Aid to the Identification
of certain Poisons.
g 33, The spectra of many of the metals, of phospbinei of arsine,
and of several other inorganic substances, are characteristic and easily
obtained*
It b, however, from the employment of the micro-sptetroacQpe that
tlie toxicologist is likely to gel most assistance
§33]
SPECTROSCOPIC APPEAKANCEB OF BLOOD.
57
Oscar Bifasch * has ivithiii the last few years studied spectroscopy in
relation to the alkaloids and organic poisons. Some of theae, when
mixed with Froehde^s reagentj or with sulphuric acid, or with sulphuric
acid and potaasic dichrornate, or with uitric acid, give charaoteriBtio
colonrSj and the resulting solutions, when examined by a spectroscope,
for the most part show absorption bands ; these bands may, occasion-
ally, assist maty rial ly in the identification of a poison. By far the best
ap|iarutus is a micro-spectroscope of the Sorby and Browning ty|ie, to
which is added an apparatus for measuring the position on a scale of
the lineH and bands, Sejbert and Kraft of Wetzlar make an excellent
instrument, in whioh a small bright triangle Is projected on the
spectrum ; thin can be moved by a screw, so that the apex may be
brought exactly in the centre of any line or band, sind its position
read on an outside scale. The first
thing to be done with such an instru-
ment is to determine the position on
the scale of the chief Fraunhofer
lines J or of the more characteriatic
lines of the alkalies and alkaline
earths, t the waTe lengths of which
are accurately known* If, now, the
aeale divisions are set out as absciasse,
and the wave lengths in mil) tenths of
a millimetre are made the ordlnates
of a diagram, and an equable curve
plotted out, as fnily explained in the
author's work on " Foods," it is easy
to convert the numbers on the scale
into wave lengths, and so make the readings applicable to any spectro-
scope. For the purpose of graphical illustration the curve method ia
convenient| and ts adopted in the preceding diagrams, all taken from
Oscar Brasch's monogmph. Where the curve is highest, the absorption
band is thickest ; where the curve is lowest^ there the band is weak*
The fluid to be examined is simply placed in a watch-glass, the watch-
glasB resting on the microscope stand.
* Uiib$r Venemdbarkeii dtr Speciroseopie zur l^niersth^'iditng def FitrltfpifWId-
fimwn rfrr Oiftt im Iniermu dgr/or^nMselmi Ch^tiit^ Darpat» 1890»
t Th« alkalies t^uA earths used for this purfTOsef with their wave lettgths, are m
foUciwa : KC1» a line in the red X 770, in the violet x 401, Lithium chloride, »d
liae, 670 '5 ; sodium chloride, yellow, 589 ; strontium chlorides, line lu the hlwa^ 401.
It ia iilso HBciul to mea^are the gr^en Hae of thallium chloride = 535*
ColliS| Proc, Rify, Soc^ \kicL 25 » IdOS^ recdtumeada & vacuum ttihe eharged with
hjfdrogeu, helium^ and mercury vapour ; thia gives no le^ thia 15 lines from the rwi
fle (700-68) to H iu the violet {434'1).
CURVES INDICATING THE POSITION OP ABSORPTION BANDS
ON TREATING CERTAIN ALKALOIDS WITH KEAGENTB.
H G F bB D CB A H a F bB B OB A
mmiimmiamttt^t m ^mf^
^■'■' ■•' ' '
l-n ■■Mil lr^i.|lPM.Il laft
H G n CB A H G F bE D CB A
NOTES Tu I URV EH INDICATING ABSORPTION BANDS.
fitryclinine^ ti'^ated with sulphuric acid and potas^ic dichromAte ^riolet).
Brucine, tieated with {Kitassic nitrate and Bulphuric acid (clfeftTr«a)»
Quehnieliiiie, treated with vanadium sulphate {dark blue).
Quinine, VogeTtt reactioji (red)*
CAffeiriGp Marexidiimction (violet- red )»
DelpMnoidin^ Ffoehdo'a reagent (cherry -red).
Veratriue, treated with TOljmuric acid (straw yellow),
t, ,t (cherry-red),
„ M I' (carajine-fed)i
Ventriue, Furftirol reaction (blue-violetj.
Sahadillin, treated witfi sulphuric acid (r«d),
Veratroidine^ ,, ,, (brown* fed )»
Jerrine, Furfbrol reacti^m (blue).
Sabadme ,, „ (bloi?),
Sabodiiief treated with nuJphiiric acid (cberry-red),
Phyaoitigmine, „ ., (grass-green).
MorphiiK?, treats witb Fro«hde*» reagent and aQgar (dark ^en).
N^nTotitte, tr«>aied with a mixture of sulphuric acid and Qitric acid (30 dropa of '
uulphtsrie to 1 drop of tiitric), (red).
Cktddnn, treated with Froehde'a reagent and sugar (dark violet),
Pap«iverin(«» treated with Frochde'e reagent (green -blue).
iftopiinariii, ,, ,, (violet-r^)*
Oh«Bdoixlii, ,t sulphate of vanadium (dark green )^
Soliuiui, t , iulphuric acid and allowed to Ataiid 4 hours ( bf own-red).
XHj^talini «; ErdmAnn'a reagont (red).
AmUnei 1^ sulphuric add and potoa^c dichronute (blue).
§34.]
SPECTROSCOPIC APPEARANCES OF BLOOD.
S9
The wave lengths corresponding to the numberB on the scale in the
diagram are as follows r^^ —
W.L.
W.L.
a
732
4
510-2
1
e&6
5
480-0
2
589-2
0
4SS
s
&49^S
7
438
Examination of Blood, or of Blood-Stains.
§ 34. Spots, supposed to be blood— whether on linen, walls, or
weapons — should, in any important case, be photographed before anj
chemical or microscopical examination is undertaken. Blood-spota,
according to the nature of the material to which they are adherent,
have certain naked-eye peculiarities — e.g. blood on fabrics, if dry, has
at first a clear carmine-red colour, and part of it soaks into the tissue.
Lf, however, the tissue has been worn some time, or was origiunlly
soiled, either from perspiration, grease, or filth, the colour may not be
obvions or very distinguishable from other stains ; nevertheless, the
stains always impart a certain stiffness, as from starch, to the tiasue.
If the blood has fallen on such substances as wood or metal, the spot is
black, has a bright glistening surface, and, if observed by a lens,
exhibits radiating fissures and a sort of pattern, which, according to
some, is peculiar to each species ; so that a skilled observer might
identify occasionally, from the pattern alone, the animal whence the
blood was derived. The blood is dry and brittle, and can often be
detached, or a splinter of it, as it were, obtained The edges of the
splinter, if submitted to transmitted light, are observed to be red.
Blood upon iron Is frequently very intimately adherent ; this is specially
the case if the stain is upon rusty iron, for hseioatin forms a compound
with iron oxide. Blood may also have to be recovered from water in
which soiled articles have been washed^ or from walls, or from the soil,
etc. In such cases the spot is scraped off from walls, plaster, or masonry,
with as little of the foreign matters as may be. It is also possible to
obtain the colouring-matter of blood from its solution in water, and
present it for farther examination in a eoncentratod form, by the use of
certain precipitating agents.
In the following scheme for the examination of blood-stains, it is
presumed that only a few spots of blood, or, in any case, a small (quantity,
is at the analyst's disposal.
(1) The dried spot vs submitted to the suction of a cold saturated
solutbn of borax. This medium (recommended by Bragendorff) *
* Un^suehimgen von Blulspurm in Masoltki'i Mandbuckt Bd, i. Half band 2.
6o POISONS : THKIR KPPKCTS AND DETBCTION. [§ 3$.
does certainly dissolve out of linen and cloth blood-colouring matter
with great facility. The best way to steep the spots in the solution is
to scrape the spot off the fabric, and to digest it in about a cubic
centimetre of the borax solution, which must not exceed 40*; the
coloured solution may be placed in a little glass cell, with parallel walls,
'5 centimetre broad and '1 deep, and submitted to spectroscopic
examination, either by the ordinary spectroscope or by the micro-
spectroscope ; if the latter is used, a very minute quantity can be
examined, even a single drop. A better solvent is Riegler's reagent,
to be described later. In order to interpret the results of this examina-
tion properly, it will be necessary to be intimately acquainted with the
spectroscopic appearances of both ancient and fresh blood.
§ 35. SpectroBCopic Appearances of Blood.— Fresh blood defibrin-
ated, filtered, and examined in a test tube or in a suitable absorption
cell by a prism spectroscope shows, when diluted sufficiently with water,
two absorption bands, the one near the sodium line well defined, the
maximum shadow being at wave length 578*1 ; the other in the green
with somewhat fluffy edges, therefore less definite in the green, the
centre of the band being at 541*7; this two-banded spectrum is that
of oxyhsBmoglobin. The spectrum is graphically represented in fig. 1,
taken from J. Formanek's paper.*
On exposure of the same solution to air, new bands make their
appearance ; these new bands are those of methsemoglobin ; the older
the solution, the more the bands of methsemoglobin tend to intensify,
the more those of oxyhcBmoglobin fade. The spectrum is, however,
with blood weeks or even months old, always a mixture of oxyhsemo-
globin and methtcmoglobin ; the wave lengths of the two methaemo-
globin bands centres are respectively 634, and a weak band in the
green 500*8 (see fig. 2).
By adding ammonium sulphide to blood the spectrum of haemoglobin
(fig. 3) is obtained; it shows a weak absorption band (619*8) and a
broad, somewhat diffuse band (554*7).
Oxyheemoglobin solutions treated with alkalies suffer change; the
oxyhsemoglobin is separated into haematin and an albuminous body.
The haematin is soluble in strong soda lye, and shows a single band in
alcoholic solution, which is situated about X 598*8 (see fig. 6). If this
alkaline solution of haematin is now treated with a reducing substance, a
third colouring substance makes its appearance, called by Hoppe-Seyler,
who discovered it, by the name of haemochromogen ; this shows two
absorption bands very similar to haemoglobin, but both bands are shifted
towards the violet end of the spectrum (X 659*1 and X 529*2) (fig. 7).
* "Ueber die Absori)tion Spectra des Blutfarbstoffe," Zeit, f. anal, Chemic,
1901, 505.
§35]
SPBCTKOSCOPIC APPEARANCES 0? BLOOD.
6i
By utilising the properiies of Kydraziu, which diisolFeB the red
blood corpuscles, and at tho eame time is a powerful redtioing agent,
lliegler * has suggested the best general test for blood at preaent known,
Riegler's reagent is prepared aa foHowa : 10 grmB. of sodium hydroxide
are dissolved in 100 cc* of water ; to this 5 grms. of hydraziti are
added, and the whole shaken ; laatly, alcohol of 96-9T per cent, ia
added in equal volume, the mixture shakeu, allowed to stand for two
hours and liltered ; the liltrate is used as the reagent.
B C «
^"u;f^"-ff
r-r-ry-i '"tK-
E b^
F
^^» ■ ! r-
«W
>GCA
^t^-
SS&
--K
" tAA
Of yhRfmOglobin,
•^ Hifethnsniogloljjiti nud
OxyhiDiuogt&bJIn.
-^ HurtnoKlobln.
~ Acid Hsmailn.
, AlkiUlnc HjetDttln
(Aleoholto loliitioQ).
-1 Biemocibrdinogflii
{fkcui iolutloti).
■-, Uji*Hmtoporpii|Tin
t&Hullue •olDtloii).
-^ SulphsQiogtciliUu
Cnj bon- inoiJ03fldB'
hmmuglublu^
The reagent can lie added to one or two drops of blood in a test
tube, or be used aa a solvent for stains on wood, irun, and so forth.
It may altto be used jia a reagent for blood in urine, milk, and other
fluids, if the blood is small in quantity. In uon-albuminous ^uidsj it
m advisable to add a little albumin, acidify with acetic acid, beat to
boiling, and treat the separated congulum with the reagent*
The solution is of a fine purple-red colour ; m\d wliether the colouring
* ^'Einueaes Re&geD?^zum Nacbwtii» der Vf^mchiedt^nen BIutf&rbetoffB oder d«r
Zei^tsaugHpitidtikto derMlbon,'' ZcU / mMlyiMi^ Ckemie, 1904, 539.
62 POISONS: THEIR KPFBCTS AND DBTECTION. [§ 3$.
matter be derived from blood, oxyhsemoglobin, metbsemoglobin, or
hsDmatin, the two bands of hssmochromogen can be seen in the suitably
diluted solution; if the solution is shaken up with air, the spectrum
changes into the oue-banded alkaline hsematin (fig. 6), as seen in an
alcoholic solution, but on standing the two-banded spectrum of haemo-
chromogen slowly comes back ; these changes can be traced with the
naked eye, for the red solution, on shaking with air, takes a greenish
tint, and then slowly returns back into purple-red. There is no dye
which possesses similar properties, hence this naked-eye change is
almost sufficient to identify a red organic substance as blood. HsBmato-
porphyrin (figs. 8 and 9) is obtained by heating blood carefully for a
short time with sulphuric acid of a. certain concentration.
Sulphsemoglobin (fig. 10) is obtained by treating diluted blood with
sulphuretted hydrogen in the presence of air ; it gives a very definite
band (619'8) ; at the same time the oxy haemoglobin bands fade ; this
is the appearance which may be seen in the blood of persons poisoned
by hydric sulphide.
The spectrum of carbon monoxide haemoglobin (fig. 11) is that of
oxyhaemoglobin with the bands slightly displaced towards the violet
end.
Formanek, in researches on guinea-pigs, has shown that the maximum
displacement only occurs when the blood has attained a certain amount
of saturation with the gas.
In four animals the blood was examined during life, when the
convulsions began, and after death, with the following results : —
In oonyulBive stage. After death.
Centre of Centre of Centre of Centre of
chief band. enbeidiary chief band. Bubsidiary
band. band.
(1) X576 X640 A 672-6 X 688-3
(2) \576 x640 \ 672-7 A 638-6
(3) A 676 A 640 A 673-0 \ 688-7
(4) ... ... A 672-7 A 688-6
The blood in CO poisoning has also other characteristics. It is of a
peculiar florid vermilion colour, a colour that is very persistent> lasting
for days and even weeks.
Normal blood mixed with 30 per cent, potash solution forms greenish
streaky clots, while blood charged with CO forms red streaky clots.
Normal blood diluted to 50 times its volume of water, and then
treated successively with yellow ammonium sulphide in the proportion
of 2 to 25 c.c. of blood, followed by 3 drops of acetic acid, gives a
grey colour, while CO blood remains bright red. CO blood shaken with
4 times its volume of lead acetate remains red, but normal blood becomes
brown.*
* M. Kubner, Arch, Hyg,, x. 897.
§ 3S-] SPECTROSCOPIC APPEARANCES OF BLOOD. 63
SoIutionB of platinum chloride or zino chloiride give a bright rad
colour with CO blocd; normal blood is coloured brown or very dark
brown,
Phoapho-molybdic acid or 5 per cent, phenol gives a carmine-coloured
precipitate with CO blood, but a reddish -brown precipitate with normal
blood (sensitive to 16 per cent.),
A mixture of 2 e.c, of dilute acetic acid and 15 o.c. of 20 per cent,
potassio ferrocyanide solution added to 10 ox, of CO blood produces an
intense bright red ; normal blood becomes dark brown.
Four parts of CO blood, diluted with 4 parts of water and shaken
with 3 vols, of 1 per cent* tannin solution, become at first bright red
with a bluish tinge, and remain so petsrateutly. Normal blood, on tht;
other hand, also strikes bright red at first, but with a yellowish tinge )
at the end of I hour it becomes brownish, and finally in 24 hours grey.
This is stated to be delicate enough to detect 00023 per cent, in air.
If blood be diluted with 40 times its volume of water, and 5 drops
of phenyl hydra^in solution be added, CO blood strikes rose-red ; normal
blood grey- violet.*
Gustave Plotrowski f has experimented on the length of time blood
renins CO- The blood of dogs poisoned by this agent was kept in
flaskSf and then the gas pumped out by means of a mercury-pnmp on
the following dates : —
Dwte, Conical, of gu La CO.
Jan. 12,1802, ....... 24*7 per oent
., 20, , 23 "5 „
ft 28| ), ,,,♦,,. 22*8 It
Fek 8 , . ■ . 2D*S
M le 15^5 .,
»» ^, M . . iO-2 „
Mufoh 3i II ■ » m . t I * '9*3 It
n 22, ,, ....... 1-2 ,,
The same dog was buried on the 1 2th of January^ and exhumed on
March 26th, and the gas pumped out from some of the blood ; this gas
gave 117 per cent, of 00 ; hence it is clear that burial preserves CO
blood from change to a certain extent.
N. Grehant I treated the poisoned blood of a dog wttl^ acetic aeid,
and found it evolved 14*4 c,c, CO from 100 c.c. of blood.
Stevenson, in one of the cases detailed at p. 72, found the blood in
the right auricle to contain 0*03 per cent, by weight of CO*
(2) Preparation of HagniAtui Crystals — (Teichmann^s crystals). — A
• A. Welzel. Cff^tin ^n^d, ff^w.^,, xivii. 732-734,
t C&mpt. Read. S&c. dU£ioL, v, 433.
X Opmpi, Mind., qvL 2$^,
64 POISONS : THEIR EFFECTS AND DETECTION. [§ 35.
portion of the borax solution is diluted with 5 or 6 parts of water, and
one or more drops of a 5 or 6 per cent, solution of zinc acetate added,
so long as a brownish-coloured precipitate is thrown down. The
precipitate is filtered off by means of a miniature filter, and then
removed on to a watch-glass. The precipitate may now be dissolved
in 1 or 2 c.c. of acetic acid, and examined by the spectroscope it will
show the spectrum of hsematin. A minute crystal of sodium chloride
being then added to the acetic acid solution, it is allowed to evaporate
to dryness at the ordinary temperature, and crystals of hsBmatiu hydro-
chlorate result. There are other methods of obtaining the crystals.
When a drop of fresh blood is simply boiled with glacial acetic acid,
on evaporation, prismatic crystals are obtained.
HsBmatin is insoluble in water, alcohol, chloroform, and in cold dilute
acetic and hydrochloric acids. It may, however, be dissolved in an
alcoholic solution of potassic carbonate, in solutions of the caustic
alkalies, in boiling acetic and hydro-
chloric acids, and in Riegler's re-
agent. Hoppe-Seyler ascribes to
^ m the crystals the formula C^gH^QNg
m 30 Fe20io2HCl. Thudichum considers
^^ ^^ that the pure crystals contain no
"'^^ ' ^ chlorine, and are therefore those of
^ hsBmatin. It is the resistance of
%0 W / the hajmatin to decomposition and
T^^ V/ to ordinary solvents that renders it"
possible to identify a certain stain
to be that of blood, after long periods of time. Dr. Tidy seems to have
been able to obtain blood reactions from a stain which was supposed to
be 100 years old. The crystals are of a dark red colour, and present
themselves in three forms, of which that of the rhombic prism is the
most common (see fig.). But crystals like 6, having six sides, also
occur, and also crystals similar to c.
If the spot under examination has been scraped off an iron implement
the hsematin is not so easily extracted ; but Dragendorff states that borax
solution at bOt" dissolves it, and separates it from the iron. Felletar has
also extracted blood in combination with iron rust, by means of warm
solution of caustic potash, and, after neutralisation with acetic acid, has
precipitated the h»min by means of tannin, and obtained from the
tannin precipitate, by means of acetic acid, Teichmann's crystals. A
little of the rust may also be placed in a test tube, powdered ammonium
chloride added, also a little strong ammonia, and after a time filtered ;
a small quantity of the filtrate is placed on a slide with a crystal of
■"^^-'ifu chloride and evaporated at a gentle heat, then glacial acetic acid
§36.]
SPECTROSCOPIC APPEARANCK3 OF BLOOD.
6S
added and allowed to cool ; iu this way hiemiD crystals ha^e been
obtained from a crowbar fifty days after having been blood-stained**
(3) GuaiECiim Test. — This tent depends upon the fact that a eolution
of boemoglobin develops a beautiful blue colour if brought into contact
with fresh tinctnre of gtiaiacnm and peroxide of hydrogen. The simplest
way to obtitin this reaction is to moisten the suspected stain with distilled
water ; after allowing sufficient time for the water to dissolve out some
of the blood constituents, moisten a bit of filter paper with the weak
solution thus obtained ; drop on to the moist space a single drop of
tinctnre of gnaiaoum which has been prepared by digesting the inner
portions of guaiacura resin in alcohol » and which has been already tested
on known blood, so as to ascertain that it is really good and eOjcient for
the purpose; and, lastly, a few drops of peroxide of hydrogen, Dragen-
dorff uaes hiii honix solution, and, after a little dilution with water^ adds
the tinctnre and then Heunef eld's turpentine solution, which is composed
of equal parts of absolute alcohol, chlorofornip and French turpeuline,
to which one part of acetic aeid has been added. The chloroform
separates, and, if blood was present, is of a blue colour
g 36. To prove by chemical and physical methods that a certain
stain is that of blood is often only one step in the inquiry, the next
question being whether the blood ts that of man or of animals. The
blood corpuscles of man are larger than those of any dom^tic animal
inhabiting Europe. The diameter of the average red blood corpuscle is
about the yi^ of a millimetre, or 7 '9 ^t The corpuscles of man and
of mammala, generally speaking, are round, those of bLrds and reptiles
oval, so that there can be no confusion between man and bii^s, fishes
or reptiles ; if the corpuscles are circular in whape the blood will be
that of a mammal. By careful measurements. Dr. Eichardaon, of
Peunsylvania, affirms that it is quite po«ialble to distinguish human
blood from that of all common animals. He maintains, and it is true,
that, by using very high magnifying powers and taking much trouble,
an expert can satisfactorily identify human hlood if he has some half-
dozen drops of blood from different animals — such as the sbeep, goat,
horse, dog, cat, etc, all fresh at hand for comparison, and */ the human
blood i$ normal. However, w^hen we come to the blood of persona
suffering from disease, there are changes in the diameter and even the
form of the corpuscles which much complicate the matter; while, in
blood-stains uf any age^ the blood corpuscles, even with the most
artfully -contrived solvent, are so distorted in shape that he would be a
bold man who should venture on any definite conclusion aa to whether
• BHi. Med, Journ., Feb, 17, 1894*
t 1^ of aa ia«rb ; Iho Greek letter |i b the mkrchmilliiiteti^, ov 1000th of i
lailUmetr*, '000OS937 inch,
5
(^ POISONS : THEIR EFFECTS AND DETECTION. [§ 36.
the blood was certainly human, more especially if he had to give evi-
dence in a, criminal case.
Neumann affirms that the pattern which the fibrin or coagulum of
the blood forms is peculiar to each animal, and Dr. Day, of Ceelong,
has independently confirmed his researches: this very interesting
observation perhaps has not received the attention it merits.
When there is sufficient of the blood present to obtain a few milligrms.
of ash, it may be possible to distinguish human blood from that of other
common mammals by estimating the relative amounts of potassium
and sodium in the blood. In the blood of the cow, sheep, fowl, pig,
and horse, the sodium very much exceeds the potassium in the ash ;
thus the proportion of potassium oxide to that of sodium oxide in the
blood of the sheep is as KjO : NajO : : 1 : 6 ; in that of the cow, as 1 : 8 ;
in that of the domestic fowl, as 1:16; while the same substances in
human blood are sometimes equal, and vary from 1:1 to 1:4 as
extremes, the mean numbers being as 1 : 2*2. The potassium is
greater in quantity in the blood corpuscles than in the blood serum ;
but, even in blood serum, the same marked differences between the
blood of man and that of many animals is apparent. Thus, the pro-
portion of potash to soda being as 1 : 10 in human blood, the proportion
in sheep's blood is 1 to 15*7 ; in horse's serum as 1 to 16*4 ; and in the
ox as 1 to 17. Since blood, when burnt, leaves from 6 to 7 per
thousand of ash, it follows that a quantitative analysis of the relative
amounts of potassium and sodium can only be satisfactorily effected
when sufficient of the blood is at the analyst's disposal to give a weigh-
able quantity of mineral matter. On the other hand, much work
requires to be done before this method of determining that the blood is
either human, or, at all events, not that of an herbivorous animal, can
be relied on. We know but little as to the effect of the ingestion of
sodium or potassium salts on either man or animals, and it is possible —
nay, probable — that a more or less entire substitution of the one for
the other may, on certain diets, take place. Bunge seems in some
experiments to have found no sodium in the blood of either the cat or
the dog.
The source from which the blood has emanated may, in a few cases,
be conjectured from the discovery, by microscopical examination, of
hair, or of buccal, nasal, or vaginal epithelium, etc., mixed with the
blood-stain.
Biological Test for Human Blood. — A test for distinguishing human
from animal blood has been devised by Jules Ogier and Herscher.*
The blood-spot is dissolved in water, and two or three cubic centimetres
of the solution are placed in test tubes 10 to 12 cm. long and 4 to 5
* Ann, Chim, Anal, 1902, vii. 241.
§ 36.] SPECTROSCOPIC APPEARANCES OF BLOOD. 67
cm. diameter. In similar tubes is placed the same quantity of control
solutions of human, pigs, oxen, dogs, or other animals' blood, of
approximately the same strength.
To each tube is now added 10 drops of serum from rabbits which
have been repeatedly subcutaneously injected with human blood.
The tubes are placed in water at 37-40* C. ; after 10 minutes
human blood will show a precipitate, which will be copious after half an
hour. A slight precipitate may be neglected. This test may be also
applied to old blood-stains. A precipitate is also said to be obtained
with blood from monkeys. Care should be taken to neutralise the blood
if it be acid, as it will, if acid, always give a precipitate. When blood
has been dried. on certain materials, such for instance as thick polished
yellow leather, it has been found impossible to get the reaction.
PART III.— POISONOUS GASES: CARBON MONOXIDE—
CHLORINE-HYDRIC SULPHIDE.
I. Carbon Monoxide.
^ 37. Carbon monoxide, CO, is a colourless, odourless gas of 0*96709
sp. gravity. A litre weighs 1*25133 grm. It is practically insoluble
in water. It unites with many metals, forming gaseous or volatile
compounds, e.g. nickel carbon oxide, Ni(C04), is a fluid volatilising
at 40*. These compounds have, so far as is known, the same effects
as CO.
Whenever carbon is burned with an insufficient supply of air, CO
in a certain quantity is produced. It is always present in ordinary
domestic products of combustion, and must be exhaled from the
various chimneys of a large city in considerable volumes. A ** smoky "
chimney or a defective flue will therefore introduce carbon monoxide
into living-rooms. The vapour from burning coke or burning char-
coal is rich in carbon monoxide. It is always a constituent of coal
gas; in England the carbon monoxide in coal gas amounts to about
8 per cent Poisoning by coal gas is practically poisoning by carbon
monoxide. Carbon monoxide is also the chief poisonous constituent
in water gas.
Carbon monoxide poisoning occurs far more frequently in France
and Germany than in England ; in those countries the vapour evolved
from burning charcoal is a favourite method of suicide, on account of
the supposed painlessness of the death. It has also occasionally been
used as an instrument of murder. In this country carbon monoxide
poisoning mainly takes place accidentally as the e£fect of breathing coal
gas ; possibly it is the secret and undetected cause of ill-bealth where
chimneys " smoke " : and it may have something to do with the sore
throats and debility so often noticed when persons breathe for long
periods air contaminated by small leakages of coal gas.
The large gas-burners (geysers) emit in burning under certain con-
ditions much carbon monoxide. It has been proved by Grehant * that
• Compt Bend. Soc. de Biol., ix. 779-780.
68
38.]
CARBON MONOXIDE,
69
a buQBen biimer *Htt below" also evolves large quantitlea of the same
poiaotioufi gas.*
§38* Symptoms.— Nearly all the experieuce with regard to the
symptoms produced by carbon monoiide is derived from breathing not
the pure gas, but the gas diluted by air, by hydrogeu or by curburetted
hydrogen, as in coal gas, or mixed with large quantities of earbon
dioiide. Two assistants of Christison breathed the pure gas: the one
took from two U* three iubalations; he inamediately became giddy,
shivered, had headache, and then became unconscious. The second
took a bigger dose, for, after emptying his lungs as much as possible,
he took from three to four inhalations; he fell back paralysed, became
unconscious, and remained half au hour insensible aud had the appear-
ance of death, the pulse being almost extinguished. He was treated
with inhalations of oxygen, but he remained for the rest of the day
extremely ill ; he had convulsive muscular movements, stupor, headache,
and quick irregular pulse; on this passing away he still suffered from
nausea, giddiness, alternate feeling of heat and chilliness, with some
fever, and in the night had a restless kind of sleep. The chemist
Chenot was accidentally poisoned by the pure gas, aud is stated to have
fell as if struck by lightning after a single inspiration, and remained
for a quarter of an tiour uuconsoious. Other recorded cases have shown
very similar symptoms-
The pulse is at the onset large, full and frequent; it afterwards
becomes small, slow and irregular. The temperature sinks from 1° to 3**
C. The respiration at first slow, later becomes rattling. As vomiting
occurs often when the sufferer is insensible, the vomited matters have
beeu drawn by inspiration into tlie trachea and even into the bronchi,
80 that death takes place by su location.
The fatal coma uiay lastj even when tlie person has been removed from
the gas, from hours to days. Coma for three^ four and live days from
carbon monoxide has been frequently observed. The longest case on
record is that of a person who was comatose for eight days, and died on
the twelfth day after the fatal inhalation. Consciousness in this case
returned, but the patient again fell into the stupor and died.
The slighter kinds of poisoning by carbon monoxide, as in the
Staffordshire case recorded by Dr. lieid {p. 73 )j in which for a long time
a much diluted gas has been breathed, produce pronounced headache
and a feeling of ill-health and malaise^ deepening, it may be, into a fatal
slumber unless the person is leraoved from the deadly atmosphere. To
the headache generally succeeds nausea, a feeling of oppression in the
* Tbori>e (X Chtm, iioc.^ xxxiii S!8^ IOCS) hm ^Uowd thut au ordinary bunaen
hiuner heating a B«ud tiay «vdv«i about 0D22 of ■ cubic foot of Cirboa moaoiide
piThour*
70 POISONS : THEIR EFFECTS AND DETECTION. [§ 39-
temples, a noise in the ears, feebleness, anxiety, and a dazed condition
deepening into coma. It is probably true that charcoal vapour is com-
paratively painless, for when larger amounts of the gas are breathed the
insensibility comes on rapidly and the faces of those who have suc-
cumbed as a rule are placid. Vomiting, without being constant, is a
frequent symptom, and in fatal cases the fseces and urine are passed in-
voluntarily. There are occasional deviations from this picture ; tetanic
strychnine-like convulsions have been noticed, and a condition of excite-
ment in the non-fatal cases as if from alcohol ; in still rarer cases tem-
porary mania has been produced.
In non-fatal but moderately severe cases of poisoning sequelsB follow,
which in some respects imitate the sequelsB seen on recovery from the
infectious fevers. A weakness of the understanding, incapacity for
rational and connected thought, and even insanity have been noticed.
There is a special liability to local inflammations, which may pass into
gangrene. Various paralyses have been observed. Eruptions of the
skin, such as herpes, pemphigus and others. Sugar in the urine is an
almost constant concomitant of carbon monoxide poisoning.
§ 39. The poisonous action of carbon monoxide is, without doubt,
due to the fact that it is readily absorbed by the blood, entering into a
definite chemical compound with the haemoglobin ; this combination is
more stable than the similar compound with oxygen gas, and is therefore
slow in elimination.
Hence the blood of an animal remaining in an atmosphere containing
carbon monoxide is continually getting poorer in oxygen, richer in carbon
monoxide. Grehant has shown that if an animal breathes for one hour
a mixture of 0*5 carbon monoxide to 1000 oxygen, the blood contains at
the end of that time one-third less oxygen than normal, and contains
152 times more carbon monoxide than in the mixture. An atmosphere
of 10 per cent, carbon monoxide changes the blood so quickly, that
after from 10 to 25 seconds the blood contains 4 per cent, of carbon mon-
oxide, and after from 75 to 90 seconds 1 8 '4 per cent. Breathing even
for half an hour an atmosphere containing from 0*07 to 0*12 per cent,
carbon monoxide renders a fourth part of the red corpuscles of the blood
incapable of uniting with oxygen.
The blood is, however, never saturated with carbon monoxide, for
the animal dies long before this takes place.
The characteristics of the blood and its spectroscopic appearances
are described at p. 62.
Besides the action on the blood there is an action on the nervous
system. Robert,* in relation to this subject, says : — " That CO has a
direct action on the nervous system is shown in a marked manner when
* Lehrbtich der IntoasiccUumen, 526.
S 40O
CARBON ftfOKOXiDE.
n
an atmoaphere of oijgen, with at least 20 per cent* carbon oxide, is
breathed ; for in the first minute there ia acute cramp or total paralysiB
of the limbs, when the blood in no way attains the saturation auflitiientlj
great to account for such symptoms. Geppert has^ through a special
research, shown that an animal suffocated by withdrawal of oxygen
increases the number and depth of the respirations; but when the
animal h submitted to CO, in which case there is quite as much a with-
drawal of oxygen as in the former case, yet the auimal is not in a condition
to strengthen its respiratory movements ; Geppert hence rightly concludes
that CO must have a primary specific injurious action on the nerve
centres. 1 (Kobert) am inclined to go a step further, and, on the ground
of unpublished researches, to maintiiin that CO not only affects in-
juriaualy the ganglion cells of the brain, but also the peripheral nerves
{ejj. the phrenic), as well as divers other tissues, as mtiscles and glands,
and that it causes so rapidly such a high degree of degeneration as not
to be explained through simple slow suBocation ; even gangrene may he
caused."
It ia this rapid degeneration which is the cause of the enormous
increase of the products of the decomposition of albumin, found experi-
mentally in animals.
§ 40. Poflt-mortMn Appearances. — The face, neck, chest, abdomen
are frequently covered with patches of irregular form and of clear rose-
red or bluish-red colour ; these patches are not noticed on the back, and
thus do not depend upon the gravitation of the blood to the lower or
most dependent part of the body ; similar red patches have been noticed
in poisoning by prussic acid ; the catise of this phenouienon is ascribed
to the paralysis of the small artenes of the skin, which, therefore,
become injected with the changed blood, The blood throughout is
generally fluid, and of a fine peculiar red colour, with a bluish tinge.
The face is mostly calm^ pale, and there is seldom any foam about the
iipe. Putrefaction is mostly remarkably retarded. There Is nearly
always a congestion of some of the internal organs ; sometimes, and
indtsed usuaUy, the membranes of the brain are strongly injected ;
sometimes the congestion is mainly in the lungs, which may be
ccdematous with efl\isioo ; and in a third class of casee the congestion is
most marked in the abdominal cavity.
The right heart is commonly filled with blood, and the left aide
contains only a little blood.
A rabbit that Kionka poisoned twelve times in as many days with
carbon monoxide, and through artificial reis pi ration restored, was tivo
days later killed and examined r there were hjiemorrhages in both lungs
occlusion of vessels and haemorrhagic infarcti in the intestines, and
haemorrhages in the liver. In aome cases there have been notioed|
72 POISONS : THEIR EFFECTS AND DETECTION. [§ 41.
small areas of softeuiug in the human brain in oases of CO poisoning :
these may be explained by the light of the appearances just described
as caused by small thrombi in the brain vessels.
Poisoning by a small dose of carbon monoxide may produce but few
striking changes, and then it is only by a careful examination of the
blood that evidence of the real nature of the case will be obtained.
§ 41. Mass poisonings by Carbon Monoxide. — An interesting series
of cases of poisoning by water gas occurred at Leeds in 1889, and have
been recorded by Dr. Thos. Stevenson.*
Water gas is made by placing coke in a vertical cylinder and heating
the coke to a red heat. Through the red-hot coke, air is forced up
from below for ten minutes ; then the air is shut o£f and steam passes
from abo\re downwards for four minutes ; the gas passes through a
scrubber, and then through a ferric oxide purifier to remove SHj. It
contains about 50 per cent, of hydrogen and 40 per cent, of carbon
monoxide, that is, about five times more carbon monoxide than coal
gas.
On November 20, 1889, two men, R. French and H. Fenwick, both
intemperate men, occupied a cabin at the Leeds Forge Works; the
cabin was 540 c. feet in capacity, and was lighted by two burners, each
burning 5*5 c. feet of water gas per hour ; the cabin was warmed by a
cooking stove, also burning water gas, the products of combustion
escaping into the cabin. Both men went into the cabin after breakfast
(8.30 A M.). French was seen often going to and fro, and Fenwick was
seen outside at 10.30 a.m. At 11.30 the foreman accompanied French
to the cabin, and found Fenwick asleep, as he thought. At 12.30 p.m.
French's son took the men their dinner, which was afterwards found
uneaten. At that time French also appeared to be asleep ; he was
shaken by his son, upon which he nodded to his son to leave. The
door of the cabin appears to have been shut, and all through the morn-
ing the lights kept burning ; no smell was experienced. At 2.30 p.m.
both the men were discovered dead. It was subsequently found that
the stove was unlighted, and the water gas supply turned on.
What attracted most attention to this case was the strange incident
at the post-mortem examination. The autopsies were begun two days
after the death, November 22, in a room of 39,000 c. feet capacity.
There were present Mr. T. Scattergood (senior), Mr. Artliur Scattergood
(junior), Mr. Hargreaves, three local surgeons, Messrs. Brown, Loe and
Jessop, and two assistants, Pugh and Spray. Arthur Scattergood first
fainted ; Mr. Scattergood, senior, also had some peculiar sensations, viz.,
tingling in the head and slight giddiness ; then Mr. Pugh became faint
and staggered ; and Mr. Loe, Mr. Brown, and Mr. Spray all complained.
* Quy*8 Hospital Reports, 1889.
§41]
CARBON UONOXIDB.
73
These symptoms were not producedj aa was at first though t^ bj some
TolatiJe gas or vapour erannatiiig from the bodies of the poisoned men,
biit> fts subsequently disco vereci, admitted of a very simple eicplanation ;
tight burners in the room were turnud partly on and not ligbted^ and
each of the eight burners poured water gas into the room.
In 1891 occurred some crises of poiaoning * by CO which are probably
unique. The cases in question happened in January in a family at
Darlaston, The first sign of any thing unusual having iiappenod to the
family most affected was the fact that up to 9 a.m., Sunday morning,
January 18, none Cff the family had been seen about, The house was
broken into by the ueighbourB ; and the fatheTj mother^ and three
children were found in bed apparently asleep, and all efforts to rouse
them utterly failed. The medical men summoned arrived about 10 A«if»
and found the father and mother in a state of complete unoonsciousnees,
and two of the chthlren, aged 1 1 and 14 years, suffering from piin and
sickness and diarrhoea ; the third child had by this time lieeu removed
to a neighbouring cottage,
Dr* Partridge, who was in attendaticCj remained with the patients three
hours, when he also began to suffer from headache j while others, who
remained in the house longer, suffered niore severely and complained of
au indefinite feeling of exhaustion. These symptoms pointed to some
exciting cause associated with the snrroiuidings of the cottage ; conse-
quently, in the afternoon the two children were removed to another
cottage, and later on the father and mother also^ All the patients, with
the exception of the mother, who was still four days after wards suffering
from the effects of an acute attack, had completely recovered* The
opinion that the illness was owing to some local canse was subsequently
strengthened by the fact that two canaries and a cat hjid died in the
night in the kitchen of the cottage ; the former in a cage and the latter
in a cupboard, the door of which was open. Also in a house on the
opposite side of the same road, the occupants of which had for some time
suffered from headache and depression, two birds were found dead in
their cage in the kitchen* It is important to notice that all these animals
died in the respective kitchens of the cottages, and, therefore, on the
ground floor, while the families occupied the first floor.
The father stated that for a fortnight or three weeks previous to the
serious illness, he and the whole family had complained of severe frontal
headache and a feeling of generjil depression. This feeling was continuous
day and night in the case of the rest of the family, but in his case,
during the day, after leaving the house for his werk^ it gradually passed
* ** Notes ou cAses of poiaooing by the inhaUtiou of carbou monoxide,** by Dr,
Otqige Bmd, Mediciil Officer of Health » County of StAiford, Putlie Mtalth^ vol, iil
Ml.
74 POISONS : THEIR EFFECTS AND DETECTION. [§ 42.
off, to return again during the night. The headaches were so intense
that the whole family regularly applied vinegar rags to their heads, on
going to bed each night during this period, for about three weeks.
About 2 o'clock on Sunday morning the headaches became so severe
that the mother got out of bed and renewed the application of vinegar
and water all round, after which they all fell asleep, and, so far as the
father and mother were concerned, remained completely unconscious
until Monday morning.
A man who occupied the house opposite the house tenanted by the
last-mentioned family informed the narrator (Dr. Beid) that on Sunday
morning the family, consisting of four, were taken seriously ill with a
feeling of sickness and depression accompanied by headache ; and he
also stated that for some time they had smelt what he termed a ''fire
stink " issuing from the cellar.
The cottage in which the family lived that had suffered so severely
was situated about 20 or 30 yards from the shaft of a disused coal mine,
and was the end house of a row of cottages. It had a cellar opening
into the outer air, but this opening was usually covered over by means of
a piece of wood. The adjoining house to this, the occupants of which
had for some time suffered from headache, although to a less extent, had
a cellar with a similar opening, but supplied with an ill-fitting cover.
The house on the opposite side of the road, in which the two birds were
found dead, had a cellar opening both at the front and the back ; but
both these openings, until a little before the occurrence detailed, had
been kept closed. The cellars in all cases communicated with the houses
by means of doors opening into the kitchens. According to the general
account of the occupants, the cellars had smelled of *'fire stink/' which,
in their opinion, proceeded from the adjoining mine.
The shaft of the disused mine communicated with a mine in working
order, and, to encourage the ventilation in this mine, a furnace had for
some weeks been lit and suspended in the shaft. This furnace had set
fire to the coal in the disused mine and smoke had been issuing from
the shaft for four weeks previously. Two days previous to the inquiry
the opening of the shaft had been closed over with a view to extinguish
the fire.
Dr. Keid considered, from the symptoms and all the circumstances of
the case, that the illness was due to carbon monoxide gas penetrating into
the cellars from the mine, and from thence to the living and sleeping
rooms. A sample of the air yielded 0'015 per cent, of carbon monoxide,
although the sample had been taken after the cellar windows had been
open for twenty-four hours.
§ 42. Penetration of Carbon Monoxide. — ^It is not always sufficient
to detect carbon monoxide in the blood to establish death from that
§43]
GASBON MONOXIDE.
75
gaa, for circHmetaRcea oaaj arise under which a corpse is exposed to
either coal gas or carhon monojidy gas. Wachholz and Lemberger*
placed the bodies of stitl-bom iiifantB in gla^ vessels and pusaed CO
throng It the ve^ds ; in half an hour the blue cadaveroufi spots beoame
bright red, and the blood exhibited the spectrum of carbon monoiido
hicmoglobin.
DoDieuic Mirto made t^ine eiperimenls of a Itke nature and
concluded —
(1) That in post-mortem ikision the anterior part of the liver
was rich in carbon monoxide, but in poisoning the gas is
equally diitused.
(2) In poBt*mortem diffusion the pia mater scarcely ever contains
carbon monoxide, the choroid plexus never.
(3) The deep parts of the body contain less tbati the BuperRoial in
the case of diffusion, the reverse is the case in poisoning.
Strausamann and Schulz, in a research on seven adult bodies, fairly
well agree with Mirto, save that they believe that, given sufficient
time, there is no part of the body into which carbon monoxide will not
penetrate.
g 43. Detection of Carbon Monoxida — it naay often be necessary to
detect carbon monoxide in air and to estimate its amount. The detection
in air, if the carbon monoxide is in any quantity, is easy enough ; but
traces of carbon monoxide are ditRcult. Where amounts of carbon
monoxide in air from half a per cent, upwards are reasonably presumed to
exist, the air is metisured in a gas measuring apparatus and passed into an
absorption pipette charged with alkaline pyrogallic acid, and when all the
oxygen has been abstracted, then the residual nitrogen and gases are
submitted to an ammoniacal solution of cuprous chloride.
The solution of cuprous chloride is prepared by dissolving 10'3 gmis,
of copper oxide in 150 c,c- of strong hydrochloric acid and hllirig the flask
with copper t^irnings ; the copper reduces the cupric chloride to cuprous
chloride ; the end of the reduction is known by the solution becoming
colourless. The colourless acid solution is poured into some 1500 c.c, of
water, and the cuprous chloride settles to the bottom as a precipitate*
The supernatant fluid is poured off as completely as possible and the
precipitate washed into a quarter litre flask, with 100 to 150 c.e, of dis*
tilled «rater and ammonia led into the solution until it becomes of a pale
blue colour The solution is made up to 200 c.c. so as to contain about
7^3 grros. j)er cent* of cuprous chloride.
Such a solution is an absorbent of carbon monoxide ; it also absorbs
ethylene and acetylene,
• *' De U jveDtitratioB de Toxyde de Cartxiti,'* Anti. d'lf^tfne jmbttque^ 4"»»
itr., iii. 175,
7^ i>oi80Ns : xaaiR effkcts and detection. [§ 44.
A solution of cuprous chloride which has absorbed CO gives it up on
being treated with potassic bichromate and acid. It has been proposed
by Wanklyn to deprive large quantities of air of oxygen, then to absorb
any carbon monoxide present with cuprous chloride, and, lastly, to
free the cuprous chloride from the last gas by treatment with acid
bichromate, so as to be able to study the properties of a small quantity
of pure gas.
A more reliable method to detect small quantities of carbon monoxide
is, however, as proposed by Hempel, to absorb it in the lungs of a living
animal.
A mouse is placed between two funnels joined together at their
mouths by a band of thin rubber ; one of the ends of the double funnel
is connected with an aspirator, and the air thus sucked through, say for
half an hour or more; the mouse is then killed by drowning, and a
control mouse, which has not been exposed to a CO atmosphere, is also
drowned ; the bodies of both mice are cut in two in the region of the
heart, and the blood collected. Each sample of blood is diluted in the
same proportion and spectroscopically examined in the manner detailed
at p. 60. The limit of the test lies at about 0*03 per cent, when large
volumes of the gas are used.
A more delicate reaction, and one which may be used for the estima-
tion of CO, is that of Nicloux and Gautier. The gas to be examined is
freed from unsaturated hydrocarbon by shaking with fuming sulphuric
acid, and from carbon dioxide by passing over soda-lime; it is then
passed over iodine pentoxide heated by means of an oil-bath to a
temperature of from 150'-200'*. The iodine pentoxide is decomposed in
accordance with the equation IgOg -H 5C0 = 10 + 500^, the liberated iodine
is caught in 10 per cent, potassium iodide, and may be determined by
N
=^r^ sodium thiosulphate. Thorpe,* using this method, has obtained
good results with as little as '0025 per cent, of carbon monoxide.
IL— Chlorine.
§ 44. Chlorine is a yellow-green gas, which may, by cold and pressure,
be condensed into a liquid. Its specific gravity is, as compared with
hydrogen, 35*37 ; as compared with air, 2*45 ; a litre under standard
conditions weighs 3*167 grms. It is soluble in water.
The usual method of preparation is the addition of hydrochloric acid
to bleaching powder, which latter substance is hypochlorite of lime
mixed with calcic chloride and, it may be, a little caustic lime. Another
* J.CS,, Ixxxiii 318, 1908.
§ 45. 46]
CHlORmX.
7f
methoci ie to treat mangnDede dioxide with hjdrochlnric acid or to aet
Oil manganese dioiide and common salt wttb stjJpbum licid.
Accidents are liable to occur with chlorine gas from its extonsiYe uae
as a disinfectant and also in its manufacture. In the " Weldon " process
of manufacturing bleaching powder, a thick lajer of lime is placed on
the floor of special chambers ; chlorine gaa is [la^ed into these chambers
for about four days ; then the gas ia turned off ; the iinabeorbed gas is
drawn off by an exhaust or absorbed by a lime distributor and the doors
opened. Two hours afterwards the men go in to pack tlje powder.
The packersj in order to he able to work in the chamberB, wear a
respirator consisting of about thirty folds of damp flannel ; this is tightlj
bound round the mouth with the no&trils free and resting upon it. The
men are obliged to inhale the breath through the flannel and exhale
through the nostril, otherwise thej would, in technical jargotii be
"gaased." Some also wear goggles to protect their eyes. Notwith-
standing these precautions they suffer generally from chest complaints.
g 45, Effects. — Free chlorine, in the proportion of 0*04 to 0^6 per
thouaandj taken into the lungs is dangerous to life^ ^ince direetlj
chlorine attacks a moist mucous membrane, hydrochloric acid is formed.
The effects of chlorine can hardly be diflTerentiated from hydrochloric
acid gas, and Lehmann found that 1^5 per thousand of this latter gas
aflfected animals, causing at once uneasiness, evidence of pain with gr^t
dyspnoea, and, later, coma. The eyes and the mucous membrane of the
uose were attacked^ Anatomical changes took place in the cornea^ as
evidenced by a wliite opacity.
In cases that recovered, a purulent discharge came from the nostrils
with occasional necrosis of the mucous membrane. The symptoms in
man are similar ; there is great tightness of the breath, irritation of the
nose and eyes, cough and, with small repeated dtjses, bronchitis with all
its attendant evils. Bleaching powder taken by the mouth is not so
deadly, HertvTig has given 1000 grms. to horses, 30 grms, to sheep and
goats^ and 15 grms. to dogs without producing death. The symptoms
in these cases were quiekeuing of the puUe and respiration, increased
peristaltic action of the bowels, and a stimulation of the kidney secretion.
The urine smelt of chlorine.
FoBt-mortem Appeara£ices.^Hyper(cmiaof the lungs, with <wchy-
mosee and pneumonic patches, with increased secretion of the bronchial
tubes. In the mucous membrane of the stomach, eechymoses* The
alkalescence of the blood is diminished and there may be eitemal signs
of bleaching. Only exceptionally has any chlorine smell been perceived
in the internal organs,
I 46. Detection of Free Chlorine. — The usual method of detection ia
to prepare a solution of iodide of potassium and starch and to soak strips
78 POISONS : THEIR BPFECTS AND DETECTION. [§ 47, 48.
of filter-paper in this solution. Such a strip, when moistened and
submitted to a chlorine atmosphere, is at once turned blue, because
chlorine displaces iodine from its combination with potassium. Litmus-
paper, indigo blue or other vegetable colours are at once bleached.
To estimate the amount of chlorine, a known volume of the air is
drawn through a solution of potassium iodide, and the amount of iodine
set free determined by titration with sodic hyposulphite, as detailed
at p. 80.
IIL— Hydric Sulphide (Sulphuretted Hydrogren).
§ 47. Hydric sulphide, SHj, is a colourless transparent gas of sp.
gravity 1*178. It bums with a blue flame, forming water and sulphur
dioxide, and is soluble in water ; water absorbing about three volumes
at ordinary temperatures. It is decomposed by either chlorine gas or
sulphur dioxide.
It is a common gas as a constituent of the air of sewers or cesspools,
and emanates from moist slag or moist earth containing pyrites or
metallic sulphides ; it also occurs whenever albuminous matter putre-
fies ; hence it is a common constituent of the emanations from corpses of
either man or animals. It has a peculiar and intense odour, generally
compared to that of rotten eggs ; this is really not a good comparison,
for it is comparing the gas with itself, rotten eggs always producing
SH2 ; it is often associated with ammonium sulphide.
§ 48. Eflfects. — Pure hydric sulphide is never met with out of the
chemist's laboratory, in which it is a common reagent either as a gas or
in solution ; so that the few cases of poisoning by the pure gas, or
rather the pure gas mixed with ordinary air, have been confined to
laboratories.
The greater number of cases have occurred accidentally to men
working in sewers, or cleaning out cesspools and the like. In small
quantities it is always present in the air of towns, as shown by the
blackening of any silver ornament not kept bright by frequent use.
In the construction of a graving dock at Hebburn-on-Tyne, July 1902,
three workmen lost their lives through breathing SHg. They had to
enter a large iron caisson, the excavation at the bottom of which had
reached some old alkali waste, and the water, as subsequent analysis
showed, contained 12*2 volumes per cent, of SHj. The first workman
had been in twenty minutes when screams were heard ; a second man
went to his assistance, shouted and fell to the bottom ; the same fate
befell a third. The post-mortem examination showed the heart normal,
right side flaccid and empty, left hard and firmly contracted. No
odour of hydric sulphide in the body. Lungs pale and oedematous.
§49-1
HTDRIC SULPHIDK.
79
Li^er dark. Blood dark and liquid. The speotroioope aba wed no
earboEk monoxide baods.*
Tt la distinctlj a blood poison, tbe gas uniting witb the alkali of the
bloody and tbe sulphide tbua produced partly decomposing figaiii in the
lung and breathed out as SHj, In one sense it acta m a reducing
agent^ for it robs cells of loose! j bound 0, and therefore kills them by
deprivation of oiygen ; it also attacks labile groups, as it suljstitutes in
the aldehyde group sulphur.
It is a poison for all organisms, even the bacteria of putrefaction
only bearing up to J per cent Lehmannt has studied the effects on
animals; au atmosphere containing from I to 3 per thousand of SH^
kills rabbits and cats witbiu ten minutes ; the symptoms are maioly
convulsions and gre^t dyspncea. An atmosphere containing from 0*4 to
0*8 per thousand produces a local irritating action on the mucous mem-
branes of the respiratory tract, atid death follows from an inflammatory
cede ma of tbe lung preceded by convulsions ; there is also a paralysis of
the nervous centres, Lehmann has recorded the case of three men who
breathed 02 per thousand of SH^; within from five to eight minutes
there was intense irritation of the eyes, nose, and throat, and after
thirty minutes they were unable to bear the atmosphere any longer.
Air containing 0*5 per thousand of SH^ is, according to Lehmann, the
utmost amount that can be breathed ; this amount causes in half an
hour smarting of the eyes, nasal catarrh, dyspncBa, cough, palpitation,
shivering, great mnscular weakness, headache and faintness with cold
Bweats, 0'7 to 0*8 per thousand is dangerous to human life, and from
1 to 1*5 per thousand destroys life rapidly. The symptoms may occur
some little time after the withdrawal of the person from the poisonous
atmosphere ; for example, Ckhn records the case of a student who pre-
pared SII.J in a laboratory and was exposed to the gas for two hours ;
he then went borne to dinner and the symptoms first commeuced in
more than an hour after tbe first breathing of pure air* Taylor | re-
cords an unusual case of poisoning in 1857 at Cleator Moor, Some
cottages bad been built upon iron slag, the slag contained sulphides of
calcium and iron i a heavy storm of rain washed through the slag aud
considerable volumes of SH*, with, no doubt, other gases diffused dur-
ing tbe night through the cottages and killed three adults and three
children.
§ 49. PoBt-mortem Appearances. — Tbe so-called apoplectic form of
SHj poisoning, in which the sufftrer dies witbiu a minute or two, shows
* '* F&tmliti^ to workmen breathing sulphuretted hydrogwa,^ by Tboa. Oliver,
t K, B. Lehmano, Arth. / Fj^ne, xiv., 1S92, 135.
t PrimipltJt and Pr^diee qf M^L JurUp.^ vol. it 122,
8o POISONS : THEIR EFFECTS AND DETECTION. [§ 50.
no special change. The most frequent change in slower poisoning is,
according to Lehmann, cedema of the lungs. A green colour of the
face and of the whole body is sometimes present, but not constant. A
spectroscopic examination of the blood may also not lead to any con-
clusion, the more especially as the spectrum of sulphur methsdmoglobin
may occur in any putrid blood. The pupils in some cases have been
found dilated ; in others not so.
Chronic poisoning. — Chronic poisoning by SH., is of considerable
interest in a public health point of view. The symptoms appear to be
conjunctivitis, headache, dyspepsia and ansemia. A predisposition to
boils has also been noted.
§ 50. Detection. — Both ammonium and hydrio sulphides blacken
silver and filter-paper moistened with acetate of lead solution. To test
for hydric sulphide in air, a known quantity may be aspirated through a
little solution of lead acetate. To estimate the quantity a decinormal
solution of iodine in potassium iodide * solution is used, and its exact
strength determined by d.n. sodic hjrposulphite solution ;t the hypo-
sulphite is run in from a burette into a known volume, e.g. 50 c.c, of
the d.n. iodine solution, imtil the yellow colour is almost gone ; then a
drop or two of fresh starch solution is added and the hyposulphite run
in carefully, drop by drop, until the blue colour of the starch dis-
appears. If now a known volume of air is drawn through 50 c.c. of the
d.n. iodine solution, the reaction I, -h SHj = 2HI -h S will take place, and
for every 127 parts of iodine which have been converted into hydriodic
acid 17 parts by weight of SHg will be necessary; hence on titrating
the 50 o.c. of d.n. iodine solution, through which air containing SH, has
been passed, less hyposulphite will be used than on the previous occa-
sion, each c.c. of the hyposulphite solution being equal to I'll c.c. or
to 1-7 mgrm. of SHj.
* 12*7 gnns. of iodine, 16*6 grms. of potassium iodide, dissolved in a litre of
water.
t 24*8 gnns. of sodic hyposulphite, dissolved in a litre of water.
PART IV.-ACIDS AND ALKALIES.
SULPHUKIC ACID— HYDROCHLORIC ACID— NITRIC ACID-^
ACETIC ACID— AMMOKtA— POTASH— SODA— NEUTRAL
SODIUM, POTASSIUM, AXD AMMONIUM SALTS.
L— Sulphuric Acid*
g 5L Salplmric acid (hydric sulphate, oil of vitriol, H^SO^) o<jcurB
in oommerce in varying degrees of Btrength or dilution ; the etropg sul-
phuric uc id of the matitifaeturer, containhig 100 per cent of real itcid
(H^SO^), has a specific gravity of IS 50, The ordinary brown atdd of
commerce, coloured by organic matter and holding in solution nietatha
impurities, chiefly lead and arsenicj has a specific gravity of about
1*750 ; and containa 67*95 of anhydrous 80^ — 85*42 of hydric sulphate.
There are also weaker acids used in connnerce, particularly in manu-
factories in which sulphuric acid is made, for especial purposes without
rectification. The British PharmacopoBia sulphuric acid is directed
to be of 1'843 specific gravity, which corresponds to 78 '6 per cent.
Bulpburic anhydride, or 98 '8 per cent* of hydric sulphate. The dilute
sulphuric acid of the Pharmacopoeia should have a specific gruvity of
1-094, and is usually said to correspond to 1014 per cent of anhydrous
sulphuric acid ; but according to the tables of Lunge and Isler this
density corresponds to 1 1 '05 per cent* Si\.
The general characters of sulphuric acid are as follows: — When
pure, it is a colourleaSj or, when impurej a dark brown to black, oily
liquid, without odour at common temperatures, of an exceedingly acid
taste, charring most organic tissues rapidly, and, if mixed with water,
evolving much heat. If 4 parts of the strong acid are mixed with 1
part of water at 0', the mixture rises to a heat of 100*; a still greater
heat is evolved by mixing 75 parts of actd with 27 of water
Sulphuric acid is powerfully hygroscopic— 3 parts will, in an
ordinary atmosphere, increase to nearly 4 in twenty*four hours; id
|i 0
82 POISONS: THEIR EFFECTS AND DETECTION. [§ 52-54.
common with all acids, it reddens litmus, yellows cochineal, and changes
all vegetable colours. There is another form of sulphuric acid, ex-
tensively used in the arts, known under the name of "Nordhausen
sulphuric acid," " fuming acid,'* formula HgSgO^. This acid is produced
by the distillation of dry ferrous sulphate, at a nearly white heat —
either in earthenware or in green glass retorts ; the distillate is received
in sulphuric acid. As thus manufactured, it is a dark fuming liquid,
of r9 speciSc gravity, and boiling at 53**. When artificially cooled
down to 0*", the acid gradually deposits crystals, which consist of a
definite compound of 2 atoms of anhydrous sulphuric acid and 1 atom
of water. There is some doubt as to the molecular composition of
Nordhausen acid ; it is usually considered as hydric sulphate saturated
with sulphur dioxide. This acid is manufactured chiefly in Bohemia,
and is used, on a large scale, as a solvent for alizarine.
§ 52. Sulphur Triozide, or Sulphuric Anhydride (SO3), itself may
be met with in scientific laboratories, but is not in commerce. Sulphur
trioxide forms thin needle-shaped crystals, arranged in feathery groups.
Seen in mass, it is white, and has something the appearance of asbestos.
It fuses to a liquid at about 18', boils at 35*, but, after this operation
has been performed, the substance assumes an allotropic condition, and
then remains solid up to 100*; above 100* it melts, volatilises, and
returns to its normal condition. Sulphuric anhydride hisses when it
is thrown into water, chemical combination taking place and sulphuric
acid being formed. Sulphur trioxide is excessively corrosive and
poisonous.
Besides the above forms of acid, there is an oflficinal preparation
called "Aromatic Sulphuric Acid," made by digesting sulphuric acid,
rectified spirit, ginger, and cinnamon together. It contains 10' 19 per
cent, of SO3, alcohol, and principles extracted from cinnamon and
ginger.
§ 53. Sulphuric acid, in the free state, may not unfrequently be found
in nature. The senior author has had under fexamination an effluent
water from a Devonshire mine, which contained more than one grain
of free sulphuric acid per gallon, and was accused, with justice, of
destroying the fish in a river. It also exists in* large quantities in
volcanic springs. In a torrent flowing from the volcano of Parc^, in
the Andes, Boussingault calculated that 15,000 tons of sulphuric acid
and 1 1,000 tons of hydrochloric acid were yearly carried down. In the
animal and vegetable kingdom, sulphuric acid exists, as a rule, in
combination with bases, but there is an exception in the saliva of the
Dolium gal^ay a Sicilian mollusc.
§ 54. Statistics.— When something like 900,000 tons of sulphuric
acid are produced annually in England alone, and when it is considered
§ss.]
SULPHURIC ACID.
83
tbat stilpbaric ncid is used in the manufacture of moBt other acids, in
the alkali trade, m the manufacture of indigo, in the soap trade, in the
manufacture of artificial niannre, and in a number of technical processes,
there ia no cause for surprise that it should be the annual cause of
many deaths.
The number of deaths from aulpliuric acid will vary, other things
l)eiug equal, in each conntrj, according to the mauufactureH in that
country employing sulphuric acid. The mimber of cases of poisoning
in England and Wales for the ten yeiu^ ending 1903 was as follows: —
DEATHS FROM SULPHURIC ACID IN ENGLAND AND WALES FOR
TUE TEN YEARS ENDINa ISOl
AtaiDKNT OR NKULlORXrF^
Tf>t-t»l,
43
SLriCJBK.
Total,
52
During the ten years^ two cases of murder through sulphurlo moid
are on record ; bence the total deaths, as detailed in the tables, amount
to 97, or nearly 10 a year.
Falek,* in comparing different countries, considerH the past statistics
to show that in France sulphuric acid has l^een the cause of 4*5 to 5*5
per cent, of the total deaths from |3oison, and in England 5*9 per cent.
In Rngland, France, and Denmark, taken together, 10 "8, Prnssia 10'6 ;
while ui certain cities, as lierlin and Vienna, the percentages are much
higher — Yleiuia showing 4 3' 3 per cent, Berlin 90 per cent
g 55. Accidental, Suicidal, and Criminal Poifloning,— Deaths from
sulphuric acid are, for the most part, accidental or suicidal, ntrely
criniinah In 53 out of 113 cases collected by Dohm, in which the
cause of the poiiKming could, with fair accuracy, be ascertained, 45'3
per cent, were due to accident, 30*2 were suicidal, and 24 '5 per oetit.
were cases of criininal poi.^oning, the victinm being children.
The cause of the comparatively rare use of stilphurio acid by the
poisoner is obvious. First of all, the ncid can never be mixed with footl
without entirely changing its aspect ; next, it is only in cases of
iuseusibility or paralysis that it could be administered to an adult,
unless given by force, or under very exceptional circumstances ; and
lastly, the stains on the mouth and ganuents would at once hetray, even
to uneducated persons, the presence of something wrong. As an agent
of murder, then, sulphuric acid ia confined in its use Co young children,
more especially to the newly l>orn.
84 POISONS : THWR EFFECTS AND DETECTION. [§ 56.
There is a remarkable case related bj Haagan,^ in which an adult
man, in full possession of his faculties, neither paralysed nor helpless,
was murdered by sulphuric acid. The wife of a day-labourer gave her
husband drops of sulphuric acid on sugar, instead of his medicine, and
finally finished the work by administering a spoonful of the acid. The
spoon was carried well to the back of the throat, so that the man took
the acid at a gulp. 11 grms. (171 grains) of sulphuric acid, partly in
combination with soda and potash, were separated from his stomach.
Accidental poisoning is most common among children. The oily,
syrupy-looking sulphuric acid, when pure, may be mistaken for glycerine
or for syrup ; and the dark commercial acid might, by a careless person,
be confounded with porter or any dark-looking medicine.
Serious and fatal mistakes have not unfrequently arisen from the use
of injections. Deutsch t relates how a midwife, in error, administered
to mother and child a sulphuric acid clyster ; but little of the fluid could
in either case have actually reached the rectum, for the mother recovered
in eight days, and in a little time the infant was also restored to health.
Sulphuric acid has caused death by injections into the vagina. H. C.
Lombard I observed a case of this kind, in which a woman, aged 30,
injected half a litre of sulphuric acid into the vagina, for the purpose of
procuring abortion. The result was not immediately fatal, but the sub-
sequent inflammation and its results so occluded the natural passage
that the birth became impossible, and a CsBsarean section extracted a
dead child, the mother also dying.
An army physician prescribed for a patient an emollient clyster.
Since it was late at night, and the apothecary in bed, he prepared it
himself ; but not finding linseed oil, woke the apothecary, who took a
bottle out of one of the recesses and placed it on the table. The bottle
contained sulphuric acid ; a soldier noticed a peculiar odour and efier-
vescence when the syringe was charged, but this was unheeded by the
doctor. The patient immediately after the operation suflFered the most
acute agony, and died the following day ; before his death, the bed-
clothes were found corroded by the acid, and a portion of the bowel
itself came away. §
§ 56. Fatal Dose. — The amount necessary to kill an adult man is
not strictly known ; fatality so much depends on the concentration of
the acid and the condition of the person, more especially whether the
stomach is full or empty, that it will be impossible ever to arrive at an
* Gross : Die Strafrechtspflege in Deutschland, 4, 1861, Heft i. S. 181.
t Freuss, Med, Verdna-ZeUung, 1848, No. 18.
t Jotnti, de Chim. M6d,f torn, vii., 1831.
§ Maschka's ffandlnieh, p. 86 ; Journal de Chimie Medicah\ t i. No. 8, 405,
1885.
§SM
SULPHUBIC ACro.
8S
Ai3ciirate estimate. Ghristison^e case, in which 3^8 grms. (60 grains) of
00Q6eiitrat«d acid killed an adult, is the smallest lethal dose on record.
Suppoifiing that the man weighed 68^ kilo. (150 Ibe,}^ this would he in
the proportion of '05 grm. per kilo* There is abo the caae of a child of
one year, recorded by Taylor, in which 20 drop^ caused death. If,
howei-er, it were aaked in a oonrfc of law what dose of concentrated
aulphuric acid would be dangerous, the proper answer would be ; so
nmull a quantity as from 2 to 3 drops of the strong midilut^pd acid
might cjiuse death, more especially if conveyed to the back of the throaty
fur if iL is improbable that on such a supposition death would he tiudden,
jet there is a possibility of permanent injury to the gullet, with the
result of subsequent contraction, and the usufd l^ng and tJiiiiifid
matmitritioii thereby induced. It may be laid down, therefore, that all
quantiticea, even the sraalle^t^ of the Mrong itmlihii^l mid come under
the head of hurtful, noxious, and injurious.
% 57, Local Action of Suiphuric Add,— The aution of the aeid on
lirittg aniiual ti^ue^ hai^ been studied by €, Ph. Falek and L Viator.*
Concentrated acid precipitates albomenj and then redissolves it ; fibrin
tt wells and becomes gelatinous \ but if the acid is weak {ejj, 4 to 6 per
cent.) it is scarcely changed. Muaeular fibre is at first coloured amber-
yellow^ swells to a jelly, and then dissolves to a red- brown turbid fluid.
When applie«i to the mucous membrane of the stomach j the mucous
tijtaue and the mu»cul&r layer beneath are coloured white, swell, and
become an oily mass.
When applied to a rabbit's e«.r,t the parenchyma becomes at first
pale grey aod semi transparent at the hack of the ear; opposite the
drop of acid appear spots like greane or fat drops, which soon coalesce.
The epidennia with the hair remains adherent; the blood-vessels are
uartxiwed in csJibre, and the blood, first in the %*eins, and then in the
arteriea, is coloured green and then black, aud fully coagulates. If the
drop, with horizontal holdiog of the ear, is dried iu, an inflammatory
Kone surrounds the burnt spot in which the blood circulates ; but there is
complete stasis in the part to which the acid has been applied. If the
point of the ^r is dipped in the acid, the cauterised part rolls inwards;
after the lapst.* of eighteen hours the part is brown and parchment like,
with scattered points of coagulated blood ; then there is a slight swelling
in the healthy tissues, and a small zone of redness; within fourteen
days a bladder^ike grceuish-yellow scab is formed, the burnt part it-
self remain iug dry. The vessels from the surrounding zone of redness
• lk%il»ch' Klinik, ISei, Mai» 1-^2, aod Vietor'si Inaugitr-Dit^ert.f Marbmgp
t S*iuiitl» Entziindiimj a. Bfumd^ m Virek&ws Arckivf, Path, Amti*, IL lift
I u. ^A a 41, IS7U.
86 POISONS : THKIR EFFECTS AND DETECTION. [§ 58.
gradually penetrate towards the cauterised spot, the fluid in the bleb
becomes absorbed, and the destroyed tissues fall off* in the form of a
crust.
The changes that sulphuric acid cause in blood are as follows : the
fibrin is at first coagulated and then dissolved, and the colouring matter
becomes of a black colour. These changes do not require the strongest
acid, being seen with an acid of 60 per cent.
§ 58. The action of the acid on various non-living matters is as
follows : poured on all vegetable earth, there is an effervescence, arising
from decomposition of carbonates ; any grass or vegetation growing on
the spot is blackened and dies ; an analysis of the layer of earth, on
which the acid is poured, shows an excess of sulphates as compared with
a similar layer adjacent ; the earth will only have an acid reaction if
there has been more than sufficient acid to neutralise all alkalies and
alkaline earths.
Wood almost immediately blackens, and the spot remains moist.
Spots on paper become quickly dark, and sometimes exhibit a play
of colours, such as reddish-brown; ultimately the spot becomes very
black, and holes may be formed; even when the acid is dilute, the
course is very similar, for the acid dries in, until it reaches a sufficient
degree of concentration to attack the tissue. Small drops of sulphuric
acid ou a Brussels carpet, which had a red pattern on a dark green ground
with light green flowers, were found to act as follows : the spots on the
red at the end of a few hours were of a dark maroon colour, the green
was darkened, and the light green browned ; at the end of twenty-four
hours but little change had taken place, nor could any one have guessed
the cause of the spots without a close examination. Spots of the strong
acid on thin cotton fabrics rapidly blackened, and actual holes were
formed in the course of an hour ; the main difference to the naked eye,
between the stains of the acid and those produced by a red-hot body,
lay in the moistuess of the spots. Indeed, the great distinction,
without considering chemical evidence, between recent bums of clothing
by sulphuric acid and by heat, is that in the one case^that of the
acid — the hole or spot is very moist ; in the other very dry. It is easy
to imagine that this distinction may be of importance in a legal
investigation.
Spots of acid on clothing fall too often under the observation of all
those engaged in practical chemical work. However quickly a spot of
acid is wiped off, unless it is immediately neutralised by ammonia, it
ultimately makes a hole in the cloth ; the spot, as a rule, whatever the
colour of the cloth, is of a blotting-paper red.
Sulphuric acid dropped on iron, attacks it, forming a sulphate, which
may be dissolved out by water. If the iron is exposed to the weather
H
aULPHURiG ACID.
^7
the rain omj wa^h away aU traces of the acid^ save the eorrosiou ; but
it would be under thoa6 drcumBtanceii imposeible to say whether the
corrosion was due to oxidation or a solvent.
To sum lip briefiy : the charactera of Bulphuric acid spots on organic
matters generally are black, browu, or red-coloured destruotiona ol tis^ue^
moisture, acid -reaction (often after years ), and lastly the chemical avi-
dence of sulphuric acid or sulphates in excess*
Caution oecegsary in judging of Spots, etc. — Au important casCi
related by Mtischka, shovTs the necessity of great cautiou iu interpreting
results, unless all the circumatancea of a case be earefuUy collated. A
live coal fell on the bed of a weakly infant, live months old. The child
screamed, and woke the father, who was doling by the fire ; the man, in
terror, poured a large pot of water on the child and burning bed. The
child died the following day,
A poat-morteni examination showed a bum on the cheat of the infant
2 inches in length. The tonguej pharynx, and gullet were all healthy ;
in the stomach a patch of mucous membrane, about half an inch in
extent, was found to be brownish, friable, and very thin* A chemical
examination showed that the portion of the bed adjacent to the burnt
place contained free sulphunc acid. Here* then, was the following
evidence ; the sudden death of a helpless infant, a carbonised bed-cover
with free sulphuric acid, and, lastly, an appearance in the stomach
which, it might he said, was not inconsistent with sulphuric acid
poisoning. Yet a careful sifting of the facts convinced the judges that
no crime had been committed, and that the child's death was due to
dtaeaae. Afterwards, experiment showed that if a live coal fall on to
any tissue and be drenched with water, free sulphuric acid is constantly
found in the neighbourhood of the burnt place,
§ 59. Symptoms. — The symptojns may be clai^sed in two divisions,
viz, : — L External effects of the acid. 2. Internal eflecta and ay mptoma
arising from its interior administration,
L External Effects.— Of late years several instances have occurred in
which the acid ha^i been used criminally to cause diafiguring burns of the
face, The offence has in all these cases been committed hy women, who,
from motives of revengeful jealousy^ have suddenly dashed a quantity of
tfio acid into the face of the object of their resentment. In such cases,
the phenomena observed are not widely different from those attending
scalds or burns from hot neutral fluids. There is destruction of tissue,
not necessarily deep, for the acid is almost immediately wiped off; but
if any should reach the eye, inflammation, so acute as to lead to blind-
ness^ is the probable consequence. The skin is coloured at first white,
%% a later period brown, and part of it may be, as it were, dissolved* If
the tract or skin touched by the acid is extensive, death may result.
88 POISONS : THEIR EFFECTS AND DETECTION. [§ 59.
The inflammatory processes in the skin are similar to those noticed by
Falck and Victor in their experiments, already detailed (p. 85).
Internal Effects of Acids generally. — It may not be out of place,
before speaking of the internal effects of sulphuric acid, to make a few
remarks upon the action of acids generally. This action differs accord-
ing to the kind of animal; at all events, there is a great difference
between the action of acids on the herb-eating animals and the camivora ;
the latter bear large doses of acids well, the former ill. For instance,
the rabbit, if given a dose of any acid not sufficient to produce local
effects, but sufficient to affect its functions, will soon become paralysed
and lie in a state of stupor, as if dead ; the same dose per kilo, will not
affect the dog. The reason for this is that the blood of the dog is able
to neutralise the acid by ammonia, and that the blood of the rabbit is
destitute of this property. Man is, in this respect, nearer to the dog
than to the plant-eaters. Stadelmann has shown that a man is able to
ingest large relative doses of oxybutyric acid, to neutralise the acid by
ammonia, and to excrete it by means of the kidneys as ammonium
butyrate.
Acids, however, if given in doses too great to be neutralised, alike
affect plant- and flesh-eaters ; death follows in all cases before the blood
becomes acid. Salkowski * has, indeed, shown that the effect of lessen-
ing the alkalinity of the blood by giving a rabbit food from which it
can extract no alkali produces a similar effect to the actual dosing with
an acid.
2. Internal Effects of Sulphuric Acid. — When sulphuric acid is
taken internally, the acute and immediate symptom is pain. This,
however, is not constant, since, in a few recorded cases, no complaint of
pain has been made ; but these cases are exceptional ; as a rule, there
will be immediate and great suffering. The tongue swells, the throat
is also swollen and inflamed, swallowing of saliva even may be im-
possible. If the acid has been in contact with the epiglottis and vocal
apparatus, there may be spasmodic croup and even fatal spasm of the
glottis.
The acid, in its passage down the gullet, attacks energetically the
mucous membrane and also the lining of the stomach ; but the action
does not stop there, for Lesser found in eighteen out of twenty-six cases
(69 per cent.) that the corrosive action extended as far as the duodenum.
There is excessive vomiting and retching ; the matters vomited are acid,
bloody, and slimy ; great pieces of mucous membrane may be in this
way expelled, and the whole of the lining membrane of the gullet may
be thrown up entire. The bowels are, as a rule, constipated, but
exceptionally there has been diarrhoea ; the urine is sometimes retained ;
* Virchow*8 Archiv, Iviii. 1.
S60.1
SULPHURIC ACID.
89
it invH.riablj containa an eicesd of sulphatea twid often albumen, ^^itb
hyaline casta of the uriniferous tubes* The pulse is small and frequent,
the brGiitbing alow, the skin very cold and covered with sweat; the
couotenance expresses great anxiety, and the extremitieB may be aO'eeted
with erampa or convulsiomL Death may talte place within from twenty-
four to thirtj-flii hour^ and be either preceded by dysipucea or by 000-
vulfiions ; oonsciousQesa is, as a rule, maintained to the end.
There are also more rapid mmn than tlie above ; a large doae of
Kulphuric acid taken on an empty stomach may al>30lutely dissolve it,
and pass into the peri ton euni ; in such a case there m really no difforuuce
if) the aymptoms between sudden i>erforation of the stomach from
diseefie, a penetrnting wouutl of the abdomen, and any mother i^udden
fatal lesion of the organs in the aMomiual cavity (for in all these
itistant'os the Hyinptoiust are thoHe of pnrt* collajjiso} ; tVic patient i^i ashen
pale, with pube quick and weak, and body huthed in tjold sweat, and
he rapidly dies, it may be without rmieh complaint of local pain*
If the p;itient live longer than twenty-four hours, the symptoms are
mainly those of inllammatiou uf the whole mucous tract, from the mouth
to the stomach ; and from this inflammation the patient may die in a
variable [>eriod, of from three to eleven days, after taking Ihe poison.
In one case the death occurred suddenly, without any immediately pre-
ening symptoms rendering imminent death probable. If this second
atage is pa^ed, then the lost^ of substance in the gullet and in the
fttomach almost invarialily causes impairment of function^ leading to a
slow and pLiinful death, The common sequence in stricture of the gullet,
combined with feeble digestion, and in a few inslainces stricture of the
pylorus. A ctirious sequel has been recor^lcd by Mannkopf, viss,,
obstinate intercostal neuralgia; it has been observed on the fourth,
seventh, and twenty-fiecond day,
§ 00. Treatment of Acute Fomotiiiig by the ICineral Adds, — ^The
immediate indication in the dihition and neutralisation of the acid. For
this purpose, finely-divided chalk, magnesia, or sodic carbonate may be
used, dissolved or suspended in much water. The use of the stoniacb-
pump ia inadvisable, for the mucous membrane of the gullet may be so
corroded by the acid that the pajss&ge of the tube down will do injury ;
unless the neutralisation is imnm'Mate^ but little good is eflected ; hetice
it will often occur that the hystanders, if at all conversant with the
matter, will have to use the lint thing which comes to hand^ such as the
plaster of a wall, etc. ; aod lastly, if even these rough antidotes are not
to l>e had, the l>est treatment is enormous doses of water, which will
dilute the acid and promote vomiting. The treatment of the after-effects
belongs to the province of ordinary medicine, and h based upon general
principlea.
90 POISONS: TMIK EFFECTS AND DETECTION. [§ 6l.
§ 61. Post-mortem Appearances.* — The general pathological ap-
pearances to be found in the stomach and internal organs differ
according as the death is rapid or slow; if the death takes place
within twenty-four hours, the effects are fairly uniform, the differences
being only in degree ; while, on the other hand, in those cases which
terminate fatally from the more remote effects of the acid, there is some
variety. It may be well to select two actual cases as types, the one
patient dying from acute poisoning, the other surviving for a time, and
then dying from ulceration and contraction of the digestive tract.
A hatter, early in the morning, swallowed a large mouthful of
strong sulphuric acid, a preparation which he used in his work —
(whether the draught was taken accidentally or suicidally was never
known). He died within two hours. The whole tongue was sphace-
lated, parts of the mucous membrane being dissolved ; the inner surface
of the gullet, as well as the whole throat, was of a grey-black colour ;
the mucous membrane of the stomach was coal-black, and so softened
that it gave way like blotting-paper under the forceps, the contents
escaping into the cavity of the abdomen. The peritoneum was also
blackened as if burnt; probably there had been perforation of the
stomach during life; the mucous membrane of the duodenum was
swollen, hardened, and looked as if it had been boiled ; while the
blood was of a cherry-red colour, and of the consistence of a thin syrup
The rest of the organs were healthy ; a chemical research on the fluid
which had been collected from the stomach, gullet, and duodenum
showed that it contained 87*25 grains of free sulphuric acid.t
This is, perhaps, the most extreme case of destruction on record ;
the cause of the unusually violent action is referable to the acid acting
on an empty stomach. It is important to note that even with this
extensive destruction of the stomach, life was prolonged for two hours.
The case selected to serve as a type of a chronic but fatal illness
produced from poisouing by sulphuric acid is one related by Oscar
Wyss. A cook, 34 years of age, who had suffered many ailments,
drank, on the 6th of November 1867, by mistake, at 8 o^clock
in the morning, two mouthfuls of a mixture of 1 part of sul-
phuric acid and 4 of water. Pain in the stomach and neck, and
vomiting of black masses, were the immediate symptoms, and two
hours later he was admitted into the hospital in a state of collapse,
with cold extremities, cyanosis of the face, etc. Copious draughts of
milk were given, and the patient vomited much, the vomit still con-
* It has been observed that putrefaction in cases of death from sulphuric acid is
slow. Casper suggests this may be due to the neutralisation of ammonia ; more
probably it is owing to the antiseptic properties all mineral acids |)osse8s.
t Cas|)er, vol. ii. case 194.
I 63.]
SULPirURIC ACID.
sistltig of black pulUceous matters, in which, otj a microicopical ex-
aminationj could be readily detected columiiar epitheliimi of the
atoniach and miicoQS tissue elements. Tlio nrine was of specific gravitj
I "033, iion-albumiuous ; on aoaljais it cuiitained 3*388 grms. of
combined sulphuric acid.
On the second daj there was some improvement in the sympt-oms;
the urine contained r276 grnu of combined sulpliuric add; ou the
third day 2 '665 grms, of combined sulphuric acid; and on the tenth
day the patient vamited up a complete caat of the mucous membrane
of the guUeL The patient remained in the hospital^ and l:>ecame
gradually weaker trom stricture of the gullet and impairment of the
digestive powers, and died, two months after taking the poison, on the
5th of January 1868,
Tlie stomach was found small, contmcted, with many adhesions to
the pancreas and liver; it was about 12 centimetres long (4*7 inches),
and from 2 to 2*b centimetres ('7 to '9 inch) broad, contracted to
somewhat the form of a nat*i intestiue ; there were several transverse
rugsB ] the walls were thickened at the Bmall curvature, meaauremeuta
giving 5 mm. (*19 inch) in the middle, and beyond about 2*75 mm.
('11 inch); in the upper two-thirds the lumen was so contracted as
scarcely to admit the point of the httle finger. The inner surface was
covered with a layer of pus, with no trace of mucous tissue, and was
everywhere pale red, uneven, and crossed by cicatricial bands. In
two parts, at the greater curvature, the mucous surface was strongly
injected in a ring-like form, and in the middle of the ring was a deep
funnel-shaped ulcer ; a part of the rest of the atomach was strongly
Injected and scattered over with uumerous punctiform, smallf traui-
parent bladders. The gullet was contracted at the upper part (just
below the epiglottis) from 20 to 22 mm. {^78 to '86 inch) in diameter ;
it then gradually widened to measure about 12 nmi, ('47 inch) at the
diaphragm ; in the neighbourhood of the last contraction the tissue was
scarred, injected, and ulcerated ; there were also small abscesses opening
into this portiou of the gullet.
E. Fraenkel and F. Reiche* have studied the eflfects of sulphuric
acid on the kidney. In rapid cases they find a widespread shedding
of the epithelium in the convoluted and straight urinary canaliculi,
with destruction of the kidney parunchyma, but no inflammation.
g 62. The museums of thedilierent London hospitals afford excellent
material for the study of the effects of sulphuric auid on the pharyni:,
gidlet, and stomach ; and it may be a matter of convenience to students
if the more typical examples at these different museums be noticed in
detail, so that the preparations themselves may be referred to,
* Virchow*s ArchiVt oxxxL 130.
92 POISONS : THEIR EFFECTS AND DETECTION. [§ 63.
In St. Barlholouuw's Museum ^ No. 1942, is an example of excessive destmction
of the stomach by sulphuric acid. The stomach is much contracted, and has a large
aperture with ragged edges ; the mucous membrane is thickened, charred, and
blackened.
No. 1941, in the same museum, is the stomach of a person who died from a large
dose of sulphuric acid. When recent, it is described as of a deep red colour, mottled
with black ; appearances whicli, from long soaking in spirit, are not true at the
present time ; but the rough, shaggy state of the mucous tissue can be traced ; the
gullet and the pylorus appear the least affected.
St, George^ s Hospital^ ser. ix. 146, 11 and 43, e. — ^The pharynx and oesophagus of
a man who was brought into the hospital in a state of collapse, after a large but
unknown dose of sulphuric acid The lips were much eroded, the mucous membrane
of the stomach, pharynx, and oesophagus show an extraordinary shreddy condition ;
the lining membrane of the stomach is much charred, and the action has extended to
the duodenum ; the muscular coat is not affected.
Ouy^s Hospital f No. 1799. — A preparation showing the mucous membrane of the
stomach entirely denuded. The organ looks like a piece of thin pa{>er.
No. 1799*. The stomach of a woman who poisoned herself by drinking a wine-
glassful of acid before breakfast. She lived eleven days. The main symptoms were
vomiting and purging, but there was no complaint of \^\n. There is extensive
destination of mucous membrane along the lesser curvature and towards the pyloric
extremity ; a portion of the mucous membrane is floating as a slough.
No. 1799^ is the gullet and stomach of a man who took about 3 drachms of
the strong acid. He lived three days without much apparent suffering, and died
unexpectedly. The lining membrane of the oesophagus has the longitudinal wrinkles
or furrows so often, nay, almost constantly, met with in poisoning by the acids. The
mucous tissue of the stomach is mised in cloudy ridges, and blackened.
No. 1799'^ is a wonderfully entire cast of the gullet from a woman who swal-
lowed an ounce of sulphuric acid, and is said, according to the catalogue, to have
recovered.
University College, — In this museum will be found an exquisite preparation of the
effects of sulphuric acid. The mucous membrane of the oesophagus is divided into
small quadrilateral areas by longitudinal and transverse furrows : the stomach is very
brown and covered with shreddy and filamentous tissue ; the brown colour is without
doubt the remains of extra vasated and charred blood.
No. 6201 is a wax cast representing the stomach of a woman who died after taking
a large dose of sulphuric acid. A yellow mass was found in the stomach ; there are
two perforations, and the mucous membrane is entirely destroyed.
§ 63. Chronic Poisoning by Sulphuric Acid— Weiske* has experi-
mentally proved that lambs, given for six months small doses of sulphuric
acid, grow thin, and their bones, with the exception of the bones of the
head and the long bones, are poor in lime salts, the muscles also are
poor in the same constituents. Robert f thinks that drunkards on the
Continent addicted to ''Schnaps," commonly a liquid acidified with sul-
phuric acid to give it a sharp taste, often show typical chronic sulphuric
acid poisoning.
• H. Weiske, Joum,f, Landwirthsch. , 1887, 417.
t Lchrbuch tier JnioxiccUionemf S. 210.
§64.]
8UXPHUBIC ACID,
93
Detection and Estimation of Free Sulphuric Acid«
§ 64. The gfineral method of separating the mineral noida ia i\s
followi : the tissues, or matters, are soaked in distilled water for some time.
If no free acid is present, the liquid will not redden Htm us- paper, or give
an acid reaction with any of the numerous tinctorial agents in use by the
nhemtat for the purposes of titration* After Buiicient digestion in water,
the lifjuid extract is made up to some definite bulk and allowed to sub-
aide. Filtration is unnecessary. A small fractional part (say, for example,
ahould the whole be 250 c,c., yths^^ ^^ ^*^ c-^-) ^^ taken, and using as an
indieator cochineal or phenolphthalein, the total acidity is estimated by a
decinormal solution of eoda* By this preliminary operation, some guide
for the condnct of the future more exact operations is obtained. Should
the liquid be very acid, a small quantity of the whole is to be now
taken ; but if the acidity is feeble^ a larger quantity is necessary, and
sufficient quinine then added to fix the acid — 100 parte of sulphuric aoid
are saturated by 342 parts of tjuinme monoliydrate. Therefore, on the
supposition that all the free acid is sulphuric, it will be found sufficient
to add 3 5 parts of quinine for every I part of acid, estimated as sul-
phuric, found by the preliminary rough titration ; and as it is inconvenient
to deal with large qimotities of alkaloid, a fractional portion of the
liquid extract (representing not more than 50 nigrms. of acid) should be
y^ken^ which will require 175 mgrms. of quinine.
On addition of the quinine, the neutralised liquid is evaporated to diy-
ness, or to approaching dryness^ and then exhausted by strong alcohol .
The alcoholic extract is, after tiltrationj dried up, and the quinine sul-
phate, nitrate^ or hydrochlorate^ as the caae may be, filtered ofiT and ex-
tracted by boiling water» and precipitated by ammonia, the end result being
quinine hydrate (which may be filtered ofT and used again for similar
puq>r>ses) and a sulphate, nitrate, or chloride of ammonia in solution.
It therefore remains to determine the nature and quantity of the acids
now combined with ammonia. Tlie solution is made up to a known
bulk, and portions tested for chlorides by nitrate of silver, for nitrates
by the copper or the ferrous sulphate teat, and for sulphates by BaCU
sohition. If sulphuric acid is present there will be a precipitate of
barium sulphate, which, from its density and insolubility in nitric or
hydrochloric iicids, is very characteristic. For estimating the sulphuric
acid thus found, a known hulk of the same liquid is heated to boiling
after acidifying by hydrochloric acid, and a sufficient quantity of baric
chloride solution added. Unless this exact process is followed, the
analyst is likely to got a liquid which refnseu to tilter clear; but if the
sulphate be precipitated from a hot liquid, it usually settles rapidly to
94 POISONS : THKIR EFFECTS AND DETECTION. [§ 6$.
the bottom of the vessel, and the supernatant fluid can be decanted clear ;
the precipitate is washed by decantation, and ultimately collected on a
filter, dried, removed from the filter and burnt up in the usual way.
The sulphate of baryta found, multiplied by *3434, equals the
sulphuric anhydride.
The older process was to dissolve the free sulphuric acid out by alcohol.
As is well known, mineral sulphates are insoluble in, and are precipitated
by, alcohol, whereas sulphuric acid enters into solution. The most valid
objection, as a quantitative process, to the use of alcohol, is the tendency
which all mineral acids have to unite with alcohol in organic combination,
and thus, as it were, to disappear; and, indeed, results are found, by
experiment, to be below the truth when alcohol is used. This objection
does not hold good if either merely qualitative evidence, or a fairly
approximate quantation, is required. In such a case, the vomited matters,
the contents of the stomach, or a watery extract of the tissues, are evapo-
rated to a syrup, and then extracted with strong alcohol and filtered ; a
little phenolphthalein solution is added, and the acid alcohol exactly
neutralised by an alcoholic solution of clear decinormal or normal soda.
According to the acidity of the liquid, the amount used of the decinormal
or normal soda is noted, and then the whole evaporated to dryness, and
finally heated to gentle redness. The alkaline sulphate is next dissolved
in very dilute hydrochloric acid, and the solution precipitated by chloride
of barium in the usual way. The quantitative results, although low,
would, in the gpeat majority of cases, answer the purpose sufticiently.
A test usually enumerated, Hilger's test for mineral acid, may be
mentioned. A liquid, which contains a very minute quantity of mineral
acid, becomes of a blue colour (or, if 1 per cent, or above, of a green) on
the addition of a solution of methyl aniline violet ; but this test, although
useful in examining vinegars (see "Foods"), is not of much value in
toxicology, and the quinine method for this purpose meets every conceiv-
able case, both for qualitative and quantitative purposes.
§ 65. The Urine. — Although an excess of sulphates is found constantly
in the urine of persons who have taken large doses of sulphuric acid, the
latter has never been found in that liquid in a free state, so that it will
be useless to search for free acid. It is, therefore, only necessary to add
HCl, to filter the fluid, and precipitate direct with an excess of chloride
of barium. It is better to operate in this manner than to bum the urine
to an ash, for in the latter case part of the sulphates, in the presence of
phosphates, are decomposed, and, on the other hand, any organic sulphur
combinations are liable to be estimated as sulphates.
It may also be well to pass chlorine gas through the same urine which
has been treated with chloride of barium, and from which the sulphate
has been filtered off. The result of this treatment will be a second
I 65.]
BITLPHDBIC ACID.
9$
preoipitate of s\i1phate derived from sulphur, in a dUferant form of
oombiti&tion than that of sulphate.
The greatest amoimt of sulphuric acid as mineral and organic
sulphate is sepa rated , according to Mannkopf* and Schultzeii^t within
five hours after ticking Bulphuric aoid ; after three days the secretion,
so far aa total sulphates is coocemed, is normal.
The aormal art;ount of sulphuric acid excreted datlj, according to
Tbudichum, is* from 1*5 to 2 "5 grms,^ and organic sulphur up to '2 grm.
in the twenty- four hours, but very much more has been excreted by
healthy persona.
Lehmann uiade some observations on hioaselfT and found that^ on an
animal diet, he excreted no less than 10*399 gnus, of sulphuric acid
per day, and on mixed food a little over 7 grnis. j aa Thudichum
justly observes^ this great amount must be referred to individual
peculiarity. The amount of sulphates has a decided relation to diet
Animal food, although not containing sulphates^ yet, from the oxidation
of the sulphur-holding allmmen^ produces a urine rich in sulphate.
Thus Vogel found that a person, whose daily average was 2*02 grms.,
yielded 7 '3 on a meat diet The internal use of sulphur, sulphides,
and sulphates, given in an ordinary medicinal way, is traceable in the
urlne^ tcicreasing the sulphates. In chronic diseases the amount of
aulphatea is decreased, in acut« increased.
Finally, it would appear that the determination of sulphates in the
urine is not of much value, save when the normal iimount that th£ iitdi'
fddual secretes is pHrmtHl^ known. On the other band, a low amonnt
of sulphates in the urine of a person poisoned by sulphuric acid has not
been observed within three days of the taking of the poison, and one
can imagine cases in which suoh a low result might have forensic
importance.
The presence of albumen in the urine has been considered by some
a constant result of sulphuric acid poisoning, but although when looked
for it is usually fo\nid, it cannot bo considered constant. 0. Smoler, t
in eighteen cases of various degrees of sulphuric acid i>oisoning, found
nothing abnormal in the unne. Wjss§ found in the later stages of a
case indican and pus. E. Leydeny and Ph. Munn always found blood
iu the urine, as well as albumen, with casts and cellular elements*
Mannkopf ^ found albuminuria in three cases out of five ; iu two of the
eases there were tibrinous casts ; iu two the albumen disappeared at the
• **Tiia:ioologje d^'r Scliwefe^aiiurB,*' Winner vied, Woeh^n,^ 1862, 1869.
t Ardtic. f. AnatirnK u. Phttsioht 1864,
I Jrchiiffhr Il€akund4', &i by E. Wagner, 1809, flft. 2, S. 18L
§ fTkni^ M^^ffviHol^Malk, 18G1, Jahr. 6, No. 46.
\i YiTchoiv'& Affhiv f\ path. Anat., 1861, Bd. %xiu lift 3 a* 4, S. 23L
f ITwfrt. fiud, SroefmstArMft, 18$2, Nro* 35 ; 18(J3, Nro. fi.
96 POISONS : THEIR EFFECTS AND DETECTION. [§ 66, 6/.
end of the second or third day, but in one it continued for more than
twenty days. Bamberger* has observed an increased albuminuria,
with separation of the colouring matter of the blood. In this case it
was ascribed to the action of the acid on the blood.
§ 66. The Blood.— In Casper's case. No. 193, the vena cava of a
child, who died within an hour after swallowing a large .dose of
sulphuric acid, was filled with a cherry-red, strongly acid-reacting blood.
Again, Casper's case, No. 200, is that of a young woman, aged 19, who
died from a poisonous dose of sulphuric acid. At the autopsy, four
days after death, the following peculiarities of the blood were thus
noted: — ''The blood had an acid reaction, was dark, and had (as is
usual in these cases) a syrupy consistence, while the blood corpuscles
were quite unchanged. The blood was treated with an excess of
absolute alcohol, filtered, the filtrate concentrated on a water-bath, the
residue exhausted with absolute alcohol, etc. It yielded a small
quantity of sulphuric acid."
Other similar cases might be noted, but it must not for a moment
be supposed that the mass of the blood contains any free sulphuric acid
during life. The acidity of the blood in the vena cava may be ascribed
to post-mortem endosmosis, the acid passing through the walls of the
stomach into the large vessel.
§ 67. Sulphates. — If the acid swallowed should have been entirely
neutralised by antidotes, such as chalk, etc., it becomes of the first
importance to ascertain, as far as possible, by means of a microscopical
examination, the nature of the food remaining in the stomach, and then
to calculate the probable contents in sulphates of the food thus known
to be eaten. It will be found that, with ordinary food, and under
ordinary circumstances, only small percentages of combined sulphuric
acid can be present.
As an example, take the ordinary rations of the soldier, viz. : — 12 oz.
of meat, 24 oz. of bread, 16 oz. of potatoes, 8 oz. of other vegetables;
with sugar, salt, tea, ooffee, and water. Now, if the whole quantity of
these substances were eaten at a meal, they would not contain more
than from 8 to 10 grains ('5 to '6 grm.) of anhydrous sulphuric acid,
in the form of sulphates.
So far as the contents of the stomach are concerned, we have only
to do with sulphates introduced in the food, but when once the food
passes further along the intestinal canal, circumstances are altered, for
we have sulphur-holding secretions, which, with ordinary chemical
methods, yield sulphuric acid. Thus, even in the newly -bom infant,
according to the analyses of Zweifler, the mineral constituents of
meconium are especially sulphate of lime, with a smaller quantity of
* fFUn, Med.Halle, 1864, Nro. 29, 80.
§6S.]
IIYDROCHIX^EIC ACID.
97
sulphate of potash. The amount of bile which ilows into the whole
traet of the inteBtinal canal m eeti mated at aljout half a litre in the
twenty-four hours; tho amount of sulphur found in bik varies from *89
to 3 per cent., 80 that in 500 c*g. we might, by oxidising the sulphur,
obtain from 2-2 to 7*5 grms, of sulphuric anhydride.
It ia therefore certain that large quautitiee of organic fiiilphur-
comiiounds may he found in the human intestinal canal, for with indi-
Tiduals who suffer from con&tipation, the residues of tbe biliary seoretion
accumulate for many days. Hence, if tbe analyst nearches for sulphates
in excreta! matters, all methods involving destruction of orgauic sub-
stances, whetlier by fire or by fluid-oxidising agents, are wrong in
principle, and there is nothing left save to separate soluble sulphates
by dialysis, or to precipitate direct out of an aqueous extract.
Again^ sulphate of magnesia is a common medicine, and so is sodic
sulphate ; a ponsible medicinal dose of magnesia sulphate might amount
to 56'7 grms. {2 ozs.), the more usual dose being half that quantity.
Lastly, among the insane there are found patients who will eat plaster-
of-Paris, earth, and similar matters, so that, in special casea^ a very
large amount of combinej] sulpburie acid may be found in the intestinal
tract, without any relation to poisoning by the free acid ; but in such
instances it must be rare, indeed, that surrounding circumstances or
pathological evidence will not give a clue to the real state of affairs*
IL— Hydrochloric Acid,
§ 08. General Properties. — Pure hydrochloric acid is a gas, com-
posed of 97^26 per cent of chlorine and 2*74 per cent, of hydrogen.
Commercial hydrochloric acid, muriatic acid, or spirit of salt is a solution
of this gas, with more or less impurity, in water,
Hydrocblorie acid is made on an enormous scale in tbe United
Kingdom, the production being estimated at about a million tons
annually.
Tbe toxicology of hydrochloric acid is modenij for we have no
evidence that anything wa.*i known of it prior to the middle of the
seventeenth century, when Glauber prepared it in solution, and, in
1772, Priestley, by treating common salt with sulphuric acid, isolated
the pure gas.
The common liquid hydrochloric acid of oommeroe has a specific
graTity of from 1'15 to 1-20, and contains usually less than 40 parts of
hydrochloric acid in 100 jjarts. The strength of pure samples of
hydrochloric acid can be told by the specific gravity, and a very close
approximation, in default of tables, may be obtained by simply multi-
7
98 POISONS : THEIR EFFECTS AND DETECTION. [§ 68.
plying the decimal figures of the specific gravity by 200. For example,
an acid of 1*20 gravity would by this rule contain 40 per cent, of real
acid, for -20x200 = 40.
The commercial acid is nearly always a little yellow, from the
presence of iron derived from metallic retorts, and may contain small
quantities of chloride of arsenic,* derived from the sulphuric acid ; but
the colourless hydrochloric acid specially made for laboratory and
medicinal use is nearly always pure.
The uses of the liquid acid are mainly in the production of chlorine,
as a solvent for metals, and for medicinal and chemical purposes. Its
properties are briefly as follows : —
It is a colourless or faintly-yellow acid liquid, the absence or other-
wise of colour depending on its purity, and especially its freedom from
iron. The liquid is volatile, and can be separated from fixed matters
and the less volatile acids by distillation ; it has a strong attraction for
water, and fumes when exposed to the air, from becoming saturated
with aqueous vapour. If exposed to the vapour of ammonia, extremely
dense clouds arise, due to the formation of the solid ammonium chloride.
The acid, boiled with a small quantity of manganese binoxide, evolves
chlorine. Dioxide of lead has a similar action; the chlorine may be
detected by its bleaching action on a piece of paper dipped in indigo
blue; a little zinc foil immersed in the acid disengages hydrogen.
These two tests — viz., the production of chlorine by the one, and the
production of hydrogen by the other — separate and reveal the con-
stituent parts of the acid. Hydrochloric acid, in common with
chlorides, gives a dense precipitate with silver nitrate. The precipitate
is insoluble in nitric acid, but soluble in ammonia ; it melts without
decomposition. Exposed to the light, it becomes of a purple or blackish
colour. Every 100 parts of silver chloride are equal to 25*43 of hydro-
chloric acid, HCl, and to 63*5 parts of the liquid acid of specific gravity
1-20.
The properties of pure hydrochloric acid gas are as follows : — Specific
gravity 1-262, consisting of equal volumes of hydrogen and chlorine,
united without condensation. 100 cubic inches must therefore have a
weight of 39*36 grains. The gas was liquefied by Faraday by means of
a pressure of 40 atmospheres at 10"* ; it was colourless, and had a smaller
refractive index than water.
Water absorbs the gas with avidity, 100 volumes of water absorbing
* Some samples of hydrochloric acid have been found to contain as much as 4 per
cent, of chloride of arsenic, bat this is very unusual. Glenard found as a mean 2*5
grammes, As^ Os per kilogramme ; but since the mass poisoning by arsenical beer
derived from glucose made by impure sulphuric acid, English manufacturers have
succeeded in putting on the market ordinary sulphuric and hydrochloric acids almost
arsenic-free.
I 69-710
HYDROCHLORIC ACID.
99
48,000 Tolaraes of the gas, and becoming 142 volumes. The solution has
ftll the properties of strong hydrochloric acid^ specific gravity TSl, The
dilute hydrochloric aeid of the Pharmaeopteia should have a specific
gravity of 1052, and be equivalent to 1058 per cent, of HCl,
§ 69* Statistics of PoiBoning by Hydrochloric Acid.^The following
table gives the deaths nud mx distribution due to hydrochloric acid for
ten years ending 1 903 :~
DEATHS FROM HYDROCHLORIC ACID IN ENGLAND AND WALES
DURING THE TEN YEARS ENDING 1^03.
AraDRNT Oft Nrqlioknck.
Malei, ,
Females,
Total,
124
SinciDE.
Total,
204
166
369
In 1889 a solitary case of the murder of a child is on record from
hydrochloric acid. The total deaths from hydrochloric acid amount to
493 iu tlie ten years, or about 49 a year.
§ 70. Fatal Dose. — The dosi^ which destroys life is not known with
any accuraoy. In two cases, adulta have been killed hy 14 j^rms. (half
an ounce) of the commercial acid ; bufc^ on the other hand, recovery is
recorded when more than tlonble this quantity has been taken* A girl,
15 years of age, died from drinkitig a teaspoonfiil of the acid.*
§ 7K Amoxmt of Free Acid in the Gastric Juice,— Hydrochloric acid
exists in the gaa trie juice. This was first aseertained by Proutt in 1824- ;
he separated it by diatillation. The observation was afterwards confirmed
by Gmelitijt ChildreUig and Braconnot,|| On the other hand, Lehnmnn^
pointed out that, as the stomach secretion contained, without doubt,
lactic acid, the act of distillation, in the presence of this lactic afsid,
would set free hydrochloric acid from any alkaline chlorides^ Blondlot
and CI. Bernard also showed that the gastric juice jjossessed no acid which
would dissolve oxalate of lime, or develop hydrogen when treated with
iron filings ; hence there cotild not be free hydrochloric acid which, even
in a diluted state, would respond to both these tests. Then followed the
researches of C* Schmidt,** who showed that the gastric secretion of
men, of sheep^ and of dogs contained more hydrochloric acid than would
• BHU Mfit Jouni , March 187L
t ^hiloaophicai Tr^madwns, 1824, p. 45.
t P* TiednnMui and L. Uuielin, Die J'^crfiituunij ua^h l^^rsti4:hent Ht^idellnirg u*
Leipaic, 1826, i.
I Annah of Philomphy, July 1824,
I) Ann, tU Chiffhj I* Hx. p* 34 S.
U Jimrttiit/. jttaki. Chemit, Bd. il 47,
•• Bidd«r il Seiimidt, Venktuitn^-Sd/te^ etc.
lOO POISONS : THEIR EFFECTS AND DETECTION. [§ 72.
satisfy the bases present ; and he propounded the view that the gastric
juice does not contain absolutely free hydrochloric acid, but that it is in
loose combination with the pepsin.
The amount of acid in the stomach varies from moment to
moment, and therefore it is not possible to say what the average
acidity of gastric juice is. It has been shown that in the total
absence of free hydrochloric acid digestion may take place, because
hydrochloric acid forms a compound with pepsin wliich acts as a
solvent on the food. The amount of physiologically active acid varies
with the food taken ; it is smallest when carbohydrates are con-
sumed, greatest with meat. The maximum amount that Jaksch found
in his researches, when meat was ingested, was *09 per cent, of hydro-
chloric acid. It is probable that anything above 0*2 per cent, of
hydrochloric acid is either abnormal or owing to the recent ingestion
of hydrochloric acid.
§ 72. Influence of Hydrochloric Acid on Vegetation.— Hydrochloric
acid fumes, if emitted from works on a large scale, injure vegetation
much. In former years, before any legal obligations were placed
upon manufacturers for the condensing of the volatile products, the
nuisance from this cause was great. In 1823, the duty on salt
being repealed by the Government, an extraordinary impetus was
given to the manufacture of hydrochloric acid, and since all the
volatile products at that time escaped through short chimneys into
the air, a considerable area of land round the works was rendered
quite unfit for growing plants. The present law on the subject is,
that the maximum quantity of acid escaping shall not exceed 2
grains per cubic foot of the air, smoke, or chimney gases; and,
according to the reports of the alkali inspectors, the condensation by
the improved appliances is well within the Act, and about as perfect
as can be devised.
It appears from the reports of the Belgian Commission in 1855, when
virtually no precautions were taken, that the gases are liable to injure
vegetation to the extent of 2000 metres (2187 yards) around any active
works ; the more watery vapour the air contains, the quicker is the gas
precipitated and carried to the earth. If the action of the vapour is
considerable, the leaves of plants dry and wither ; the chlorophyll be-
comes modified, and no longer gives the normal spectrum, while a
thickening of the rind of trees has also been noticed. The cereals suffer
much; they increase in stalk, but produce little grain. The legumi-
nosse become spotted, and have an air of dryness and want of vigour ;
while the potato, among plants utilised for food, appears to have the
strongest resistance. Vines are very sensitive to the gas. Among trees,
the alder seems most sensitive; then come fruit-trees, and last, the
§ 7h 74]
HTDEOCHLOKIC ACID.
lOI
bardy forest trcoa — -the poplar, the aah, the lirae^ the elm, the raaple,
the birch, and the oak,*
g 73. Action upon Cloth and Manufactured Articles. ^ — On black
cloth the acid produces a green Btaiii, vrbich in not moi^t and ahows no
corrosion. On mosjt matters the stain is more or less reddish ; after a
little time no free acid nmy be detected, by simply moistening the spot ;
but if the stain is cut out and l.*oilod with water, there may be aome
evidence of free acid* The absienee of nioisture and corroBion distin-
guiahes the stain from that produced by sulphuric acid*
§74, Poiflonons Effects of Hydrochloric Acid Gas.— Euleu berg t
hsis studied the effects of the vapour of this acid on rabbits and pigeons.
One of these experiments may be cited hx detail, llydrochloric acid giis,
prepared by heating together common salt add sulphuric aeid^ was passed
into a glass shade supported on a plate, and a rabbit was placed in the
transparent chamber thus formed. On the entrance of the vapour, there
was immediate blinking of the eyes, rubbing of the pawa against the
nostrils, and emission of white fumes with the eitpired breath, while the
respiration was irregular (40 to the minute). After the lapse of ten
minutes, the gaa was again introduced, until the atmosphere wa^ quite
thick; the symjitoms were similar to those detailed above, but more
violent; and in fourteen minntet^ from the commencement, the rabbit
sank down on iU right yide (respirations 32). When twenty-two minutee
had elapsed, the gas was again allowed to enter. The rabbit now lay
quiet, with closed eyes and laboured reapiratioUt and finally, after half
an hour of intermittent exjiosure to the gas^ the animal was removed.
The conjoa were oimlesceut, and the eyes tilled with water j there was
frequent shaking of the head and w^orking of the forepiiws. After three
minutes' exposure to the iiir, the respirations were found to be 128 per
minnto ; this quickened respiration lasted for an hour, then gave place to
a shorter and more superficial breathing. On the second day after the
esperimentj the nibbit suffered from laboured respiration (28 to the
minute) and pain, and there was a rattling in the bronchial tubes. Tlte
ainmaJ died on the third day, death Ijeing preceded by slow respiration
(12 to the minute).
The api>eamnces twenty-four hoars after death were as follows : — The
* Thusse wIjo dimvG t*i stuiJy more closely the t!trt*ct of ncids goiieraOy on vpgeui-
tiuii niAy conssult the yfitious |Mi|)ers of iht; alkuli iuspectoi^ coutttiuijd in th« Local
Govoiijmettt R^^lKlrt». See also SFwihubartb, Bifi mueren Qa^^ vxtefu SL'hiiv/€tmur4
mid Soda-Fabriken t^jreiku, Fkrhuttdittngen dm Fernm zur Btfiirdcrimg dm
Qetem^fl^eiases in PrttMMa, 1867, 8. 135. Dingler's Joitmaf, Bd cidv, S. 374-427,
Chriatel, Iff.her die Biiueirkutiif vofk Sdurat-lMmpfeit a^fd'U Kageiatimu
Afth,/, Pharnmeis 1871, p. 252,
VitrtdjaktimrhTiftfUrQfrii^hUickt Mahdn^ X^lh S* 404, 1872,
t Gcwctbc Mi/tfitnct lifirliii, 137t>, S> 15.
102 POISONS : THEIR EFFECTS AND DETECTION. [§ /J.
eyes were coated with a thick slime, and both cornea were opalescent ;
there was strong rigidity of the body. The pia mater covering the brain
was everywhere hypersemic, and at the hinder border of both hemi-
spheres appeared a small clot, surrounded by a thin layer of bloody fluid.
The plex, venos, spin, was filled with coagulated blood, and there was also
a thin extravasation of blood covering the medulla and pons. The lungs
were mottled bright brown-red ; the middle lobe of the right lung was
dark brown, solid, and sank in water ; the lower lobe of the same lung
and the upper lobe of the left lung were nearly in a similar condition,
but the edges were of a bright red. The parenchyma in the darker places
on section did not crepitate. On the cut surface was a little dark fluid,
weakly-acid blood ; the tracheal mucous membrane was injected. The
heart was filled with thick coagulated blood ; the liver was congested, of
a reddish-brown colour, and rich in dark, fluid blood : in the vena cava
inferior was coagulated blood. The kidneys were not hypersemic ; the
intestines were superficially congested.
There can be little doubt that the symptoms during life, and the
appearances after death, in this case are perfectly consistent with the
following view : — The vapour acts first as a direct irritant, and is capable
of exciting inflammation in the lung and bronchial tissues ; but besides
this, there is a secondary eflect, only occurring when the gas is in sufficient
quantity, and the action sufficiently prolonged— viz., a direct coagulation
of the blood in certain points of the living vessels of the lungs. The
consequence of this, is a more or less general backward engorgement, the
right side of the heart becomes distended with blood, and the ultimate
cause of death is partly mechanical. The hyperaemia of the brain mem-
branes^ and even the haemorrhages, are quite consistent with this view,
and occur in cases where the obstruction to the circulation is of a coarser
and more obvious character, and can therefore be better appreciated.
§ 75. Effects of the Liquid Acid.— There is one distinction between
poisoning by hydrochloric and the other mineral acids — namely, the
absence of corrosion of the skin. Ad. Lesser * has established, by direct
experiment, that it is not possible to make any permanent mark on the
skin by the application even of the strongest commercial acid (40 per
cent.). Hence, in any case of suspected poisoning by acid, should there
be stains on the lips and face as from an acid, the presiunption will be
rather against hydrochloric. The symptoms themselves differ very little
from those produced by sulphuric acid. The pathological appearances
also are not essentially different, but hydrochloric is a weaker acid, and
the extensive disorganisation, solution, and perforation of the viscera,
noticed occasionally with sulphuric acid, have never been found in hydro-
chloric acid poisoning. We may quote here the following case : —
* Virchow's Archivf, path. Anal,, Bd. xxxiiL Hft 2, S. 216, 1881.
§ 7^-]
HYDROCHLORIC ACtD.
105
A woman J uudor the itifluenue of great and sudden grief — not unmixed
with passion — drew a bottle from her pocket, and emptied it verj
quickly. She iramediatelj uttered a crjj writhed, and yomited a yellow-
green fluids The abdomen also became enlarged. Milk wa« given her,
but she could not swallow it, and death took place, in convulsion a, two
hours after the drinking of the poison.
The poat-morteni appearances were briefly as follows *^Mouth and
tongue free from teittural change : much gas in the abdomen, more espe-
cially in the stomach: the membraties of the i>raiti congested; the lungs
filled with blcH>d* The stomach vvas strongly pressed forward, of a dark
brown-red, and exhibited many irregular blackish spots, varying from
two lines to half an inch iu diameter (the spots were drier and harder
than the rest of the stomach) ; the mucous membrane, internally, waa
generally blackened, and changed to a carbonised, shaggy, slimy mass,
while the organ was filled with a blackish homogeneous pulp, which had
no odour. The gullet was also blackened. A considerable quantity of
hydrochloric acid was separated from the stomach,*
The termination in this instance was unusually rapid, In a case
detailed by Caaper,t in which a boy drank an uuknown quantity of acid>
death took place in seven hours. In Guy^s Hospital museum, the duo-
denum and stomach are preserved of a patient who is said to have died
in nine and a half hours from half an ounce of the acid. The same
quantity, in a case related by Taylor, caused death in eighteen hours.
From these and other instances, it may be presumed that death from
acute poisoning by hydrochloric acid will probably take place within
twenty-four hours. From the secondary effects, of course, death may
take place at a remote period ; e.*;., in a case recorded by Dr, Duncan
{Lanfei^ April 12, 1890), a man drank about 1 0%. of HCl accidentally,
wa,s admitted to Charing Cross Hospital the same day, and treated with
small quantities of sodium carbonate, and fed by the rectum. On the
eighth day he brought up 34 oz. of blood ; in a month he left apparently
perfectly well, but was admitted again iu aliout six weeks, and died of
contraction of the stomach and stricture of the pylorus on the ninety-
fourth day,
§76. Foet-mortem Appearances,— The pathological appearances are
very similar to those found in the case already detailed; though the
skin of the face tn&y not be eroded in any way by the acid, yet the more
delicate mucous membrane of the mouth, gullet, etc*, appears moatly to
be changed, and is usually white or whitish-brown. There is^ however,
in the museuoi of the Royal College of Surgeons the stomach and gullet
• Frtms, Mad, KerHnsseit, H. fYicdiriehs Biatierf. gen>hU. Anthr^fpd&gU, l$$Bt
t Otts« 2n<i.—acrichllkhe Mudimn, Uli 0I, Berlin, 1876.
1
104 POISONS : THKIR KFFBCTS AND DETECTION. [§ 76.
(No. 2386c.) of an infant 13 months old; the infant drank a teacupful
of strong hydrochloric acid, and died nine hours after the dose. The
pharynx and the upper end of the gullet is quite normal, the corrosiye
action commencing at the lower end, so that, although the acid was con-
centrated, not the slightest effect was produced on the delicate mucous
membrane of the throat and upper part of the gullet. The lower end of
the gullet and the whole of the stomach were intensely congested ; the
rugsB of the latter were ecchymosed and blackened by the action of
the acid. There were also small haemorrhages in the lungs, which were
ascribed to the action of the acid on the blood. Perforation of the
stomach has not been noticed in hydrochloric acid poisoning.
In Guy's Hospital museum (prep. 1799^^), the stomach and duodenum
of the case mentioned exhibit the mucous membrane considerably
injected, with extravasations of blood, which, at the time when the
preparation was first arranged, were of various hues, but are now some-
what altered, through long keeping in spirit. In St. George's Hospital
museum (ser. x. 43, d. 200) are preserved the stomach and part of the
duodenum of a person who died from hydrochloric acid. The case is
detailed in the Medical Times and Gazette for 1853, vol. ii. p. 513. The
whole inner surface appears to be in a sloughing state, and the larynx
and lung were also inflamed. In St. Bartholomew's Hospital museum
(1946, f. 1899) is preserved the oesophagus and stomach of an infant
aged 1 year who died from hydrochloric acid poisoning. The mucous
membrane of the gullet is white and shrivelled, that of the stomach
covered with large patches of a dark brown colour which represent
altered blood. The effect ceases at the pylorus.
A preparation, presented by Mr. Bowman to King's College Hospital
museum, exhibits the effects of a very large dose of hydrochloric acid.
The gullet has a shrivelled and worm-eaten appearance ; the stomach is
injected with black blood, and was filled with an acid, grumous matter.*
Looking at these and other museum preparations illustrating the
effects of sulphuric and hydrochloric acids, it is difficult (in default of
the history of the cases) to distinguish between the two, by the naked-
eye appearances, save in those cases in which the disorganisation was so
excessive as to render hydrochloric acid improbable. On the other hand,
the changes produced by nitric acid are so distinctive, that it is im-
possible to mistake its action for that of any other acid. The nitric
acid pathological preparations may be picked out at a glance.
* A drawing of parts of the gullet and stomach is given in Guy and Femer's
Forensic Medicine,
%77-]
HYDROCaLORlC ACID.
los
Detection and Estimation of Free Hydrochloric Acid.
I 7T. (1) Detection. — A large number of colouring reagents have
been proposed as testtj for the presence of free mineral acid. Among the
best is junthijl-anUine violet decoliirised by a large aroouTit of hydrochloric
acid; the violet turns to^reeD with h moderate quantityi and to blue
with a small quantity.
TropB&olin (00), in the presence of free mineral acidj strikes & nibj-
red to a d^irk brown- red.
Congo-red is used in the form of paper dyed with the material;
large amounts of free hydrochloric acid strike blue-black, small quan-
tities blue.
Gtlnzburg's test ia 2 parts phloroglucin and 1 part vanillin, dissolved
in 100 ]ydrtA of alcohol. Fine red crystals are precipitated on tlie
addition of hydrochloric acid. To test the stomach cotitents for free
hydrochloric acid by means of this reagmt^ equal parts of the fluid and
the test are evaporated to dryness in the water-bath in a porcelain dish.
If free hydrochloric acid be present, the evaporateil residue shows a red
colour ; 1 mgrm. of acid can by this test be detected. The reaction ie
not interfered with by organic acids, peptones, or albntnip.
Jaksch speaks highly of hemjfj^urpnrin a^ a test. Filter-paper is
soaked in a saturated aqueous solution of bunKopurputin G B (the variety
1 or 4 C is not so sensitive), and the filter- paper thua prepared allowed
to dry. On testing the contents of the stomach with the reagent, if
there m more than 4 parts per 1000 of hydrochloric acid the paper la
stained ioteosely blue-black; but if the colour is brown-black, this ia
from butyric or lactic adds, or from a mixture of these acids with
hydrcjchloric acid, If the paper is w^rished with pure ether, and the
colour was due only to organic acid, the original hne of the paper is
restored ; if the colour produced was due to a mixture of mineral and
organic acids, the brown- black colour is weakened ; and, lastly, if duo to
hydrochloric acid alone« the colour is not altered by washing with ether.
Acid salts have no action, nor is the test interfered with by large
amounts of albumins and peptones.
A. Villiers and M, Favolle * have published a sensitive test for
hydrochloric acid. The test consists of a saturated aipieons solution of
colourless aniline, 4 party ; glacial acetic acid, 1 part ; Q'l mgrm, of
hydrochloric acid strikes with this rimgent a blue colour, 1 mgrm. a
black oolour* The liquid under eianiination is brought by evapomtion,
or by the addition of water, to 10 c.c. and placed in a flask ; to this is
added 5 c*c, of a mixture of equal parts of sulphuric acid ami water,
lo6 t»OlSONS : TttElll E^FlECtS ANl) DKTftCTION. [§ JT.
then 10 c.c. of a saturated solution of potassic permanganate, and heated
gently, conveying the gases into 3 to 5 c.c. of the reagent contained in
a test tube immersed in water. If, however, bromine or iodine (one or
both) should be present, the process is modified as follows: — The
hydracids are precipitated by silver nitrate ; the precipitate is washed,
transferred to a small flask, and treated with 10 c.c. of water and 1 c.c.
of pure ammonia. With this strength of ammonia the chloride of silver
is dissolved easily, the iodide not at all, and the bromide but slightly.
The ammoniacal solution is filtered, boiled, and treated with SHg; the
excess of SHg is expelled by boiling, the liquid filtered, reduced to 10
c.c. by boiling or evaporation, sulphuric acid and permanganate added
as before, and the gases passed into the aniline. The process is
inapplicable to the detection of chlorides or hydrochloric acid if
cyanides are present, and it is more adapted for traces of hydrochloric
acid than for the quantities likely to be met with in a toxicological
inquiry.
(2) Quantitative estimation of Free Hydrochloric Add. — The
contents of the stomach are diluted to a known volume, say 250 or 500
c.c. A fractional portion is taken, say 10 c.c, coloured with litmus or
phenolphthalein, and a decinormal solution of soda added drop by drop
until the colour changes ; this gives total acidity. Another 10 c.c. is
shaken with double its volume of ether three times, the fluid separated
from ether and titrated in the same way ; this last titration will give the
acidity due to mineral acids and acid salts ; * if the only mineral acid
present is hydrochloric acid the results will be near the truth if reckoned
as such, and this method, although not exact for physiological research,
is usually sufficient for the purpose of ascertaining the amount of
hydrochloric acid or other mineral acids in a case of poisoning. It
depends on the fact that ether extracts free organic acids, such as
butyric and lactic acids, but does not extract mineral acids.
The free mineral acid, after extracting the organic acid by ether, can
also be saturated with cinchonine ; this hydrochlorate of cinchonine is
extracted by chloroform, evaporated to dryness, and the residue dissolved
in water acidified by nitric acid and precipitated by silver nitrate ; the
silver chloride produced is collected on a small filter, washed, and the
* To distinguish between acidity due to free acid and acid salts, or to acidity due
to the combined action of acid salts and free acids, the method of Leo and Uffelmann
is useful. A fractional portion of the contents of the stomach is triturated with pure
calcium carbonate ; if all the acidity is due to free acid, the fluid in a short time
becomes neutral to litmus ; if, on the other hand, the acidity is due entirely to acid
salts, the fluid remains acid ; or, if due to both acid and acid salts, there is a propor-
tionate diminution of acidity due to the decomposition of the lime carbonate by the
free acid. A quantitative method has been devised upon these principles. See Leo,
Diagnostik der KrankJieiten der VerdauvmgsorgwM, Hirschwald, Berlin, 1890.
1 77:\
HTDROCITLORIC ACID,
107
filter, with its contents, drie<l and ignited in a porcelain crucible j the
silver chloride^ multiplied by 0*25426, equals HOL
The best method of estimating free hydrochloric acid in the stomach
is that of Sjokvist as modified by v, Jaksch ; * it \\m the disadvantage
of its aoeumey being interfered with by phosphates } it also does not
distinguish between actual free HCl and the loosely bound HCl with
al bum i nous matters^ — this in a toxicologital case i& of small importance,
because the quantities of HCl found are likely to be large*
The method is based upon the' fact that if carbonate of liaryta be
added to the coutents of the stomach, the organic acids will decompose
the barium carbouate, forming butyrate, acetate, lactate, etc., of barium ;
and the mineral acids, such as hydrochloric acid, will combine, forming
salts of barium.
On ignition, chloride of barium will be unaffected, while the organic
salts of barium will be converted into carbouate of barium, practically
insoluble in carbonic acid free water.
The contents of the stomach are coloured with litmus, and barium
carbonate added until the fluid is no longer acid (as shown by the dis-
a[ij3caiance of the red colour) i then the contents are evaporated to
dryness in a platinum disb, and ignited at a dull red heat ; complete
burning to an ash is not neccBSary. After cooling, the burnt mass is
repeatedly exhausted with boiling water and filtered ; the chloride of
barium is precipitated from the filtrate by means of dilute Bulphuric
acid ; the barium sulphate filtered oft* washed, driedjand, after ignition,
weighed; 233 parts of barium sulphate equal 73 parts of HCL
A method sumewhat quicker, but depending on the same principles,
has been suggested by Brauu.t A fractional piirt, say 10 c.c., of
the fluid contents is coloured by litmus and titrated with decinormal
soda. To the &ame quantity is added 2 or 3 more c,c. of decinormal
soda than the quantity used in the first titration ; this alkaline
liquid is evaporated to dryness and ultimately ignited. To the ash
is now added exactly the quantity of decinonnal sulphuric add as the
decinormal soda last used to make il alkaline^ that is to say, if the
total acidity was equal to 3'G d.n. soda^ and 5*6 d.n. soda was added to
the 10 c.c* evaporated to dryness and Imniedj then 5*6 e,o. of d*n*
sulphuric acid is added to the ash. The solution is now warmed to get
rid of carbon diojcide, and, after addition of a little {ihenolphthalein,
titrated with dai* soda solution vmtil the change of colour shows stitura-
tion, the number of c.c. used, multiplied by 000365, equals the HCU
' Klitiisch*: Diatjmdik, Dr, Rudolph v, J*kachj Wiei* u. lieifizigi 1S92, Clinicai
Dia^ntisia, English tmnalation. Fifth edition, LoDdon : Ch Aries OriMn k Co.,
LiiaiU'd,
!08 POISONS : THEIR EFFECTS AND DETECTION. [§ 78, 79.
§ 78. In investigatiug the staius from hydrochloric acid 011 fabrics, or
the leaves of plants, any free hydrochloric acid may be separated by
boiling with water, and then investigating the aqueous extract. Should,
however, the stain be old, all free acid may have disappeared, and yet
some of the chlorine remain in organic combination with the tissue, or in
combination with bases. Dr. Angus Smith has found weighed portions
of leaves, etc., which had been exposed to the action of hydix>chloric
acid fumes, richer in chlorides than similar parts of the plants not thus
exposed.
The most accurate method of investigation for the purpose of separat-
ing chlorine from combination with organic matters is to cut out the
stained portions, weigh them, and bum them up in a combustion tube,
the front portion of the tube being filled with caustic lime known to be
free from chlorides; a similar experiment must be made with the
unstained portions. In this way a considerable difference may often be
found ; and it is not impossible, in some instances, to thus detect, after
the lapse of many years, that certain stains have been produced by a
chlorine-holding substance.
IIL-NitPic Acid.
§ 79. Gleneral Properties.— Nitric acid — commonly known in England
as aqua fortisy chemically as nitric acid, hydric nitrate, or nitric mono-
hydraie — is a mono-hydrate of nitrogen pentoxide (NgO^), two equi-
valents, or 126 parts, of nitric acid containing 108 of NgOg, and 18 of
HgO. Anhydrous nitric acid, or nitrogen pentoxide, can be obtained by
passing, with special precautions, dry chlorine over silver nitrate ; the
products are free oxygen and nitrogen pentoxide, according to the fol-
lowing equation : —
Silver Nitrate. Chlorine. Silver Chloride. Nitrogen Pentoxide. Oxygen.
AgaO,N205 + 201 = 2AgCl + NA + 0
By surrounding the receiver with a freezing mixture, the acid is con-
densed in crystals, which dissolve in water, with emission of much heat,
forming nitric acid. Sometimes the crystals, though kept in sealed tubes,
decompose^ and the tube, from the pressure of the liberated gases, bursts
with a dangerous explosion.
Pure nitric acid has a specific gravity of 1*52, and boils at 98'. Dr.
Ure examined the boiling point and other properties of nitric acid very
fully. An acid of 1*5 specific gravity boils at 98 •8" ; of specific gravity
1-45, at 115-5'; specific gravity 1-40, at 118-8' ; of specific gravity 1*42,
at 122-8°, 123'*-124'. The acid of specific gravity 1*42 is the standard
acid of the British Pharmacopoeia. It can always be obtained by
§ 80-82.]
NITRIC Acrn.
109
distilling either Bfcrong or raoderatoly iveak nitric acid; for^ on the one
handj the acid on distillation gel^ weaker until the gravity of 1^42 m
reached, or, on the other, it beooiueB stronger.
It has been held that acid of 1*42 gravity is a definite hydrate,
(2NO3H, SH^O); it correapond^ to 70 per cent, of the liquid acid HNO^,
There are also at Icaat two other hydrates known^one an acid of 1 '484
apeeiOc gravity, 2N0^B, H/), b.p. 121" ; the other an acid of sp<}cifie
gravity 1-405, iNO^H.TH.O, h.p, 125^
In Germany the officinfil acid ia of 1*185 specific gravity, correspond-
ing to about 30 per cent* of HNO.j. The dilute nitric acid of the
Pharmacopoaia is a colourlesa liquid, of specific gravity I'lOl, and should
ootttain about 17-4 per cent, of acid. The acids used in varioufi in-
dustries are known respectively as dtjers^ and mgrarers^ acid. Dt/^n's'
acid has a specific gravity of 1-33 to 1*34 (66" to 08" Twad.), that ia,
strength from 56 to 58 per cent, of IINOjj, Em/rat'ers* acid is stronger,
being of r40 specific gravity (80" Twad,), and contains 70 per cent of
HNOg. Although the ^i^rc acid of commerce is (and should be) almost
colourless, most oonuTiercial specimens are of hues from yellow up to
deep red. An acid saturated with red oxides of nitrogen is often known
us "fuming nitric acid/'
§ 80. ITse in the Arts. — Nitric acid ia employed very extensively in
the arts and mauufactures. Tlie dyer uses it as a solvent for tin in the
preparation of valuable mordanta for calico and other fabrics ; the
engraver uses it for etching copper. It is an in dispensable agent in the
manufaoture of gun-cotton ^ nitro-glycerin, picric acid, and sulphuric
acid ; It is also used iti the manufacture of tallow, in pre|)aring the felt
for hats, and in ttie gilding trades. It is said to be utilised to make
yellowish or fawn coloured spots on cigar leaves, so as to give them the
appeamnce of age and quality. It is also used as a mediciue,
g 81. Statistics of Poisoning by Nitric Acid, — In the ten years
ending 1Q03 one case of uiurder was ascrilied to nitric acid, and it
caused accidentally 21 deaths, and was used in 69 cases of suicide.
The following table gives the sex distribution of these deaths ; —
DEATHS IK ENGLAND AHD WALES DURING THE TEN YEARS
ENDING 1903 FROM NITRIC ACID.
AOOIDRST Oa NET^LIOENOa.
Males 13
Feinalf^^ * .... 8
Total,
21
Stricins.
Femaloa,
Total,
m
g 82. Fatal Bose. — Tiie dose which cau^eii death has not been aacer-
taiQed with any exactness* As in the case of sulphuric acid^ we may go
I lO POISONS : THEIR EFFECTS AND DETECTION. [§ 83, 84.
SO far as to say that it is possible for a few drops of the strong aoid
to be fatal, for if brought into contact with the vocal apparatus, fatal
spasm of the glottis might be excited. The smallest dose on record is
7'7 grms. (2 drachms), which killed a child aged 13.
§ 83. Action of Nitric Acid on V^etation. — Nitric acid acts on
plants injuriously in a twofold manner — viz., by direct corrosive action,
and also by decomposing the chlorides which all plants contain, thus
setting free chlorine, which decomposes and bleaches the chlorophyll.
The action is most intense on soft and delicate leaves, such as those of
clover, the cabbage, and all the crucifersB. The tobacco plant is particu-
larly injured by nitric acid. Next to all herbaceous plants, trees, such
as the apple, pear, and other fruit trees, generally suffer. The coniferse,
whether from their impregnation with resin, or from some other cause,
possess a considerable resisting-power against nitric acid vapours, and
the same is true as regards the cereals ; in the latter case, their siliceous
armour acts as a preserving agent.
§ 84. Nitric Acid Vapour.— -The action of nitric acid in a state of
vapour, as evolved by warming potassic nitrate and sulphuric acid
together, has been studied by Eulenberg. A rabbit was placed under a
shade into which 63 grammes of nitric acid in a state of vapour were in-
troduced. From the conditions of the experiment, some nitric peroxide
must also have been present. Irritation of the external mucous mem-
branes and embarrassment in breathing were observed. The animal in
forty-five minutes was removed, and suffered afterwards from a croupous
bronchitis, from which, however, it completely recovered in eleven days.
A second experiment with the same animal was followed by death. On
inspection, there was found strong injection of the cerebral membranes,
with small extravasations of blood; the lungs were excessively con-
gested ; the right middle lobe especially was of a liver-brown colour, and
empty of air : it sank in water.
0. Lassar * has also made a series of researches on the influence of
nitric acid vapour, from which he concludes that the acid is not absorbed
by the blood, but acts only by its mechanical irritation, for he could not
trace, by means of an examination of the urine, any evidence of such
absorption.
There are a few instances on record of the vapour having been fatal
to men ; for example, the well-known case of Mr. Haywood, a chemist of
Sheffield, may be cited. In pouring a mixture of nitric and sulphuric
acids from a carboy of sixty pounds capacity, the vessel broke, and for
a few minutes he inhaled the mixed fumes. He died eleven hours after
the accident, although for the first three hours there were scarcely any
symptoms of an injurious effect having been produced. On inspection,
* Hoppe-Seyler's Zeiischrifbf. physiol, Chemie, Bd. i. S. 166-173, 1877-78.
§85-]
NITKIC AOID*
III
there was found intense congestion of the windpipe and broucbial tubes,
with effimion of blood in the latter. The lining membrane of the heart
and aorta was inflamed ; iinfortunatelj, the larynx was uot examined,*
A verj similar case happened in Edinburgh in 1863. t Two young
men were carrying a jar of nitric add ; the jar broke, and they attempted
fco wipe up tho acid from the floor. The one died ten hours after the
j«3cident, the other in leas than twenty- four hours. The symptoms were
mainly those of difhcult breathing, and it is probable that death was
produced from autfocation* Dr. Taylor relatea also, that having accident-
ally inhaled the vapour in preparing gun -cotton ^ he snft'ered from severe
constriction of the throat, tightness in the chest, and cough, for mora
than a week. J
S 85. Effects of Liquid Nitric Add. — Criminal poiaouing by nitric
acid, though still rare, is naturally more frequent than formerly. At
the beginning of the 1 9th century, Tartra § wrote a most eicellent mono-
graph on the subject, and collated all the cases he could find, from the
at recorded instances related by Bembo || in Venetian history, down to
^liis own time. The number of deaths in those 400 yeai*s was but fifty*
five* while, in the 18th century, at least fifty can be numbered in England.
Most of these (74 per cent.) are auicidalj a very few homicidal, the reat
accidentah In one of Tartni^s cases, some nitric acid ivas placed in the
wiue of a <lrunken woman, with fatal effects Oseubriiggerifl relates the
case of a father murdering bis six children by means of nitric acid ; and
C. A. Buchner ** that of a soldier who poured acid into the mouth of bis
illegitimate infant. A curious ciise is one in which a man poisoned his
drunken wife by pouring the acid into her right ear ; she died after six
weeks* illness. All these instances prove again, if necessary, that the
acid is only likely to be used with murderous intent in the case of
young cbildreu, or of sleeping, drunken, or otherwise helpless people.
As an cKample of the way in w^bicli accidents are brought about by
heedlessness, may be cited the comparatively recent case of a woman
who bought a small quantity of aqua for tie for the purpose of allaying
toothache by a local application. She attempted to pour the acid
direct from the bottle into the cavity of the tooth ; the acid went down
her throat, and the usual symptoms followed. She threw up a very
• Lan^t, April 15, 1854, p. 430,
t Chtmkal Netts, March 14, 1863, p, 132,
^ Pditcipft^and Pradm qf Mffiiiiftl AfitH^ifTitdmrf, vol, i. p, 218, 1873*
I Tartra, A. Ev, Dr., Traile dti r£!mpQimuntfn4^ii par PActde NUt*qH€^ P&ri'i,
An. 10(1802), \ip, 300.
\\ Bfffttbo Carditialiiij Iicrn:m Vcniittrium Ili^ifrttt^ lib, i. p, 12, pAriBEd,^ 1551.
IT Allf^m^'Dmlx^ BiTftfeeehtszeUung^ htramiftg. ik JVe, w HoUzcndorff^ 5
Jilifg., Hft, 6, 8. 278, 1865,
*' Friedericb's BhiUerf, ^r. MttL, \%m, Hft, S, S, 187,
112 POISONS : THEIR EFFECTS AND DETECTION. [§ 86, 87.
perfect cast of the gullet (preserved in University College museum),
and rapidly died. Nitric acid has been mistaken for various liquids,
and has also been used by injection as an abortive, in every
respect having a toxicological history similar to that of sulphuric
acid.
§ 86. Local Action. — When strong nitric acid comes in contact with
organic matters, there is almost constantly a development of gas. The
tissue is first bleached, and then becomes of a more or less intense
yellow colour. Nitric acid spots on the skin are not removed by
ammonia, but become of an orange-red when moistened with potash
and a solution of cyanide of potassium. The yellow colour seems to
show that picric acid is one of the constant products of the reaction ;
sulphide of ammonium forms a sort of soap with the epidermis thus
attacked, and detaches it.
§ 87. Symptoms. — The symptoms and course of nitric acid poison-
ing differ in a few details only from those of sulphuric acid. There
is the same instant pain and frequent vomiting, destruction of the
mucous membranes, and, in the less severe cases, after-contraction of
the gullet, etc.
One of the differences in the action of nitric and sulphuric acids is
the constant development of gas with the former. This, without doubt,
adds to the suffering. Tartra made several experiments on dead
bodies, and showed that very considerable distension of the intestinal
canal, by gaseous products, was the constant result ; the tissues were
corroded and almost dissolved, being transformed, ultimately, into a
sort of greasy paste. The vomited matters are of a yellow colour,
unless mixed with blood, when they are of a dirty brown hue, with
shreds of yellow mucus, and have the strong acid reaction and smell
of nitric acid. The teeth may be partially attacked from the solvent
action of the acid on the enamel. The fauces and tongue, at first
blanched, soon acquire a citron-yellow, or even a brown colour; the
whole cavity may swell and inflame, rendering the swallowing of liquids
difficult, painful, and sometimes impossible. The air-passages may
also become affected, and in one case tracheotomy was performed
for the relief of the breathing.* The stomach rejects all remedies;
there are symptoms of collapse ; quick, weak pulse, frequent shivering,
obstinate constipation, and death (often preceded by a kind of stupor)
in from eighteen to twenty-four hours. The intellectual faculties
remain clear, save in a few rare instances.
C. A. Wunderlich has recorded an unusual case, in which the
symptoms were those of dysentery, and the large intestine was found
acutely inflamed, while the small one was little affected. The kidneys
* Arnott, Med. Qaz. , vol. xii. p. 220.
§ 88.]
NITRIC ACID.
"3
*
had the same appearance as in Brighfc*a disease.* Should the dose
of nitric acid be insiifficient to kill at once, or, what amounts to
the samB things ahould the acid be immediately diluted with water,
or tti Bome way be neutralised, the patient, as in the cose of
sulphuric acid, iiiaj yet die at a variable future time from stenosis
of the gullet, impi^ired digest ion, eto. For example, in an interest-
ing case related by Tartra,t a woman, who had swallowed 42
grma. (15 oz.) of nitric acid, feeling acute pain, took immc<iiately a
qnautiky of water, and three hours afterwards nas adnittted into
hospital, where she received appropriate treatment. At the end of a
month she lett, believing herself cured ; but in a little while returned,
and was readmitted^ sntTering from roarasmos, extrenie weakness, luid
constant voraiti tig ; ultimately she died. The post-mortem examination
revtiftled extreme contraction of the intestinal canal tfiroughont. The
lumen would hardly adn>it a penholder* I'he stomach wus no larger
than an ordinary intestine, and was adherent to adjacent organs; on its
internal surface there were spots, probably cieatriecs ; there were also
changes in the gullet, but not so marked. A somewhat similar case
is related by the same author in his thirteenth observation. In the
Middle^s Hospital there is preserved the stomach (No. 1363) of a
man who died forty days after swallowing 2 ozs. of nitric acid diluted
in a tumbler of water. The stomach is contracted, the mucons mem-
brane of the lower part of the gullet, the lesser eurvature, and the
pyloric end of the stomach is extenaively corroded, showing ulcerated
[latches conunencing to ciaitriao.
g 88, Poet-mortem Appearances. — The pathological changes in
the tougnej gullet, and stomach can be readily studied from the
prejmrations in the different museuma. The staining by the nitric
aeid appears unchanged to the naked eye for many years; hence,
most of the nitric acid preparations are in on e?ceellent state of pre-
servation. A very good example of tlie pathological changes is to lie
found in Nos, 1049 and 1050, University College museum.
No. 1049 firea^ntfi the tongue, pharynx, Ai\d I&iyiix of a nmn who liad awallimi^d
a te^cujiful of nitric acid. Tlie epithelium of the ojsophagiiH m for the nio^t p^rt
wautingT and haugs in »lirt'ds; the dorsum of iha tongiie^ in front of the circum-
vallate papillffi, ia excavated, ai^d over its central part su|«?rfictally ulcerated \ in
other places the tongue is encrusted with a tliick, loose, fawn-coloured lajer, r!>nn(?d
prtil^hly of desquamated ^plthelinm. The whole of the mucona surface i^ stained u
dirty yellow*
No. 1050 id a preparation showing the tongue, gulli^tt and stomach of a person
Trho died from the effects of nitric acid* The tongue in pliw;es ia amooth and gj^y-ed :
• Be Adicfnihun qtsihimlam Acidt Mirici Caviiim in Cvrpwt Hmrmnnm (m-
ffiim. Frogramma A cat fan,, Lipstn, 1&57, 4.
t Op, cil,
8
114
POISONS : THBIR KFFKCT8 AND DETECTION.
[iS8.
in oth«rs slightly depressed t^nd excavatal. On the ftnt'erior wall and upper portioti
of the gullet two l&rg€ sloQghs exist,
Altbouglj pflrfomtioE of the fitom*ch h not so common with tntric ns with sul-
phuric acid, such an accident maj occur^ as showTi In a pi'ep&nition at Guy's Hob-
pitalf In which thero is a. p^rfamtiou at the oardiac end. All the mucous m^mbraue
baa diMppearedi and the inner nurfoce is for the most {«rt covered yvith flijcculent
shreds. Three ouDces of uitrio acid aro said to have been swallowed, aud the
patient tired aeventeen hours. There m the usual gtaining. Thero h al^o in the
MiddleBcx Hosipita! (No. 1361) tbe iusopbagtis and stomach of a woman nged 30^
who died mx houra after swallowing 2 to S ozs. of strong mtJic acid. Thf inner
Cimi6 of the miii<oii» mombjane of the gullet and stomach are in purt couvert^^d intci
opaijue yellow and black eachars, and in part to a sbfeddj pulpy condition. At
the most dei>ending part of the stomach is a large ragged perforation, with pulpy
marginSj whicli allowed the contents of the atomaeh ttJ eHCajje into the peritoneal
cavity.
In Bir Bartholomew^H muBeum there is a very good specimen (No. 1&70) of the
app«aranceti in the gullet and stomach after poisoning by nitric acid. The case is
detailed in Si. Ear£MlQfneiG*s B'a'ijtifal Report ^^ VoL v. p. 247» A male dtefl in
ftfteeu hotiii after swallowing 1 02. of nitric acid. The whole mucous niembrano
is wrinkled, or ratlrer ploughed ^ into longitiidiual furrown, the yellow disco loration
Htops abruptly, ■ftith an irregular border, at the commencement of the stomach, the
epithelial and raucoua coats of which are wanting — its surface being rough and of a
brownish-red colour.
The following prepamtions are to be found in the museqm <if the London
Hospital: — A. k 1, and A. h. 8. — A- b* 1. shows the pharynx, o^soithaguSj larynx,
and stomiu^h of a young woman, who, after taking half iin ounee of nitric aoid, died
in eight hoursi. The staining is very intense ; as an unusual feature, it may be
noted that the larynx is almost i^s yellow as the oeisophagus. The abroEiion or ^lu*
tion of the epithelium op the dorsum of the tongue has dissected out the eircum vallate
and fungiform papilla ^ so that they project with nn usual djBtiuctness. The lining
membmne of the gullet throughout is divided into minute squared by longitiidjaal
and transverse furrows. The mucous membrane of the stomach appeara wholly
destroyed, and presents a woolly appearance.
A. b, 8. shows a very perfect eatit of the oesophagus. The cohc was that of a
worn an J aged 35, who swallowed half an ounce of nitric acid. The symptoms for the
first four days weiti the us^ial pain in the throat and stomach, which might be
expected ■ the Iwwela were freely oi»en, and the stools dark and olTeiisive, On the
sixth duy^ there waF; constant vomiting with oneusive breath ; on the niuth^ the
appearance of the |Hitieut was critical , and ithe threw up the cast preserved. She died
oil the tenth day after the taking of the acid. The gulletj stomachy trachea, and
larynx were found after death much inflamHl.
^ ' The following preparations are in St, lliomas' Hospital : — P. 5. — A stomach with
gullet attached. The stomach is covered with yellowish -green patches of false mem-
hraue and deposit ; the gullet has the usual langitudinal funows no oharoc^teristic
of corrosive fluids.
P. 6. is ali^o from a case of nitric acid poisoning. It »hows the lining membrane
of the stomach partly destroyed and shreddy, yet but little discoluured, the hue being
a sort of delieate fawn.
To these may he added a case described and flgured by L*^er ^ to a baby, a few
days oldj an unknown quantity of fuming nitric acid was given \ the cbiltl made a
gurgling, choking sound, and died in a few minutes. The corpse, nine days after
death| showed no signs of decompoaitiou. The tongue and gums were yellow, the
gullet less so J the stomach 9 til I less, and the small intestine had no yellow tint ; the
whole of the month, is^llet^ and Btomatih showed the corrosive action of the acid. The
§89^]
KTTRIC ACTB.
gr«<!iiAtio'U of tint, Leswr reiDnrks, ia wliat is not seen vben tlie joUow colour is dne
to poisoning by chromic acid or by strong aolntion of ferric pcrchloride ; in such
OAsett, wljeceirer the liquid has gone, thc^re ia u yellowniisH. •
% 89. Deteetioa and Estimation of Nitric Acid, —The detection
either of free nitric acid or of its salts h not difficult. Free nitric acid,
after prelimiuarj eatiniatiou of the total acidity by decinormal soda,
may Ije separated by the cinchonine process given at p* 106. On pre-
cipitation by ammonia or soda golntian, the nitrate of ammonia or soda
(andf it may l>e, other similarly combined acid a) remain in Bolution.
If free nitric acid is present in small quantity only, it may be necessary
to evapurftte the filtrate from the cinchonine nearly to dryness, anil to
test the concentrated liquid for nitric acid. The ordinary tests are aa
follows :—
(1) Nitratf^, treated with mercury or copper and strong sulphnric
acid, develop nitric oxidCj recognised by red fumes, if mixed with nir
or oxygen.
(2) A nitrate dissolved hi a small qnantity of water, with the addition
of a crystal of ferrous sulphate (allowed to partially dianolve), and then
of strong sulphuric acid — poured through a funnel with a long tube
dipping to the bottom of the test tube, so a» to form a layer at the
bottom— strikes a brown colour at the junction of the liquid, When
the test is properly performed, there will be three layers — the upper-
most being the nitrate solution, the middle ferrous sulphate^ and the
lowest aulphuric acid ; the middle layer becomes of a smoky or black
hue if a nitrate is present. Organic matter interferes much with the
reaction,
(3) Nitrates in solution, treated in the cold with a zinc copper couple,
are decomposed first into nitrites, and then into ammonia. The nitrites
may be detected by a solution of ni e ta phetiy Id 1 amine, which strikes
a red colour with an infinitesimal quantity. Hence, a solution which
gives no red colour with metaphenyldi amine, when sxibmitted to the
action of a zinc copper con pie, and tested from time to time, cannot
contain nitrites; therefore no nitrates were originally present.
(4) Nitrates^ on being treated with strong sulphuric acid, and then
a solution of indigo carnune dropped ioj ilecoloriso the indigo ; this is
a useful test— not conchiBive in itself, but readily applied, and if the
Ginchonine method of separation has been resorted to, with few sources
of error*
There is a process of separating nitric acid direct from any organic
tissue, which may sometimes be useful i — Place the substance in a strong,
wide-mouthed tlank, closed by a caoutchouc cork, and in the flask put
A small, short teat tube, charged with a strong solution of ferrous
• A, Leaser, Aii&$ der pmiehilkhen M^icin, BotIjp, 1884, T^^fel i, fig, 2,
Il6 POISONS: THBIR EFFECTS AND DBTKCTION. [§ QO, 9I.
chloride in hydrochloric acid. The flask is connected to the mercury
pump (see fig. p. 50), and made perfectly vacuous by raising and
lowering the reservoir. When this is eflected, the tube is adjusted so
as to deliver any gas evolved into a eudiometer, or other gas-measuring
apparatus. By a suitable movement of the flask, the acid ferrous
chloride is allowed to come in contact with the tissue, a gentle heat
applied to the flask, and gases are evolved. These may be carbon
dioxide, nitrogen, and nitric oxide. On the evolution of gas ceasing,
the carbon dioxide is absorbed by passing up under the mercury a
little caustic potash. When absorption is complete, the gas, consisting
of nitrogen and nitric oxide, may be measured. The nitric oxide may
now be absorbed by a strong solution of sodic metasulphite, and from
the contraction the nitric oxide determined.
It is also obvious that, by treating nitric oxide with oxygen, and
absorbing the nitric peroxide present by an alkaline liquid of known
strength and free from nitrates or ammonia, the resulting solution may
be dealt with by a zinc copper couple, and the ammonia developed by
the action of the couple directly estimated by titration by a decinormal
hydrochloric acid, if large in quantity, or by " nessifrmng" if small
in quantity.
IV.~Acetic Acid.
§ 90. In the ten years ending 1903, 21 deaths (10 males and 11 females) occurred
in England and Wales from drinking, by mistake or design, strong acetic acid.
A few cases only have been recorded in medical literature, although there liave
been many exi>eriments on animals.
The symptoms in the human subject consist of pain, vomiting, and convulsions.
In animals it causes colic, ]>araly8is of the extremities, bloody urine, and oedema
of the lungs. The lethal dose for plant-eating animals is about 0 *49 gramme )>er kilo.
There should be no diflSculty in recognising acetic acid ; tlic odour alone is, in
most cases, strong and unmistakable. Traces are detected by distilling, neutralising
the distillate by soda, evaporating to dryness, and treating the residue as follows : —
A portion warmed with alcohol and sulphuric acid gives a smell of acetic ether.
Another ])ortion is heated in a small tube of hard glass with arsenious acid ; if
acetic acid is present, or an acetate, a smell of kakodyl is pnxluced.
v.— Ammonia.
§ 91. Ammonia, (NH3), is met with either as a vapour or gaa, or as
a solution of the pure gas in water.
Properties. — Pure ammonia gas is colourless, with a strong,
irritating, pungent odour, forming white fumes of ammonic chloride,
if exposed to hydric chloride vapour, and turning moist red litmus-paper
§92]
AMMONIA.
It;
strongly blui^ By iiit^nae cold^ or by a preasur<i of 6.J atiiKMjphcres
ttt the ordiiuiry temperature, the gaa m readily liquefied j thts lj<|uid
iimmouia boib at 38"* ; its observed speciiie gravity is *73l ; it freezes
at -57"1*. Aiumonia i» readily ubsorl>cd by watur; at 0' water will
take up 1000 times its own volumt% and ut ordinary temf>e rati i res
abuut 600 times its volume. Alcohol also absorbs about 10 per cent.
Ammouia is a strong base, and forms a number of salts. Amuioula is
one of the egiiataut products of tbe putrufaetiou of nitrogenous sub-
atanccs ; it exists iu the atmo^phero iu small proportions^ and iu ev€ry-
thing that uoiitains water. Indeed, water m the only compound equal
to it iu its uuivei-sality of diftiisiou. The minute quantities of ammonia
thus diffused tlironghout nature are probably never in the free state,
hut combinations of ammonia with hydric nitrate, carbon dioxide, etc.
§ 93, Ufiee, •'^A solution of ammouiii in water bits uiiiuy applications
in the arts and industries ; it is used in medicine, and is an indispensable
laboratory r exigent.
The oihcinal caustic preparations of ammonia are — ammoftim liquor
foriior (strosnj mhdiini of avtmfjnia}^ whieh should contain 32*5 per
cent, of ammonia^ and have a specific gravity of *891.
LiquifT ajtiinojwf: {i>fjlutiofi of ainmonia)^ specific gravity *959> and
containing 10 per cent, of ammonia. There iu also a tinifnejd of
atnmonm^ composed of olive oil, 3 parb^, and ammonia^ 1 parL
Sj/iHltu Amtfimiid; Ftrtidtui (Jteiid i^irlt of avivimda). — -A solution
of asafmtida iti rectilied spirit and ammonia solution; 100 parts by
measure, contain 10 of strong solution of ammonia.
Strong sol at ion of ammonia is an important ingredient in the '^ ^tVit-
fnenhmi eamphonn compomta^^ (compotuid lijiimenf of eatttphtft')^ the
composition of which is as foUowt* : — ^jamphor, 2*5 parts ; oil of lavender,
'125; strong solution of ammonia, 5^0; and rectiBai spirit, 15 parts.
Its content of Btrong solution of ammonia is then about 22'6 per cent*
(e<iuivalent to 7*3 of NH^).!
The carbofioie of ammonia is also caustic ; it Is considered to be a
compound of acid carbonate of ammonium^ NH^HCO^, with carbamate
of amniouinnij NH^NIl^C^,^, It is in the form of colourlesSp crystalline
masses ; the odour is powerfully aunuoniacal ; it is strongly alkaline, and
the taste is acrid. It completely volatilises with heat, is soluble in
water, and somewhat soluble in spirit.
The officinal preparation is the " Mfimim ammoniw aror/wxftViw," or
* Sir B, Wt Eii^hardsoD ha& showa that aniJnoDi& poaflen^a powerful aati0cpti0
[jrojiertieai.— i^rji. M^, Joumttl, 1862.
f Thure is a e«Miunon liniment for horse* used in st»ble», and papnlurly kuniVTi
^ '* wliite oil/* It cunUiiiii 1 part oF iimmi]»ritA, and 4 putfl of olive or t»|Hi oU i aot
aufreqijuntly tiir(ietitine h addi^ Auother velerinury Unimont, called **fifgii qU,^*
coutifcinti otuutuok, oil of origanuio, turpuutin^, ftud ttie y«illu of eggs^
!l8 P0I80KS: THEIB EKFBCT8 AND DKTKCTION. [§93-95-
aromatic spirit of ammonia. It is made by distilliDg in a particular way
ammonic carbonate, 4 ozb. ; strong solution of ammonia, 8 ozs. ; rectified
spirit, 120 ozs. ; water, 60 ozs. ; volatile oil of nutmeg, 4^ drms. ; and oil
of lemon, 6| drms. Aromatic spirit of ammonia is a solution in a weak
spirit of neutral carbonate, flavoured with oil of lemon and nutmeg ; the
specific gravity should be 0*896.
Smelling salts («a/ volatile) are composed of carbonate of ammonia.
§ 93. Statistics. — Falck has found throughout literature notices of
thirty cases of poisoning by ammonia, or some of its preparations. In
two of these it was used as a poison for the purpose of murder, and in
eight with suicidal intent ; the remainder were all accidental The two
criminal cases were those of children, who both died. Six out of eight
of the suicidal and twelve of the twenty accidental cases also terminated
fatally.
Ammonia was the cause of 123 deaths (60 male, 63 female) by
accident, and of 93 (39 male, 54 female) by suicide, making a total of
186 during the ten years ending 1903 in England and Wales.
§ 94. Poisoning by Ammonia Vapour. — Strong ammoniacal vapour
is fatol to both animal and vegetable life. There are, however, but few
instances of poisoning by ammonia vapour ; these few cases have been,
without exception, the result of accident. Two cases of death are re-
corded, due to an attempt to rouse epileptics from stupor, by an
injudicious use of strong ammonia applied to the nostrils. In another
case, when hydrocyanic acid had been taken, there was the same result
An instance is also on record of poisonous effects from the breaking of a
bottle of ammonia, and the sudden evolution in this way of an enormous
volume of the caustic gas. Lastly, a man employed in the manufacture
of ice, by means of the liquefaction of ammonia (Carre's process), breathed
the vapour, and had a narrow escape for his life.
§ 95. Symptoms. — The symptoms observed in the last case may well
serve as a type of what may be expected to occur after breathing
ammonia vapour. The man remained from five to ten minutes in the
stream of gas ; he then experienced a feeling of anxiety, and a sense of
constriction in the epigastrium, burning in the throat, and giddiness. He
vomited. The pulse was small and frequent, the face pule, the mouth
and throat strongly reddened with increased secretion. Auscultation
and percussion of the chest elicited nothing abnormal, although during
the course of four days he had from time to time symptoms of suffocation,
which were relieved by emetics. He recovered by the eighth day.*
In experiments on animals, very similar symptoms are produced.
There is increased secretion of the eyes, nose, and mouth, with redness.
The cry of cats becomes remarkably hoarse, and they generally vomit.
• Schmidt's Jalirbuch, 1872, I S. 30.
§96-98]
AMMONIA.
iig
Great difficulty io breathing and tetanic conviilBioiis are present. When
the animal is confined in a amall closed chanihyr^ death takes place in
about a quarter of an hour.
On section^ the bronchial tubes, to the finest ramificatioits, are found
to be filled with a tenacious mucus, and the air-imsBages^ from the glottis
throughout, reddened. The kniga arc etnphyseniatous, but have not
always anj special colour; the heart contains but little coagulated
blood ; the blood ha» a dark red colour*
§96. The chronic eH'eots of the gas, aa shown in workmen engaged in
manufactures in which tlic fumes of ammonia are frequent^ appear to bo
an inflammation of the oyes and an affection of the skin. The latter la
thought to be due to the ammonia uniting to form a soap with the oil
of the iuhri eating skin gland a « Some observers have also noticed deaf-
ness, and a peculiar colour of the skiu of the uoee and fDrehead, among
thme who work In guano manufactories. Its usual action on the body
appears to be a diminution of the healthy oxidation changes, and a
general lowering of btdily strength^ with evident anoimLa.
§97. Ammonia in Solution. — A€tion on Plants.— -Solutions of
strong ammuuia, or holutiouxs of the carbonate, act injuriously on vege*
table life, while the neutral salts of ammonia are, on the contrary,
eiecllent manures. A 30 per cent solution of ammouic carbonate kills
most plants within an hour, and it is indifferent whether the whole plant
is watered w^itli this solution^ or whether it is applied ouly to the leaves.
If, after this watering of the plant with ammonic carlxinate water, the
injurious salt is washed out as far as possible by distilled water, or by a
weakly acidulated fluid, then the plant may recover, after having shed
more or less of its leaves. Those facts sufficiently explain the injurious
ejects noticed when urine is applied direct to plants, for unue iu a very
short time becomes essentially a ^ohUion of ammonic carlx>nate.
§ 9S^ Action on Human Beings and Animal Life, — The violence
of the action of caustic solutions of ammonia almost entirely depends on
the state of concentration.
The local action of the strong solution appears to be mainly the
extriustion of water and the saponifying of fat, making a soluble soap*
On delicate tissties it has, therefore, a destructive action ; but S. Samuel *
has shown that ammonia, when applied to the mibrokeu epidermis, does
Qot have the same intense action aa potash or soda, nor does it euaguJato
albumen. Blood, whether exposed to amnionia gas, or mixed with solu-
tion of ammonia, becomes immediately dark red ; then, later, through
destruction of the blood corpuscles, very dark, even black ; lastly, a dirty
brtjwn-red. The oxygen is expelled, the haemoglobin destroyed, and the
blood corpuscles diseolved.
* Vii^how*8 Afckii>/. path, Am&t., M, It Utl 1 ti. 2, S, il, ©to,, 1870.
126 POISONS: THEIR EFFECTS A^D DETECTtON. [§ 9^.
The albumen of the blood is changed to alkali-albuminate, and the
blood itself will not coagulate. A more or less fluid condition of the
blood has always been noticed in the bodies of those poisoned by
ammonia.
Blood exposed to amtnonia, when viewed by the spectroscope, shows
the spectra of alkaline haematin, a weak absorption band, in the neigh-
bourhood of D ; but if the blood has been acted on for some time by
ammonia, then all absorption bands vanish. These spectra, however, are
not peculiar to ammonia, the action of caustic potash or soda being
similar. The muscles are excited by ammonia, the functions of the
nerves are destroyed.
When a solution of strong ammonia is swallowed, there are two main
effects — (1) the action of the ammonia itself on the tissues it comes into
contact with, and (2) the effects of the vapour on the air-passages.
There are, therefore, immediate irritation, redness, and swelling of the
tongue and pharynx, a burning pain reaching from the mouth to the
stomach, with vomiting, and, it may be, nervous symptoms. The saliva
is notably increased. In a case reported by Fonssagrives,*^ no less than
3 litres were expelled in the twenty-four hours. Often the glands
under the jaw and the lymphatics of the neck are swollen.
Doses of from 5 to 30 grammes of the strong solution of ammonia
may kill as quickly as prussic acid. In a case recorded by Christison,t
death occurred in four minutes from a large dose, doubtless partly by
suffocation. As sudden a result is also recorded by Plenk: a man,
bitten by a rabid dog, took a mouthful of spirits of ammonia, and died
in four minutes.
If death does not occur rapidly, there may be other symptoms —
dependent not upon its merely local action, but upon its more remote
effects. These mainly consist in an excitation of the brain and spinal
cord, and, later, convulsive movements deepening into loss of conscious-
ness. It has been noticed that, with great relaxation of the muscular
system, the patients complain of every movement causing pain. With
these general symptoms added to the local injury, death may follow
many days after the swallowing of the fatal dose.
Death may also occur simply from the local injury done to the
thi-oat and larynx, and the patient may linger some time. Thun, in a
case quoted by Taylor, J in which none of the poison appears actually to
have been swallowed, the man died nineteen days after taking the
poison from inflammation of the throat and larynx. As with the strong
acids, so with ammonia and the alkalies generally, death may also be
♦ L' Union Mtkiicale, 1857, No. 13, p. 49, No. 22, p. 90.
t Christison, 167.
X Principles of JiirisjjrudencCf i. p. 235.
§ 99. >o^0
AMMONIA.
121
caused many weeks and even inoutha aftcfwards from tlie efTects of con-
tmction of the j^ullet, or frDiu the impaireLl nutrition coime^ueiit upon the
dei&tructiou, more or lorn, of portions of the atomach or intestinal canal,
g 99, FoBt-mortem Appearances. — Tn recent cases there h an
InteuMe redness of the iuteKtinal canal^ froiti the mouth to the stomaohf
and even heyond, with hero and there deatruetion of the mucous mem-
brane, and even perfomtioti. A wax preiMmition in the museum of
University College (No. 237S) shows the c fleets on the stomach produced
hy B wallowing strong ammonia ; it is ash en -gray in colourj and most of
the mucous membrane is, as it were, dtsaolvcd away ; the cardiac end is
much congested.
The contents of the stomach are usually coloured with hlood ; the
Vjronchial tubes and glottis are almost constantly fomid iuflamed — even a
croupdrke (or diph then tie) condition lias been seen. (Edema of the glottis
ihould also be looked for : in one aisG this alone seems to have accounted
for death. The blood is of a clear red colour, and fluid, A stnoll of
ammonia may be present.
If asnflicient time has elapsed for secondary efleuts to take place, then
there may bo other appearances. Tlius, in the case of a ^irl who, falling
into a fainting tit, was treated with a draught of undiluteii spirits of
ammonia and lived four weeks afterwards, the stomach (preserved in
St. George's Hospital mnseumj 43 b, ser. ixj is seeti to be much dilated
and covered with cieatricesi and the pylorus is so uontnicted as hardly to
admit a small bougie. It has also been noticed that there is generally a
fatty degeneration of both the kidneys and liver.
It need scarcely be oliserved that in such cases no free ammonia
will be found, and the qucstiou of the cause of death must neoesaarily
be wholly medical and pathological.
§ 100. Separation of Ammonia. ^ — Ammonia is separated in all cases
by distillation, and if the organic or other liquid is already alkaline,
it is at once placed in u retort and distilled. If neutral or acid, a little
burnt magnesia may be added until tbe reaction is alkaline. It is gener^
ally laid down that the contents of the stomach in a putrid condition
cannot he examined for ammonia, because animonia is already present cis
a product of decomposition ; but even under these circumBtanccs it is
possible to give an opinion whether ammonia m e^f^eti^ Is present. For
if, after carefully mixing the whole conteuta of the stoinat^hi and then
drying a portion and reekoniug from tliat weight tiie total nitrogen
(considering, for this purpose, the contents to consist wholly of albumen,
which yields about 16 per cent, of Tiitrogen) — under these conditions,
the contents of the stomach yield more than 16 per cent, of nitrogen as
ammonia reckoned on the dry substance, it is tolerably certain that
ammonia twl derived from the food or the tissues is present.
J 22
POISONS : THKJR EPFECTS AND Dl
[§ lor-ioj.
If, also, tbere ia a Bufficlent evolution of ammonia to cause white
fume% when a rod moistened with hydrochlonc acid is brought near to
the liquid, an effect never noticed with a normal decom|x»sitioii^ the
presenoe of extrinsic anmionia ia probable.
An alkaline-reacting distiUate^ which gives a brown colour with the
"Nessler" reageut, and which, when carefully neutrabssed with sul-
phuric acid, on evaporation to drjnesa by the careful heat of a water-
bath, loiives a crystalline mass volatilisahle by heat, and giving a copigufl
precipitate with an alcoholic solution of pktiuio oliloridc, but m hardly
at all soluble in absolute alcohol, can be no other aub^atance than
aumioina,
g 101. Estiiiiatioii.— Ammonia is most quickly estimated by distil-
hug, receiving the distillate in deciuormal acid, and then titrating bauk.
It may also be estinmted a& the double chloride of amuionium and plati-
num (NH^Cl)3jPtCl4. The distiOate is exaetlj neutrabaed by HCI,
evaporated to near dryness, and an alcoholic sob it ion of platinic chloride
added tn sufficient quantity Ui be always in slight excess, as shown by
the yellow colour of the supormitant fluid. The precipitate is collected,
washed with a little alcohol, dried, and weighed on a tared filter j 100
parts of the salt are equal to 7 "6 of NH^*
VI.— Caustic Potash and Soda.
g 102, There is so little diflerence in the local effects iiroduced by
potash and soda respectively, that it will be convenient to treat them
together.
Fotaab (potassa caustica).— Hydrate of potasainni (KHO), com-
bining weiglit 5G, specific gravity 2-L
Properties. — ^Pure hydrate of jjoUissium is a comfMict* white solid,
uiiLially met with in the form of sticks. When heated to a temperature
a little under redness, it melt** to a nearly colourless liquid ; in thist state
it is inteosely corrosive. It rapidly absorbs moisture from the air, and
moist potiish also absorbs with great avidity carbon dioxide; it is power-
fully alkaline^ changing red litmus to blue. It is sohible in half its
weight of cold water, grejit heat being evolved during solution ; it forms
two detinitc hydrates-^onc, KHQ-i^HgO; the other, KH0 + 2H,0. It
ii spariugly soluble in other^ Imt is dissolved by alcuhol, wo*jd-spirit,
fusel oil, imd glyceriiJ*
§ 103. Pharmaceutical Prepar&tionfi.— Potassium hydrate, as well
tk& the solution of potash, is officinal in all plmrmacopcoias. The liquor
poiasoeif, or solution of pwtashj of the British I'harmacojxuia, is a strongly
^ alkaline, oauiitic li<)uid, of 1*053 specific gravity, and containing 5 84
§ I04''I08.] CAUSTIC POTASH AND SODA, 123
per oeot. by w«ight of KUO. It should, theoretically, not effervesce
when treated with an acid, but its affinity for COj is so great that all
solutions of potash, which have been in any way exposed to air, contain
a little carbonate. Caustic sticks of potash and lime used to be officinal
in the British Pharmacopoeia. Filho's caustic is stiU in conmierce, and
is made by melting together two parts of potassium hydrate and one
part of lime in an iron ladle or vessel ; the melted mass is now moulded
by pouring it into leaden moulds. Vienna paste is composed of equal
weights of potash and lime made into a paste with rectified spirit or
glycerin.
§ 104. Carbonate of Potash (K2CO2+ l^H^O), when pure, is in the
form of small white crystalline grains, alkaline in taste and reaction,
and rapidly deliquescing when exposed to moist air ; it gives all the
chemical reactions of potassium oxide, and carbon dioxide. Carbonate
of potash, under the name of scUt of tartar ^ or potashes, is sold at oil
shops for cleansing purposes. It is supplied either in a fairly pure state,
or as a darkish moist mass containing many impurities.
§ 105. Bicarbonate of Potash (KHCO3) is in the form of large
transparent rhombic prisms, and is not deliquescent. The effervescing
solution of potash {liquor poUusiB effercescens) consists of 30 grains of
KUCO3 in a pint of water (3*45 grms. per litre), and as much CO^ as
the water will take up under a pressure of seven atmospheres.
§ 106. Caustic Soda— Sodium Hydrate (NaHO).— This substance is
a white solid, very similar in appearance to potassium hydrate; it
absorbs moisture from the air, and afterwards carbon dioxide, becom-
ing solid again, for the carbonate is not deliquescent. In this respect,
then, there is a great difference between potash and soda, for the former
is deliquescent both as hydrate and carbonate ; a stick of potash in a
semi-liquid state, by exposure to the air, continues liquid, although
saturated with carbon dioxide. Pure sodium hydrate has a specific
gravity of 2*0 ; it dissolves in water with evolution of heat, and the
solution gives all the reactions of sodium hydrate, and absorbs carbon
dioxide as readily as the corresponding solution of potash. The luiuor
sodcB of the B.P. should contain 41 per cent, of NaHO.
§ 107. Sodse Carbons*— Carbonate of Soda— (Na^COjlOHp).— The
pure carbonate of soda for medicinal use is in colourless and transparent
rhombic octahedrons ; when exposed to air, the crystals effloresce and
crumble. The sodtn carbonas exsiccaia^ or dried carbonate of soda, is
simply the ordinary carbonate, deprived of its water of crystallisation,
which amounts to 62*93 per cent
§ 108. Bicarbonate of Soda (NaHCO,) occurs in the form of
minute crystals, or, more commonly, as a white powder. The liquor
8od(je effervescens of the B.P. is a solution of the bicarbonate, 30 grains
124 POISONS: THEIR KFFECTS AND DETECTION. [§ IO9-III.
of the salt iu 20 ozs. of water (3*45 grms. per litre), the water being
charged with as much carbonic acid as it will hold under a pressure of
seven atmospheres. The bicarbonate of soda lozenges (irochisci sodce
bicarbonatis) contain in each lozenge 5 grains (327 mgrms.) of the
bicarbonate. The carbonate of soda sold for household purposes is of
two kinds — the one, " seconds," of a dirty white colour and somewhat
impure; the other, "best," is a white mass of much greater purity.
Jai^le water {Eau de Javelle) is a solution of hypochlorite of soda ; its
action is poisonous, more from the caustic alkali than from the chlorine,
and may, therefore, be here included.
§ 109. Statistics. — Poisoning by the fixed alkalies is not so frequent
as poisoning by ammonia. Falck has collected, from medical literature,
27 cases, 2 of which were thp criminal administering of Eau de Javelle,
and 5 were suicidal ; 22, or 81*5 per cent., died — in 1 of the cases after
twenty-four hours ; in the others, life was prolonged for days, weeks, or
months — in 1 case for twenty-seven months. In the ten years ending
1903, in England and Wales there were 23 deaths from poisoning by
the fixed alkalies, 12 males and 11 females, all due to accident, not a
single case of suicide or murder.
§ 110. Effects on Animal and Vegetable Life.— The fixed alkalies
destroy all vegetable life, if applied in strong solution or in substance,
by dehydrating and dissolving the tissues. The effects on animal
tissues arc, in part, due also to the affinity of the alkalies for water.
They extract water from the tissues with which they come in contact,
and also attack the albuminous constituents, forming alkali-albuminate,
which swells on the addition of water, and, in a large quantity, even
dissolves. Cartilaginous and horny tissues are also acted upon, and
strong alkalies will dissolve hair, silk, etc. The action of the alkali is
by no means restricted to the part first touched, but has a remarkable
faculty of spreading in all directions.
§ 111. Local effects. — The effects of strong alkali applied to the
epidermis are similar to, but not identical with, those produced by
strong acids. S. Samuel * has studied this experimentally on the ear
of the rabbit ; a drop of a strong solution of caustic alkali, placed on the
ear of a white rabbit, caused stasis in the arteries and veins, with first a
greenish, then a black colour of the blood ; the epidermis was bleached,
the hair loosened, and there quickly followed a greenish coloration on
the back of the ear, opposite to the place of application. Around the
burned spot appeared a circle of anastomosing vessels, a blister rose, and
a slough separated in a few days.
The whole thickness of the ear was coloured yellowish-green, and
later the spot became of a rusty brown.
* Vircliow*s Archivf. path. AruU.^ Bd 11., 1870.
§ n2, U3J
CAUSTIC POTASH AND SODA.
§112. Symptoms. — ^The ayraptoms observed when a pei'aon has
swallowed a dangeroiia dose of caustic (fiied) alkali are very similar to
those noticed with amniotiiaj with the imp>rt^int exception that there is
no respiratory trouble, unleaa the liquid has come into contact with the
glottis 'j nor has there been hitherto remarked the rapid death which
has taken place with a few ammonia poisonings, the shortest time
hitherto recorded being three hours, as related by Taylor in a case
in which a boy had swallowed 3 ozs, of a strong solution of carl K>n ate of
potash.
There is instant pain extending from the mouth to the stomach, and
a persistent and nupleasant taste; if the individual is not a detenmned
suicide, and the poison (as is mostly the case) has been taken accidentally,
the liquid should be immediately ejected as much as possible, and wii-tor
or other liquid at hand drank freely. Shock may at once occur, and the
patieut die from collapse ; but thia, even with frightful destruction of
tissue, appears to be rare. Vomiting supervenes ; vfhni is ejected is
strongly alkaline, and streaked with blood, and has a soapy, frothy
appearance. There may be disirrhfca, great tenderness of the abdomen,
and quick pulse and fever.
With caustic jjotash, there may be also noticed its toxic eftects {aj.>art
from local action) on the heart ; the pulse in that case is slow and
weak, and loss of consciousness and convulsions are not uncommon.
If the collapse and after-ieflammation are recovered from, then, m in the
case of the mineral acids, there is all the horrid sequence of symptoms
pointing to contractions and strictures of the gullet or pylorus, and
the sabsefjuent dyspepsia, difficulty of swallowing^ and not un frequently
actual starvation,
§ 113. Post' mortem Appearances. — In cases of recent poisoning,
spots on the cheeks, lips, clothing, etc., givinp; evidence of the contact
of the alkali, should be looked for; but this evidence in the case of
persons who have lived a few days may be wanting. The mucous
membrane of the mouth, throat, gullet, nud stomf*ch is generally more
or less white — here and there denuded, aiid will be found in various
stages of infiammation and erosion, according in the amount taken, and
the concentration of the alkali. Where there is erosion^ the base of the
eroded parts is not brown-yellow, but, as a rule, pale red. The gullet
ia most affected at its lower part, and it is this part which is mostly
subject to stricture. Thus Bobm * found that in 18 cases of contraction
of the gullet, collected by him, 10 of the 18 showed the contraction at
the lower third.
The changes which the stomach may present if the imtient has lived
some time are well illustrated by a preparation in St. George's museum
• Centramm/HrduMctL Wi^iu.Uli.
126 POISONS: THEIR EFFECTS AND DETBCTIGN. [§ II4.
(43 a. 264, ser. ix.). It is the storaaoh of a woman aged 44, who had
swallowed a concentrated solution of carbonate of potash. She vomited
immediately after taking it, and lived about two months, during the
latter part of which she had to be nourished by injections. She died
mainly from starvation. The gullet in its lower part is seen to be much
contracted, its lining membrane destroyed, and the muscular coats ex-
posed. The coats of the stomach are thickened, but what chiefly arrests
the attention is a dense cicatrix at the pylorus, with an aperture so
small as only to admit a probe.
The colour of the stomach is generally bright red, but in that of a child,
preserved in Guy's Hospital museum (No. 17982^), the mucous membrane
is obliterated, the rugse destroyed, and a dark brown stain is a noticeable
feature. The stomach is not, however, necessarily affected. In a pre-
paration in the same museum (No. 1 798^^) the mucous membrane of the
stomach of a child who swallowed soap-lees is seen to be almost healthy,
but the gullet is much discoloured. The action on the blood is to
change it into a gelatinous mass ; the blood corpuscles are destroyed,
and the whole colour becomes of a dirty blackish-red ; the spectroscopic
appearances are identical with those already described (see p. 60).
The question as to the effects of chronic poisoning by the alkalies
or their carbonates may arise. Little or nothing is, however, known
of the action of considerable quantities of alkalies taken daily. In
a case related by Dr. Tunstall,* a man for eighteen years had taken
daily 2 ozs. of bicarbonate of soda for the purpose of relieving
indigestion. He died suddenly, and the stomach was found ex-
tensively diseased; but since the man, before taking the alkali, had
complained of pain, etc., it is hardly well, from this one case, to draw
any conclusion.
It is important to observe that*the contents of the stomach may be
acid, although the death has been produced by caustic alkali. A child
aged 4 drank from a cup some 14 per cent, soda lye. He vomited
frequently, and died in fifteen hours. The stomach contained 80 c.c. of
sour-smelling turbid fluid, the reaction of which was acid. There were
hsemorrhagic patches in the stomach, and signs of catarrhal inflamma-
tion ; there was also a similarly inflamed condition of the duodenum.f
§ 114. Chemical Analysis. — The tests for potassium or sodium are
too well known to need more than enumeration. The intense yellow
flame produced when a sodium salt is submitted to a Bunsen flame, and
the bright sodium-line at D when viewed by the spectroscope, is a delicate
test ; while potassium gives a dull red band in the red, and a faint but
very distinct line in the violet. Potassium salts are precipitated by tar-
* Afed. Times, Nov. 80, 1860, p. 664.
t Lesser, Atlas d, geruM, Med. , Tafel ii«
I n;, rr6.] sooaTM, potassium, anb ammoioum salts*
127
taric acid, while sodium salts do uot yield this precipitate; potaagium
salts also give a precipitate with platinic chloride insoluble in strong
alcohol, while the compound salt with sodium is rapidlj dissolved by
alcohol or watar* This fact is utilised in the separation and estimation
of the two alkalies,
§ 115. Estimation of the Fixed Alkaliea.^ — To detect a fixe<l
alkali in the contents of the stomachy a convenient process ii to proceed
by dialysis, and after twenty-four hours, to concentrate the outer liquid
by lx>iljng, und then, if it ib not too much coloured, t^ titrate directly
with a decinormal sulphuric acid. After exact neutralisation, the liquid
is eTaporated to dryness, carbonised, the alkaline salts lixiviated out with
water, the sulphuric acid exactly precipitated by baric chloride, and then,
after separation of the sulphate, the liquid treated with milk of lime.
The filtrate is treated with a current of CO.j gas, boiled, and any pre-
cipitate filtered off\; the final filtrate will contain only alkalies* The
liquid may now be evaporated to dryness with either hydrochloric or
sulphuric acids, and the total alkalies weighed as sulphates or chlorides.
Should it bo desirable to know exactly the proportion of potassjum to
sodium, it is beat to convert the alkalies into chlorides— dry gently,
ignite, and weigh ; then dissolve in the least possible quantity of water,
and precipitate by platinic chloride, which should be added so as to be a
little in excess, but not much* The liquid thus treated is evaporated
nearly to dryness, and then extracted with alcohol of 80 per cent., which
dissol vea out nnj of the double chloride of platinum and sodiu in* Finally,
the precipitate is collected on a tared filter and weighed, after drying at
100°. In this way the analyst l>oth diatinguishea between the salts of
sodium and potassium, and estimates the relative quantities of each. It
is hardly necessary to observe that, if the double chloride is wholly
soluble in water or aleoliolj sodium alone is present. This, however, will
never occur in operating on organic tissues and fluids^ for botli alkalies
are invariably present A correction must be made when complex organic
fluids are in this way treated for alkalies which may be naturally in the
fluid. Here the analyst will be guidefl by his preliniinary titration,
which gives the total free alkalinity. In cases where the alkali has been
neutralised by acids, of course no free alkali will be found, but thecorre
sponding salt
VIL — Neutral Sodium, Potassium, and Ammonium Salts,
§ lis. The nmlml m\i» of the alkAliea am poisDuouS; if adminiatertHl in flnfflcimit
doBea, uid the poiaonous effvct of tbt' suiphnte^ chloridej brumide, iodide, t&rtr»t«,
aud dtmte appeal to depend on the speuilic lotion of the alkali metal, rather than
on tlie midf or halogen iti (^mbiaation. According to the reaeiftrohee of Dr, Einger
T28
poisoirs : TnKiR kppects and DKTacTioN* [§ 117-122,
and Dr. Harringbon Sflintsbiiry,* with regard t^i the relatlvp ttjxicity of the three] as
ahc»wji by their effect an the heart of & frog — first, the jMitassium swAU were found to
exert Uie most poisonous action, next cqtho the anunoniuni, aiid^ l^tly, the sodium
esXtA. The higbeat eatim&te would be that sodimo suits are only one < tenth ns
poisonous as those of ammonium or potassium ; the lowcat, that the sodium salts
are one-fifth : although tho i^xperimenta mainly tlirew light Ufwn the action of the
alkftliefi on nn6 organ only, yet the indications obtained probably hold good for the
organism as a whole, and are pretty well bome out by clinj<^ ex|)erience.
Tlfjere apjtcjir to be four eases otj recort! of poisoning by the above neutral salts ;
none of them belong to recent times^ but lie between the years 1S37-'18S6. Hetice,
tb<» main knowledge which we possess of the poiBonous octiou of the [mtsssium salti
is dorivi'<i from eijHirimcnts on aninnils.
S 117, Sodium Salts. ^ — Common salt in such onormoufi quantity aa half a pound
to a pound ban d octroy ed human life^ but thefle cases are so eseeptional that the
|Mjisonou8 action of sodium salLn is of scicntilie rather than pmctioal int<jreat^
g 118* Potaiilum Salts. — Leading fnr future consideration the nitrate and thi>
chlorate of potasshuui [lotaBsia Mulphato and tartrate are sub^itanccs which hava
deHtroycd human life,
PotaBaic Sulphate (K-jSOi) is in the form of eolourless rhomMo crystals, of hitler
fill in 0 taate. It is soluble in ten parts of water.
Hydropotaaaic Tartrate (KHC^H^Ofl), when pure, is in the form of rhombic
crystals, tasting feebly acid. It is solublo in 210 parts of water at n"",
% 110. Action on the Frog^s Heart. — Botli excitability and contractility aro
affected to a powerful degree'. There ia a remarkable slowing of the pulsations,
irftgtdarity, atidj lastly, cessation of pu] nation altogether,
§ 120< Aotion on Warm-blooded AtumaJs.— If a aufiiaient quantity of a
solution of a potaado salt ii Ipjectcd into the blood -vosielfl of an animal, there is
almost imntGdlate d^th from arrest of the beart^a action. Smaller dosfy*, aub-
cutaneoualy applied j produce slowing of the pulse, dyapuceai and convulaions, ending
in death. Small doses produce a transitory diminution of the force of arterial
pressure, which quickly passes, and the blot>d- pressure risfis. There is at first, for
a few seconds, increase in the number of pulsations, bat later a remarkable slowing
of the pulse* The rise in the blo&i-preseure occurs even after stjction of the apinal
cord. Somewhat larger doses cause rapid lowering of the Ijlood-prettsure, and ap|mrent
oessation of the hearths action ; but if the thomi be tbi'n opened, the Ite^irt is seen
ta be contracting regularly, making sr-me 120-160 rhythmic raovementa in the
minute. If the respiration ha now artilicially maintained, and suitable proaf^uro
made on the walls of the ehest, so as to empty the heart of blood, the bhxid- pressure
quickly risesj and natural respiration may follow. An animal which lay thirty -six
miuutea apparently dead Wz*s in this way brought to life again (Bohm). The action
of the aaltfi of potassium on the blood ia the aame an that of Siiidium salta. The blood
jji coloured a brighter red, and the form of the corpuacles changwl ; they become
shrivelled through loss of water. Voluntary muaele losea quickly its contractility
when a aoludon of potaab is injeoted into its vessels, Kerv^ also, when treated
with a 1 per cent, solution of fH>tasaic ehloridei become inexci table,
% 121, EUmiaation. — The potas^iium salts appear to leave the body through the
kidneya, but are excreted mueh more alowly than the corruapondiiig sodium salts.
Thus, after injection of 4 grms. of potjwiaic chloride — in the first sixteen hours
*74S grm. of KCl was excreted in the uriu^, and iji the following twenty-four hours
2 '67 7 grma*
§ 122. Nitrate of Fotosh (KNO5).— Pure |M)tassic nitrate crystal liaes iu large
anhydroufl bciagonal prisms with dihedral ^ummit^ ; it dovs not absorb water, and
* itancetj June 24 » 1882.
§ I23'*I3S0 SODIUM, POTASSIUM, AND AMWONI0M SALTS.
139
doeft not ddiqttcsG^. Its fusing poinfc is ^bont 340' ; when melt«d it tomm u traoa-
parent liquid^ und losea a little of it^ oxygen, but this m for the moHt pdri retained
by the liquid given oHT wbi^n tha ^It aclidifji^. At a red- heat it otqIvb^ ojcygeili
ftttd is reduces I tn^t to oi trite ; if tho hmt h continuod, potassic oxido renuiniL
Tlie apecifie gravity of tlio fuued sfdt m 2*06. It la not very Bolnblu in cold water,
100 imrtH dissolving oidy U6 at 15 '6*' ; but boiling witter dissolvea it freely, 100 parta
dissolving 240 ot the sail,
A solution or nitmte of potash, when treated with a due oouplo (see "Foodi/*
p. 525), is deconipo(^, the nitrate being first reduced to nitrite, as ahowti by its
atrikiog a red colour with raetaphEnylene'diflmine, and then the nitrite farther
decomposing, and ammotiia appearing in the liquid. If the solution is alkalised,
and treated with aluminium foil, hydrogen is evolyod^ and the same eJfeot produced.
As with all nitrates, potassic nitrate, on being heated in a teat tube with a little
water, sotne copper filings, and snlphnrie acid, evolves red fumeti of nitric ptjroxide.
§123* StatlBticB.— Potaseic nitrati?, under the iH>pular name of **»/iri?,** i^ a
very common domestic remedy, and Ia also largely ustd as a tnedietno for cattle.
There appear to be at leaat twenty coses of potossic nitrate [poisoning on rctiord : of
the^ic^ eight were cau&ed by the salts having been accidentally miataken for maguesic
sulphate, sodic sulphate, or other purgative fnilt ; two euM were due to a simitar
mistake for common salt. In one instance, the nitrate wis used in Strang ^lution
as an enema, but most of the cases were due to the taking of too large an internal
dotie.
§ 124. Uaea In the Afti, etc^Both sodic and potos^ie nitrated are called
'* nitre ** by the public Ludiscriminately, Sodic nitrftte h Imported in large quantltieti
from the rainleas districts of Peni as a manure, Potousic nitrate h much used in
the manufacture of gunj.H>wder, in the preaervatiun of animal substances, in the
manufacture of gun-cotton, of sulphuric and nitric acids, etc. The nmdrauin
medicinal dose of potassium nitrate is usuiiUy stated to he 30 grains (1"0 grm, ).
§ 125. Action of Nitrates of Sodium and Fotaasinm. — Both of these salts are
fM>isoiii>us, Potassic nitrate ha« Ijeen taken with fat^l result by man ; the poiiionoas
nature of ^^wlic Tiitraie is established by cx(>erimL'nts on animals^ The action of the
nitrate^i of the aLkailefl ia seimrated from that of the otlier neutral salts of potjisstumi
etc., be<^^u:w in tJm eo^ the toxic action of the combined nitric oeid plays no iil^^-
ni&ant part. Lai^ doses, 3-5 grma, (46~3-77*S grains)j of |K)tassie nitrate cauiie
eotisiderahle uneftoiness in the stomach and bowels ; tlie digestion is disturbed ]
there may he vomiting an<! dlarrlio^, and there is generally present a desire ti^
urinate frequently i ^till larger dose;:^, 15-30 grms* (231 '5-463 grains), rapidly
produce all the symptoms nf acute gost ro» eii ten tia— great jialn^ frequent yomiting
(the ejet-'tisfi matters hciing ofterj hhaotly), with irregularity and slowing of the pulse ;
weakness, cohl sweats, painful eramjis tn single muscles (es|>ecially in the calves of
the leg») ; and, later, convulijions, aphonia, quick collapse, and death.
In the case of a pn*gnaut woman, a handful of **uiti'ti" taken in mistake for
fJlaulter's salts produced abortion after hiilf an hour. The woman reeuverod, Bodic
nitrate snlicutaneously appliod to fitjgs kills them, in fliJses nf ^0^26 grm« (^ grain),
in about two hours ; there are fibrillar twi rollings r>f single gron]»tf of ni unfiles and
narcosis. The heart dies lust, but after ce^ising tti beat nmy, by a ^itiniuliiji, lie made
again to oontnict Rabbits, |»oi»oned similarly by stidic nitmte, exhibit also narfutic
^mptoms ; they lose conscion.sness, He upon their side, and resjnmd only to the
aharjjest stimuli. Tlie lirtsathing, as well as the heart, is *' slowed," and deatli
Jbihiws after a few s|vasmodic inspirations.
Sodic nitrite was fuund hy Barth t« be a more powerful poison, lees than 0
mgrmM, ( '1 grain) being sufficient to kill a rabbit of 455'5 grms. (7023 grains) weight,
when subcutaneously tnJLHT^'d, The symptoms were very similar 1.0 tliose produced
hjf the nitrate.
13°
POISONS: THEiK KKFECTS AND DETECTION, [§ 126-I30,
N
§ 126, Tlie |>o^t-mcirtenj npjfeamjuiea from pota^ic nitrate arc as fciUoWB : — An
inOaniPfl cuuditiou of the stoniatili, with tke ujuctiuf* merabrane dark in cnlouj-, aiid
readily tearing ; the contants of the utomach are uften miied with blood. In a oaee
related by Oi'iila» there was even a «mall iierforation hy a large dose of potAiiaic
nitrat^j And a remarkable {ireservAtkm of the body was noted.
It ijs believed that the action of the nitrateij is to Ih; jjartly explained by a rednc-
tion to nitrites, circQlating in the bloiid &b Jincli* To detect nitrites in the blood, the
best method ia to place the hlood in a dialyaer, tiie outer liquid b^iDg aleobeL The
alcoholic »olution may be evaporated tti dryiie^s, extracte^l with water, and then
tested by motapheiiylone-diaTnine^
§ 127. Fota^ic OMorate (KCIO,,).— Potjiajic chlorate is in the fonn of colonr-
lesa, tabular crystals with fooi!' or six sides. About 6 parts of the salt are disaolved
by 100 of water at 15"^ the aolubOity increaairig with the temjMarature, m that at 100*
nearly 60 parte disaolve j if strong sulphuric acid be drtipijoti on the ciyttals, peroxide
of cMorine is evolved ; when rubbtxl with Bulphur in a roortar, iHitaeaic chlorate
detonat^^ When the salt is heated strongly, it first raelt8» and then decompoaesL,
yielding oxyg^ g^f And is transformed hi to the perehlorate. If the heat is ooii-
tinued, this alio h dftcomjmsed, and the final it'stilt is |)otasaie chloride,
§ 128- UaeB. — Potasaio chl f irate U largely used &b an ojtidiiser in calico printing,
and in dyeing, especially in the preparation of aniline black. A considerable
quantity is consumed in the manufa^^tur^ of luclfer matches and fireworks ; it ia also
a convenient source of oxygen. Detonators for ei[iloding dynamite are mixtures of
fulminate of mereury and potasaic chlorate. It is employed as a medieine both as an
applieation to inflamed mucous membraneSj and for interna! ad minis tration ; about
2O00 tona of the Bait for these various purpiJ^es are manufactured yearly in the United
Kingdom*
I 129. PoiionouB propertiet . —The facility with which potassic ehlomte paais
with its oiygen hy the M of heat, led to it^ V6iy extensive employment in niediciuea.
No drug, indeed, baa been given more recklewily, or on a leas scientific basis, Wber*
ever there were sloughing w^ounds, low fevers, and malignant sore tbroatft, especially
thoae of a diphtbentie character, the practitioner MminiBtered potas.>9ie ehlorate in
ooloffflal doises. If the patient died, it was aaeribed to tli^ malignity of the dt^'ase — if
he tieoovered, to the oxygen of the salt ; and it is pfjssible, from the light which of
recent years haa l»een thrown on the action of pota^ic chlorate, that its too reckless
use has led to many unrecorded accidentB.
§ 130. Expeiimettta on AnlmalB.-^F, Marchand* has studied the effects of
potassic cldorate on animals, and on l>looch If either ptitassic chlorate or sodic chloi-ate
is mixed with fresh blocMJ, it shows after a little while peculiar changes ; the clear
ted colour at first produce<l pa^isus^ within a few hours, into a dark red-brownj which
gradually lijecomee pni-e brown. This change is piwlueed by a 1 per cent, &<jlution
in from fifteen to aiiteen houi-s ; and a 4 per cent, solution at 15* destroys every tiace
of oxyhiemoglohiti within four hours. Boon the blood takes a syrupy consistence
and, with a 2-4 yier cent, solntion of the salt, i>asSBg into a jelly like mass. The
jelly has much [leiTnan^nce^ and i-esists putrefactive cliangesi for a long time.
Various bloods whow various rcsifitances ; similarly the effect of )K>ta^^ic chlorate
is nnefjual in different animals ; it t^kes lai^ doses to kill mbbitH ; cats are leas
Teaiflring* Rabbit^j are killpxi by enlicutaneous doses of from 5-6 gnns, ; cats from
1-li grm. Dogs require larger druses than cat*, but le^ than rahbita. The resistance
of human Wings is ^ibout the same as that o( dogs.
Marehand fed a dog of 17 kilos, in weight with 6 grms. of potassic chlorate for a
week. As there were no apparent symptomsi the dose was doubled for bfi'o days ;
and as there w^as still no visible effect, laatly, 60 grms, of sodic chlorate were given in
' Virehow's Archin. /, path. Ami., Bd. !it3tviL Hft 3, S. 465, 187S.
§131, 1 32-] SODIUM, POTASSIUM, AND AMMONIUM SALTS.
'31
:
fi dmeA, lu the following night the dog died, Tlie blood w^ Tuund i^fter d^tb to
ha dF a :A^int\'hiowT\ colour, and remaiucd utialtei^d wlieii exposed to the ^ir* The
orgaos weie gifiiemlly of tin unnatural br^iwii colotir ; th« »j>!ecn was enormously
oularged ; tho kidiioys waro swollen, and of a rlark chocolate' brown ^on section,
iilmost Iilttck-brown^ tli« eolour lieiu^ nonrly tH|ual, lM>th in the .sntwitajice iiud hi the
Cttpsatu. A luit^roscoj^ical e.taminiLtiuo of iha kidut^y Mhowt^ iha caualiunii to ba
filled with bifjwnifth cylinder's conHiJ^ting uf altercft hlood* A Jipectroseojiic t'xauunii-
tiijii tt( the blood «liow(^l weak bipmoglohln biiiitb, and a Ui*rrow band in tht? red.
With farther dilution, the hLeuioglobhi biiiid» vauiBhi^i, hut the band In the red
reuittined. The diluted bhK>dj when eK[M>sed to the light, still rcmaiutHi of a
coif efl- brown colour ; and on shaking, a white-brown froth wae jirodiicod on the
surface.
A Aocood experinieut, in whioh a hound of from 7-8 kilos. In weight wan gi^en
three 6 giio. doses of i>otaBsic cUloratfi Jn sixteen hours, and killed by bleMing seven
to eight hours after the last dose, showed very aiiuilar ai^iearuucfK. The kidneys
were iotenaely eongested, and the i>Bculiar brown eolour was noticeable.
g 131. Effects on Han. — -In litetiitur<> thero are more than forty c&,se» rt^eoitledf
ill which i>oic5ononf^ ftyiupt<*nifl wem direetly afsrriWl to th© action of chlorate of
potassium ; tweoty-nine of these temiiuated fatally. At Morecumbe a Uttle hoy took
al»ut eO graina of |H)tassia ohiomte and died in mx bout^ {L/nft^ct, Aug. 23, 1903).
A quadruple inntauce of itoisoningi reconled by Brouaitlel and Lllotfi,* illustratt^
inany of the pnnts relative to tlie tiiiiti ut wldcli the Hymptonia may be ex|K*cted to
eonunence, mid the general ^isi>ect of |H>t4isHic chlorate jioiaoniug. The !fitpt-ri^urt
of A reljgioufi institutiou waii in the habit of giving, for charitable purjMiscis, a jM>tioii
dontmniug 15 gnus. (3*8 dnuK.) of prrtAssio chlorate, di»aolYed in 360 c.c, (about
]2| OZE^) of a vegetable infusion.
This i>otiou was aiinvidirftefeel to four cbtldren— viz*^ David, aged 2 J ; Couidr?,
igcid 31^ Salniont, 2^ ; and tJumn, 2^, David bmk the whole lu two and a half
hours; the ^yniptoiu& eoiuuietK^eii aft«r the ^lotiou was finnihed, aurl the child died
tivo an<] a half lionn?; after taking the tirrit close ; there were voqdting and diaiThtea,
iViusiii toijk the niediciue in seven houra ; the myniptouis also commeuced after the
last sjioouful, and the deoth took place eight and a half hours from the first spoonful ;
the aymptotnH were nminly those of great dejiTCi^Hioir ; tlie lips weit> bUu\ the pulse
fwhle, thei*© was no vomiting, no diaiThrea. Sahuout took thf medicine io nine
houra, and died io twelve j there was sonn? diarrhoea, the Htools were of a green
colour. Gu^rin took the whole in two hours ; the sy nip tenia crimnienced in four
hours ; the lijii wero very pale, the guuii blue ; di'ath t-ook place in four day^.
There was an autopsy in the case i>f David otdy. The stomach showed a largo
MTchyniesia on it^ niuoous nieuibratie, aa if it hmi bi^en burnt by an acid i the spleen
Waa gorged with tiloofi, ar»d its tissue friable ; the kidney a do not ^eem to tiave been
thoroughly examined, but are said to have been tumefied. Potaasic chloTiite was
dbcovertHl by ilialysiss. In the cases of tho cbildrou jaat detailed, the «ymj>tomi)
appe-ar U^ ^m a loiKture of the depressing action of the potasaium, and irritaut action
of the ehloMta.
g 1^2, In adults, the main symptoms are thoae of nephritis, and the fatal dose
for an adult is Bomewhisre about an ounco (2S*3 gnn^Oi ^^'^t half this i^uaiitity would
proWbly Imj daugeroua, esj^ecially if given to a pernon who had congestion or disease
of the kidneys.
Dr. Jaeobl f gir^sa the following ca^ea,
Dr, Fouotaio, in lSt*Bj cxperimeuting on himself, took 20*2 gnns. (S'7 drms.)of
poto^ie chlorate ; he died on the nevonth day fiom nuiihritia* A young hwiy
* Annaica d'Uyifltn^ pMiqm^ lUi^ pw 232*
132 POISONS: THEIB EFFECTS AND DETECTION. f§ I33-I35.
swallowed 30 grms. (8 '5 dims.), when using it as a gargle ; she died in a few days
from nephritis. A man, 30 years of age, died in four days after having taken 48
grms. (12*3 drms.) of sodic chlorate in six hoars. The shortest time in which
the salt appears to have been fatal is a case related by Dr. Manouvriez, in which a
woman took 45 grms., and died in five hours. The smallest dose which has proved
fatal is one in which an infant 3 years old was killed by 3 grms. (46*3 grains).
Jacobi considers that the maximum dose to be given in divided doses during
the twenty-four hours, to infants under 3, should be from 1-1*5 grm. (15'4-28*1
grains) ; to children from 3 years old, up to 2 grms. (30*8 grains) ; and adults from
6-8 grms. (92-6-123*4 grains).
§ 133. Elimination.— Potassic chlorate is quickly absorbed by mucous mem-
branes, and by the inflamed skin, and rapidly separated from the body by the action
of the kidneys. Wohler, as early as 1824, recognised that it in great part passed
out of the body unchanged ; and, lately, Isambert, in conjunction with Hime,*
making quantitative estimations, recovered from the urine no less than 95 per cent,
of the ingested salts. Otto Hehner has also made several auto-experiments, and
taking 2^ drms. , found that it could be detected in the urine an hour and a half
afterwards. At that time 17*23 i>er cent of the salt had been excreted, and, by the
end of eleven hours, 93*8 |)er cent was recovered. It is then difficult to believe that
the salt gives any oxygen to the tissues, for though it is true that in all the investi-
gations a small ])ercentage remains to be accounted for, and also that Binz,t making
experiments by mixing solutions of ]K)tassic chlorate with moist organic substances,
such as pus, yeast, fibrin, etc., has declared that, at a blood heat, the chlorate is
rapidly reduced, and is no longer recognisable as chlorate — yet it may be affirmed
that potassic chlorate is recovered from the urine as completely as anything which is
ever excreted by the body, and that deductions drawn from the changes undergone
by the salt in solutions of fibrin, etc., have only an indirect bearing on the question.
§ 134. The essential action of ]K)tassic chlorate seems to be that it causes a
peculiar change in the blood, acting on the colouring matter and cor))Uscles ; the
latter lose their property as oxygen carriers ; the haemoglobin is in part destroyed ;
tlu^ corj)Uscles dissolved. The decomposed and altered blood cor^mscles are crowded
into the kidneys, spleen, etc. ; they block up the uriniferous canaliculi, and thus the
organs present the curious colouring seen after death, and the kidneys become
inflanxnl.
Detection and Estimation of Potassic Chlorate.
§ 135. Organic fluids are best submitted to di^ysis ; the dialysed fluid should
then W concentrated and qualitative tests a])plied. One of the best tests for the
presence of a chlorate is, without doubt, that recommended by Fresenius. The fluid
to l>e teste<l in acidulated with a few dro])s of sulphuric acid ; sulphate of indigo
added suflicient to colour the solution blue, and finally a few drops of sulphurous
acid. In presence of potassic or sodic chlorate, the blue colour immediately vanishes.
This method is capable of detecting 1 jwirt in 128,000 ; provided the solution is not
originally coloured, and but little organic matter is present
The urine can be examined direct, but if it contain albumen, the blue colour may
disap])car and yet chlorate be present ; if too much sulphurous acid be also added,
the test may give erroneous results. These are but trivial objections, however, for
if the analyst obtains a rcsi>onse to the test, he will naturally confirm or disprove it
by the following process : —
♦ Oaz. M6d, de Paris, 1876, Nro. 17, 35, 41, 48.
t Berlin klin, Wochenschr,, xi. 10, S. 119, 1874.
§ U6.]
DETECTION OF ALKAU SALTS.
133
Tbi^ liquid under ^0.111 1 nation^ i>rgiiuia or otJienmOj La dividi&d into twi> cf^Uftl
imrts. In tbi^ ono^ iill tliu chlorine present m ptiecipiti&ted hh clilorlde by silver
nitrate in the usuii! wny^ and tho oliloridu of silyer collected and weii^hod. In the
other, the liquid i8 evapomtt'd to dryue^ and well cliurrod by » dull n^l heat^ thu
ttnh dissolved iu w«jak nitric acid, and the chlo rides OHtiniatefl bj^ iu the hi-itt cituG* It'
chlortitea wer^ present, thet-e will b@ a diOTerence butWtieQ tlie Lwu esidnhitiiiuTn, pm-
portionate to tho amount c^f chlorates whidi have been uouveitcd into chlorides by
the carbonisation^ nnd the Hrst silver chloride subtrtveted from the fsecond will ^ivu
An argentic i^hloridc which is to bu rEftHTcd to chlonvto. In this way also the afnriiint
present may b^ quantitatively i^tiniuUxl, 10 0 {>arti^ of nil vet cbloride Ci]UJilling S&*4
of f>otttS8ic chlorate.
Toxicological Deteetion of Alkali Salts.
(See nliKj itrit^^ p, 1'47,)
§ 136. Su^Iiauj, in eoiubiiiL^Uon^ especially with chl^niiiLS aindalauwitb .Hiidphnriti,
ciirbouic, and pho?5phui ie acUh^ k finmd in tluj plasma uf the hkio*!, in tho urin^iry
iiecrctioni in tho panereatic jutee^ in bunuiii bUo, and in serous tranandationttf ek%
potiMisiain, in coinbinatiop, is esjMJcially found in the ix^ bh.>od corpuscle*?, in tlic
luusclea, tti tbi^ nervous tissucti, and in milk. AnuuoTiia, in combination with acids,
h itaturaliy found in tho ittomacb, in tbo contents of the intostine ; it i£ aItK> a
ijjfctural conatituent of thn blood in snjall traces, and in a corjiso ia copiously ovolvod
Iroui putrefactive chaugeja.
It hence follows, that mere qualitative tests for these elements in thn iissnea or
Huids of the l>o<:ly ar^ of not the slightest use, for they art* always lu'csant dnrinf? tho
life of the healthiuiit individual, and can bo ton nd after death in jj^i^ons dying from
any tuahkdy whatever. To establiiih the fact of & j^er^on having taken an unusual
dose of any of the alkali s+vlts, by dimply ehofnicJil evidence, it must l*e prnverl that
tho alkalii.^ are pn-sent in tinm^nal i|nantttics or in an abnormal state of cnmhination.
In cases of rapid df:^th, c&usi^l by ¥^r1lc or {lotassic i^alt^j Lliey will be found in
t>Ueh quantity in tlie eonteiits of the sloiuach* or in mattors vumitod, that ilmr^ will
probably Ixs im diMculty in f^ondng to a diittct coueluiijion ; hut if aome time has
elapsed, the analyst may not find a huUieieut ground for giving a decided judgment,
the excretion of the alkali «alha l»eing very rapid.
In most easeSf it will be well to proceed as follows : — The contents of tbi) atoumch
ait), if ueceaaaiy, diluted with distilled water, and divide<i inUj three [►art*, ono of
which is submitt£4l to dialysis, and tlien tho dialyswl liquid eva[Hj rated lo a small
hulk and examined qualitatively, in order to ascertain whether a huge amount of
the alkaiina salts in present, and in what form. In Hm way, the presence or i^boeiico
of oitrftte of potassium or sodium may he pn:»ved, or the iodide, bromide, sulph&ta,
and chlorate detected.
To find, in thia way, rdtrate of potassium, a cfittrso teat ia preferable to the liner
testa dependent u|>on ean version of the nitrate into nilritoa or into ammonia, for
theise teats an& sjo delicate that nltitites may be detected in traces ; whereifta» in this
examination, to find traeee ia of no value, Hence, the old-fashioned test of tmating
the concentrated liquid in a test tube with eopjn^r filings and then with sulphuric
aeid^ and looking for the red fumes, is best, and will act very well^ even should^ as
is cunmionly the coae, soma or^inic matters have i>ASsed through the dialyscr.
Qhlorat«a ftre mdioited if the liquid ia divide«l inte two fxirts and tested in the
luatMier recommended in the previous section. If pretient in any quantity, ehloratos
or nitrates may be indicated by tlie^ brilliant combustion of the r>rganic matter when
134 POISONS: THEIR EFFECTS AND DETECTION. [§ 1 36.
heated to redness, as also by the action of strong sulphuric acid on the solid sub-
stances—in the one case, yellow vapours of jieroxide of chlorine being evolved — in the
other, the red fumes already mentioned of nitric iMjroxide.
With regard to a substance such as the hydro- potassic tartrate, its insolubility in
water renders it not easy of detection by dialysis ; but its very insolubility will aid
the analyst, for the contents of the stomach may be treated with water, and thus all
soluble salts of the alkalies extracted. On now microscopically examining the
' insoluble residue, crystals of bitartrate, if present, will be readily seen. They may
bo picked up on a clean platinum wire and heated to redness in a Bunaen flame, and
spectroscopically examined. After heating, the melted mass will have an alkaline
reaction, and give a precipitate with platinic chloride. All other organic salts of
potassium arc soluble, and a wliite crystal giving such reaction must be hydro-
potassic tartrate.
Ammonium Salts. — If the body is fi-esh, and yet the salts of ammonium present
in large amount, it is safe to conclude that they have an external origin ; but there
might be some considerable difficulty in criminal |)oisoning by a neutral salt of
ammonium, and search for it in a highly putrid cori>sc. Probably, in such an excep-
tional case, there would be other evidence. With regaid to the (quantitative seitara-
tion and estimation of the fixed alkalies in the ash of organic substances, the reader
is referred to the processes given in ** Foods," p. 96 el acq.y and in the present work,
p. 27.
PART V -MORE OR LESS VOLATILE POISONOUS SUB-
STANCES CAPABLE OF BEING SEPARATED BY DISTIL-
LATION FROM NEUTRAL OR ACID LIQUIDS.
HY DROCARBONS— CAMPHOR— ALCOU(JL— AM YL NITRITE-^
ETHER— CHLOROFORM AKD OTHER AN.ESTHP:TICS-
CHLORAL— CARBON DLSULPHI DE— CARBOLIC ACID—
NITRO-BENZENK— PRUSSIC ACID— PHOSPHORUS.
L— Hydrocarbons.
L PETftOLEUM.
g 1S7. Pctvuleunx is u geiiaral term for a mixturiJ nf hydivxrarbnuii of tlje jwimffiii
Splirr, which t^te found naturally tu cortatn fuirtf; of thv w^rld, tind ni'& in com-
miroe tinder liquid and solid foniis i*f variuus density, Crudu iietmleum k not im-
l^iFted into Enfilftnd, the original aubstanee having previously undi*jgone more f*r
lesi f^ctificivtion. The lighter and mora voliitilo portions uro known uiidt^r the n&me
of cymogeut?, rbigoleiiei, gaaoleiie, lind naphtha.
§ 138. Gymogene h^ & specific gravity of '590, (Uid boi]& nt 0°, It hm bueij
employed m idfiigumting inAchinea^ It diiiKJura to consist cbi« tly of butane
g 13&- Ebigolone is now mi^l in mcdkino in the form of spray to produce local
anmtti^ia. It boiti^ nl lB°t Jind him u de unity of '550,
§ 140. Oasoiene him a density of ^68D--SS3 ; it h^ r^oived techttioil appUoa-
tious itt tliu ** iijiphtlmlieiiing " nf »ir and gii8^
§ 1 U. Benzotine (mineral naphtha, petroleum tuphtliA, petroleiuii spirit,
petroleum ether, petrol) is a mixture of the lighter soric?^ of hydrt>ciirbonB ; the
great*! r jMirt conaista of heptane, and there ia also a. eonsldf^rablo quantity of fi«Fiitano
(Calljg^) present* The atK'Lific gravity varies from '69 t*i 71. It is very IntlammAble,
ainl is Urietl iri mot^ir cun^, sponge larnp.H^ and ako as a w^lvent for ^'iitta-porcbaj
jmplithah'nc, parallin, wax, atid mar^y other hodira* Tho otxHnary p«.'tn>l that la
uaml iii fAi*s haa a ja^vity of '680^708 at tS^ C. and a boiling -|Hjint of 85" C, It is
much em pi oy etl hy th<! practical die mis t.
The siniiiarity of the temiii bifnz&H}ie oitd btm^^nt hns caus^ benzoliiie to im often
confuMd with benzol or teuBciw, the leading cons titnent of coal- tar naphtha (CflHs)*
lir. Albn * gives in the following table a sutmnary of the chlief ptiiuts of diitinotion,
(hm^merekii Organic Ane^^Hs^ vot li* yu 31,
136
POISONS: THEIR EFFECTS AND DETECTION. [§ I42, I43.
both between petroleum naphtha, shale naphtha, and coal-tar naphtha. The table
is founded upon the examination of particular samples, and commercial samples may
present a few minor deviations.
TABLE OF THE VARIETIES OF NAPHTHA.
Petroleum Naphtha.
Shale Naphtha.
Coal-tar Naphtha.
Contains at least 75 ]>er
cent, of heptane, CyHu,
and other hydrocarbons of
the mareh gas or parafiin
series ; the remainder ap-
jiarently olefins, CnHgn,
with distinct traces of
benzene and its homo-
logues.
Specific gravity at 15",
•600.
Distils between 65** and
IOC
Dissolves coal-tar pitch
but slightly ; liquid, but
little coloured even after
prolonged contact.
On shaking throe mea-
sures of the sample with
one measure of fused crys-
tals of absolute carbolic
acid, no solution. Liquids
not miscible.
Combines with 10 per
cent, of its weight of
bromine in the cold.
Contains at least 60 to
70 per cent, of heptylene,
C7H14, and other hydro-
carbons of the olefin
scries ; the i-emainder
paraffins. No trace of
Denzene or its homologues.
S()ecific gravity at 15**,
•718.
Distils between 65° and I
lOO^
Behaves similarly to
|)etroleum naplitha with 1
regard to the solution of
pitch. I
When treated with
fused carbolic acid crys-
tals, the liquids mix per- 1
fectly.
Combines with ujiwards
of 90 yteT cent, of its
weight of bromine.
Consists almost wholly
of benzene, CgHg, and
other homologous hydro-
carbons, with a small per-
centage of light hyaro-
carbons in some samples.
Si>ecitic gravity •876.
Distils between 80° and
120°.
Readily dissolves pitch,
forming a deep brown
solution.
The liquids form a
homogeneous mixture
when treated with fused
carbolic acid crystals.
Combines slowly with
30-40 i)er cent, of its
weight of bromine.
§ 142. Paraffin Oil (or kerosine mineral oil, photogen, etc. ) is the cliief product
resulting from the distillation of American iHjtroleum — the usual sjwxjific gravity is
about '802 — it is a mixture of hydrocarbons of the paraffin series. It should be free
from the more volatile constituents, and hence should not take fire when a fiame is
applied near the surface of the cold liquid.
§ 143. Effects of Petroleum. — Since we have here to deal with a commercial
substance of such different degrees of purity, and various samples of which are com-
I)Osed of such various proportions of different hydrocarbons, its action can only be
stated in very general terms. Eulenberg * has experimented with the lighter pro-
ducts obtained from the distillation of Canadian petroleum. This contained sulphur
products, and was extremely poisonous, the vapour killing a rabbit in a shoit time,
with previous insensibility and convulsions. The autopsy showed a thin extravasa-
tion of blood on the surface of each of the bulbi, much coagulated blood in the heart,
congested lungs, and a bloody mucus covering the tracheal mucous membrane. An
* Gewerbe- Hygiene,
§ »44. »45.]
HTOROCABBOHB.
137
pxpenmeiit mMii> ou «i daI with the l%hter |>otrQl«um (which had no cxcefis of
sulfibur) 111 thi? alAto of vAjioiirj »how6(! Lhivt it wiih nij tiniegiliotb, thv ifcusefith««iiii
kniig tticcamiianiod hy coMvubions, which towards thcj t'lid wt^rc tefamic and vioii*uL
The vvftijorutiou of I'l* grm, in a tdose chairiher killi.*d tho nijiiiial in three Uoura.
The liiugB were* tbuud uoiig^Uid, but Uttle film wa^ itiuiiiikiible. Much (icttxilQUtu
vajiour is hn^uithed in CL^rtaln factories, f&jieciully thosse in wluch [x^troieuni in
re(iu<«d.* Friim thi^ cuiisi^ thcri^ have bi^eu rattier frbqitent tojcic sjmpkutu^ atnotig
the workmen* Kuleiiberg + describe* the syirij) kirns m followa r^A {lersoii, aft<*r
bfBithliig an overdose of the vapoui'i l>eeoiii(?3 very juile, the lips atx* livid, th^
re5|iiratioii alow, the hejirt^a action weak and Ncarcely to hi? felt> If he dfn* not
immediately go into the ojieu nir away ffoijx tlju jroitMinnus vajujur^ these Hympttini*
n»y pawoD to msentdbility, connil&iontij and death. It ofttn oocftsionfl a condition
of tlie voJimUoy musdej* Jiimilar to t!mt iiidncivi by cJi inik»uneiSB, and on ri.Mx>very
the [Mtleut is troiiblefl by ajngiug in ihe ears and tjuiyea iii the head. The Bmell
and tasU of the (nison may ix^main for a long time.
§ 144. Foi»otiii)g by taking Ught jjetroleum into thi^ stomach w notoomiuon* Id
a cask} recorded by Taylor, t a woman, for thii parjiow? of suicidej Hwal lowed a irint
6f Xwtroletim* Tliero followed a slight [lain in the stomach, and a little febrile di»-
tnrlAanee, aud a jjowerfnl amell of iKstroloum remained nbout tlie Iwxiy ri>r ^ix tlwys ;
but bhe completely recovered. In Angust 1870 a sca-caqitain drank ik quantity ol
[»amffin^ that is, lighting ^letroleutn, and died in a few hour^ In au uncoiifleious utati*,
A child, 2 years old, wm hronght to King^a Ctjllegt^ Hojtpitai wttlun ten miuntes
ftfler taking a teasi^oonfu] of i>araflin. It was semi-oomatoao and pale, with con-
tmctod pujiib ; there wim* no vomiting or purging. Kmciticii of sulphate of zinc were
adniioislerfsd, iMid Ihe child recovered in twenty- four honi-s. In another case treated
ftt the iatne hos}iital, a child had swallowed aji unkuo>vn qtiantity of parafliin It
foil into a comaloefi state, which ijimnlated tubereuUr meningitis, and lasto^l for
tMarly three weeks. § In a e^iso recorded by Mr* Ititbirt Bmith, 1 a child, 4 years of
age, had swallowed an unknown quantity of jHtralfin. A few niinuks aftorw'ard^
the ayraptuuiH conirneneed ; they were those of BUllV-watiun, with a constant cough j
tbei-c was no ex(iectoration ; the tongue, gums, and ohcekti weiie blanched and
swollen where the lluid touched Ihem ; recovery followed. A woman, aged Si!,
who bad takin a quarter of a pint of pamffin, waa found unconscious and very cold ;
the stomach 'jui nip wiw used, aud she rceovored,lJ Hence it in t<jlerAbly certain i from
the almvp iniitnneeai, that should a ease of petmleum }poi«oning occur, the exj«i t will
not huvc to deal T^-ith inhnitesiiuial quantities ; btit while the odour of the oil will
pi*ibably be distiiietly |>ereeptiblej there will l)e alwo a »uffieient amount olttained
either from matters vomited, or the eoutonts of the stomach, etc., so that no difli'
ctilty will be exjierienced in identifying it.
S 145. In order to aejiaTate jietroleum from any liquid, tlie substancci» under
examination niuat be carvfuHy distilled in the manner recomtnende<i under '* Ether.''
The lighter |ietroleums will distil by Ihe aid of a water-bath ; but the heavier require
a stronger heat ; redistillation of the distillate may be nec««8ary. The odour of the
liquid, its inflammable chamcler, and its other projiertiea, will be snflicient fur
idontilicatioiL
* The Vapour meet likely to rbe at the ordiitftiy t6mja<«rature, and mix with the
attuosiphere, is that of the lighter series, fr^m cymogeue to henzoUue.
t Op. cit. t P(ti»/ns, p* 655*
I MrU, Med, Jmrn,f Sept. 16, 187tl, 11. 365.
II BHL Mt*L Jifurn,, Ot. 14, l&7a*
f Fhann. Jounu^ Feb. 12, 1875 ; also for other cuatis aoo BrU,. MM* J^UktH*,
^»v, 4, UU ; and Kohler's Phi/sioL Tlt^mjt., {k 42tT,
<
138 POISONS: THEIK EFFECTS AND DETECTION. [§ 1 46- 1 49.
2. COAL-TAR-NAPHTHA— BENZENE.
§ 146. Coal- tar- naphtha, in its crude state, is an extremely complex liquid, of a
most disagreeable smell. Much benzene (CgHg) is present with higher homologucs of
the benzene series. Toluene (Cyll,,), naphthalene (C]^H(j), hydrocarbons of the
paraffin series, especially hexane (CgHi4), and hydrocarbons of the olefin series, especi-
ally pentylenc, hexylene, and heptylene (CgHjojCgHia and C7H14). Besides these,
there are nitrogenised bases, such as aniline, picoline, and pyridine ; phenols, especi-
ally carbolic acid ; ammonia, ammonium sulphide, carbon disulphide, and probably
other sulphur compounds ; acetylene and aceto-uitrile. By distillation and fractional
distillation are produced what are technically known '*(mce run" naphtha, 90 per
cent, benzol, 50 and 90 per cent, benzol,* 30 per cent, benzol, solvent naphtha, and
residue known as **last runnings,"
§ 147. Taylor t records a case in which a boy, aged 12, swallowed about 3 ozs. of
naphtha, the kind usually sold for burning in lamps, and died with symptoms of
narcotic poisoning. The child, after taking it, ran about in wild delirium ; he then
sank into a state of collapse, breathing stertorously, and the skin became cold and
clammy. On vomiting being excited, he rejected about two tablespoon fuls of the
naphtha, and recovered somewhat, but again fell into collapse with great muscular
relaxation. The breathing was difficult ; there were no convulsions ; the eyes were
fixed and glassy, the pupils contracted ; there was frothing at the mouth. In spite
of every eH'ort to save him, he died in less than three hours after taking the poison.
The body, examined three days after death, smelt strongly of naphtha, but the post-
mortem appearances were in no way peculiar, save that the stomach contained a pint
of semi-fluid matter, from which a fluid, having the characteristics of impure benzene,
was separated.
§ 148. The effects of the vapour of benzene have been studied by Eulenberg in
experiments on cats and rabbits, and there are also available observations on men X
who have been accidentally exposed to its influence. From these sources of informa-
tion, it is evident that the vaiK)ur of benzene has a distinctly narcotic effect, while
influencing also in a marked degree the spinal cord. There are, as symptoms, noises
in the head, convulsive trembling and twitchings of the muscles, with difficulty of
breathing.
DETECTION AND SEPARATION OF BENZENE.
§ 149. Benzene is separated from liquids by distillation, and may be recognised
by its odour, and by the properties described at p. 136. The best process of identifica-
tion, perhaps, is to purify and convert it into nitro-benzene, and then into aniline, in
the following manner : —
1. Purification. — The liquid is agitated with a solution of caustic soda ; this
dissolves out of the benzene any bodies of an acid character, such as phenol, etc. The
purified liquid should again be distilled, collectiug that portion of the distillate which
passes over between 80" and 120** ; directly the thermometer attains nearly the 120*,
the distillation should be stopped. The distillate, which contains all the benzene
present, is next shaken with concentrated sulphuric acid in the cold ; this will
dissolve out all the hydrocarbons of the ethylene and acetylene series. On removing
the layer of benzene from the acid, it must be again shaken up with dilute soda, so
as to i-emove any trace of acid. The benzene is, by this rather complicated series of
* Or 50/90 benzol, this indicates that 60 per cent, distils over below 100" ; and
40, making in all 90, below 120*.
1 Op. cit., p. 657.
: Dr. Stone, Med. Oaz., vol. xii. p. 1077, 1848.
§ 'SO. IS'
HYDHOCABBON9.
'39
o|»Brfttionfi, obUined in a vf'vy fnir at»te of purity, ttud may b« cpu verted itit*» niLro-
2. Oonversion into Nltro-Bei3£etie,^i--Tlie oily liquid Li pluccd iu u tbtik^ aiid
ttfjiled with Toui ttiuea ita vohunn of finning iiitrie acid* T}ii> fbisik iiuiiJit Imj fm nisbed
with on upright coiidedser ; a vigorous ifccUou ai<iBtIy t^kea pliicc witliout the
■ppliobtioti of b@at, but if this does not occur, the (l»»k may be -wanu^ for a fcrw
mimLtesL
After tljo oouYpmoij is uvur, tbo Hqiudj wbile aliU warm, must be tmiisfBrrt'd
ill to n bumtte funj]»bi-d ^ith u gloss tsp^ or tt> a sejioratiug funnel, uud all, excejit
the top layer, nn\ into cuhl -ftater ; if beu^i*c* w«« ox-igiiially j>ics4?nt, t?itbpr oily
dropSi of nitro-benjsciio ^vill full, or if ilie beuzeui* Via& only in Ainull qunniityj a fine
j.*rw;i[jitjvto will giitdnuUy aettk down to tbe liottom of tlie reewl, and a distinct
hitttr-iilnjond &moll b« ijba^rved ; but if tliere be no benzene ui the original liquid,
and, couHequeiitly, no nitrubenzeue fonueil, no such a|i|jearance will bit observt*d»
3. ConverBiou into Aniline. — The nilrti-beujsene umy itself be ideiitiJied by
eollectitig it on a \fet fdtei, dissolving it otf the filter by Bloobol, acidifying the
alcoholic solution hy hydruijhluiic acid, and then lH>iling it for sonu' time with
metallic zinc. In this way aniline h fotmcd by txHjTjttion. On neutruU»iiig and
diluting the litjnid, ami cautiously adding a litlk clear tkilntion of bl^Hiehiug-powdi^r,
a blue 01 pni pic colour lussiug to brown is iu a little time produced.
8. TERPEKES— ESSEI^TIAL OILS— OIL OF TURF'EI^TINE.
S 150. Tbu tcrpcnes ai^e bydrocarljenH of the geneml fomiula C,,H^-i. The
natural lei'|u;ni'& are tHvided into thrc^ claHGcs ; —
1. The true terpeneB, /or inukt (0||,Hj^) — a Imgcj number of essential oils, Kucb
ii^ thos^e of turjM^ntiue, tirauge peel, nutmeg, caraway, auiite, tbyme, otc,^ ar*3 mumly
c^mjxihLti *jt teriwrijijiu
2. The c&diGneaj fijrmtda {Ci^H^} — the ciBijentiiil oil of cloves, ro^ewoud, cubohe,
calcinius, cawiaiillii, und pal<^hi>nli belong t^i thia class,
'6. The colopbeue hydrocftrbonfl^/orrtiii/r^ (C*<jjH^), represented by C(»Iophony*
Of all these, oil of t^irtientinc ahirii: han any loiicological signilitance ; it ib, how-
evei', tmc llial all the e^iseutial oil», if taken in con»idembk dot^es, arc poisonuoij,
and cauiie, for the niotit part, vascular excitement atjd complex nervousi ]ittcnuunina^
but their action lum not l>i*eii very completely studied. They may all be svimh rated
by distillation, but a more cimvenient process for iticovering an esfi*?ntial oil firtm a
liquid is to shake it up with petroleum ether, sejiarating tbe pettoleuni and evajio-
mtiiig s)ioutaueously ; by thiif means the oil is left in a fail' state of ptiiity*
4, OIL OF TUHrENTINE^SriRlT OF TURPENTINE— *'TURm'*
1 15L Various si«cies of pine yield a crude turpentine, holding in solution more
iHpIesar^in. Tb« tuqjenttne maybe obtdned from this exudation by distillation,
Kod when the MrBt jtortiun of the distilli^te is treated with alkali, and then redistilled,
the final pri>duet ik kmiwn under the naiiiu of*' rectified oil of turpentine,'* aud is
sometimes called ^^raniphcne," It nniinly consists of iereWntbene. Terebenthene
obtaincv^l fr< jn French tnriK'Uthie dillers in Aoriie n'spects fntrn thai ebtainc-ti from
English or Anierican lui|K^ntinis They ure both mobile, eolourles* Hquid;*, having
the welbknowu odour of tnqjiuitine and highly rt'fntctive ; but the Fi*eneh teres*
benthene turns a ray of iwlaris^sl light to the left - 40*3' for the sodium ray, and
th« English to the right ^-^I'D"; the latter tereltentheuo i.s known ttciL^nlificary as
ifciuitra-terel>euthene, Tliis actiun on polarised light in i-ctained in the varioiLH
oompounds and polydiei^ of the two turpentiue oiIsl
I40 POISONS: THEIR EFFECTS AND DETECTION. [§ 152.
The specific gravity of turpeutiue oil is '864 ; its boiling- point, when consisting of
pure terebenthene, 156", but impurities may raise it up to 160" ; it is combustible
and bums with a smoky flame. Oil of turpentine is very soluble in ether, petroleum
ether, carbon disulphide, chloroform, benzene, fixed and essential oils, and by the
use of these solvents it is conveniently separated from the contents of the stomach.
It is insoluble in water, glycerin, and dilute alkaline and acid solutions, and very
soluble in absolute alcohol, from which it may be precipitated by the addition of
water.
It is j)olymerisod by the action of strong sulphuric acid, the i>olymer, of course,
lK)iIing at a higher tempcmturo than the original oil. With water it forms a crys-
talline hydrate (CioH-joOg, 11.^0). On jMissing nitrosyl chloride gas into the oil, either
pure or diluted with chloroform or alcoliol, the mixture being cooled by ice, a white
crystalline body is deposited, of the formula C,oHie (NOCl). By treating this com-
pound with alcoholic potash, the substitution product (CjoHigNO) is obtained. By
treating turpentine with an equal bulk of warm water, and shaking it in a large
bottle with air, camphoric acid and peroxide of hydrogen are formed. When
turpentine oil is left in contact with concentrated hydrochloric acid, there is formed
terebenthene dihydrochloride (CioHjg2HCl), which fomis rhombic plates, insoluble
in water, and decomposable by boiling alcoholic j)otash, with foniiation of terpinol,
(Ci^H27)20. The dihydrochloride gives a colour-reaction with ferric chloride. This
is an excellent test — not, it is true, confined to oil of turi^utine, but common to the
dihydrochlorides of all the terpenes. A few dro]>s of the oil ai*e stiri-ed in a jwrcelain
capsule with a drop of hydrochloric acid, and one of ferric chloride solution ; on
gently heating, there is produced first a i-ose colour, then a violet-i-ed, and lastly
a blue.
§ 152. Effects of the Administration of Turpentine. — L. W. Licrsch * exposed
animals to the va^Kjur of tur{»entinc, and found that a cat and a rabbit died within
half an hour. There was ol)served uneasiness, reeling, want of power in the limbs
(more esi»ecially in the hinder extremities), convulsions |>artial, or general, difficulty
of respiration ; and the heart's action was quickened. Death took place, in part,
fi-om asphyxia, and in juirt was attributable to a direct action on the nervous centres.
Tlie autopsy showed congestion of the lungs, ecchymoses of the kidney, and much
blood in the liver and spleen. Small doses of turi)entine-vaj>our cause (according to
Sir B. W. Richaixlson) t giddiness, deficient appetite, and anaemia. From half an
ounce to an ounce is fre<iuently p!*escribod in the country as a remedy for tajteworm ;
in smaller quantities it is found to be a useful medicine in a gi-eat vaiiety of ailments.
The larger doses produce a kind of intoxication with giddiness, followed often by
purging and strangury ; not unfi-equently blood and albumen (or both) is found in the
urine. When in medical practice the senior author has given the oil, and seen it given
by othei-s, in large doses for tajKJWonn to adults, in perhaiis 40 cases, but in no one
instance were the symptoms severe ; the slight intoxication subsided quickly, and in a
few hours the {tatients recovered completely. Nevertheless it has been known to destroy
the lives of children, and cause most serious symptoms in adults. Tij^'o fatal cases
are mentioned by Taylor ; one was that of a child who died fifteen houi-s after taking
half an ounce of the oil ; in another an infant, 5 months old, died rapidly from a
teaspoonful. The symptoms in these fatal cases were profound coma and slight
convulsions ; the pupils were contracted, and there was slow and irregular breathing.
Turpentine is eliminated in a changed form by the kidneys, and im{»arts an odour of
violet to the urine ; but the nature of the odoriferous principle has not yet been
investigated.
• Clarus in Schmidt's Jahrbuchcrt Bd. cxvii., i., 1863 ; and Vicrtdjahrsschr. f&r
gcr. Sled,, xxii., Oct. 1862.
t Brit, and For. Jdcd.-Chir. lUview, April 1863.
§ T53-IS5-]
CAMPHOR.
141
ir. — Camphor.
1 153. A great rnatiy CHAt^iilbl uiln dcjioi^itj rvftei' ex^iosure to air, canij^Iioi's iirrj-
InOid by oxidAtian of Iheir terpeii*v<i. OMlnaf)' cftrnphor is imported in tlit' rough
state from Chiim tttid Ja|iaDr and ia jitflj>ared l>y tliwtilliiig with wat*?r tht: wnixl nf
Cinnmnmnum mmph&ra ; it i» resi:iMini(?d in England, The ftirmula of caiiijiliftr m
GjfjUjrtO ; it lias a rbiisity t)f '^86 t^i '996 ; m^lts at 175"*, and l>ciila at 205°, It is
ritsadilj subliitied, cjipecially in iv vat^imnij and i« indeed so volatile at all tomjwra
tures, that a lump t^f catsipln>i iixpoF^tsfi to the air wastesi /tway. It in slightly
saluhlti in water (jiboiit 1 jiwrt in ]000), but tliis is enougli U* imj^rt a distinct
taato to the wat4?i ; it is insoluble in chloioform^ ether ^ acfttoue, acetic aeid, carl ion
diaulpbide, and oils. It baa a frngiuiit cniotir and a burning taste* A 10 per cent.
s*jlution in alcobo! ttjrns a lay of |M)larjii«l light to the right +42'S". By dktiOation
with Kinc chloride, cymenp and othtjr prriducta are produced* By prc4<mg^ treat -
Tnent with nitric atndj camphor is oxidiEicd to campfaona acid (CinHigO^)* Camphor
unites with bnimine Ui ftirtn a ctjfitj&Miiie^ uuHtable dibromidet which splits up on
distillation into hydrobrornic acid and raonobrom-eamplior (Cj^HjEtBrO). The latt«r
ia u&ed in medicine ; it crystal lisPs in prisma fuaible at 7^'\ and is rwidilj soluble in
ftlcolioi
§ 154. Fh&rmacenticftl Pre para tioni.^Tbe preparations officinal in tliB Britif^h
Phanna/CMipft ia arc tamphor trsiicrr— i^'ater saturatfld with camphor, eontatniiig about
1 part jicr 1000.
Camphor linimatit.^A Bolution of camphor in olive oil, H&rength 25 per eent.
Compound Camphor tinimaiit.^-ComiioHed of camphor^ oil of lar endear, strong
Bolotioij ofamratMHJi ami alciibol ; strength in camphor about 11 per cent*
Spirit of Camphor*— A mint ion of camphor in spirit; streugtb, IQ fiercent
Can^pbtir in als<j a constituent of the compound tincture of r^viphftr ; but in this
case* it may bo i::6>nsidoi^d uidy a flavouring agenL There is a homasofiathic tsolution
iif camphor in s]]irit (Rubini*a EsHcuco of Campbor)^ The solution is matle hy satu*
rating alcohol with camphor ; it is, thereforej very stronjf — aliout half the bulk can-
iisting of c4imphor* Camphor u UHod in veterinary medbine, iKjtb externally and
interna! ly.
g 155* Symptomfl. — Camphor acta energetically on the brain and nervous system,
e«ftecially if it is given in strong alcoholic fsolutjon, and thiiH j>laced under conditions
favouring absorption. Some years ago, Dr, G. John son* publiahed a acHes of cases
arising from the injudicious use of '* homo3opat.hic solutirin of camphor,*' frcjm 7 to
iO drof>a of Rubini's bomfifojiatbic camtihor taken for colds, sore thnM4t( ett%, having
pnHluce<) coma, f(>anung at the mouth, convuiHinnH, and paitial [laralysis* All the
[tatietJts,ii?covcre*l, but their cnudition was for a little lime alarming.
The c.a*cs of fatal poUtuiing by camidior are very rare, A woman, aged 46, prf-g-
liant four months, toiik 12 gmis* (about 184 grains) in a glaa^ of brandy for tbc
pur)ioae of procuriug aliortion- In a very short time the ayniptoms commeneed \
she had intolerable headache, the face waji flushed, and there was a actasfitifUi of
burning in the stomach. In eight hour^ after baking the dosie she haij strangury
aufl vonnting, aiul the pain in the ejiig^istriutn wa.^ intense. Tliese symptoms con-
tinued with more or Icftw severity nntil the ttnrd day^ when she lH?catne much worse.
Her face was jtale and livid, the eyes tiollow, the skin cold and iuijenHible, pulse
weak and tlireadyj bii?atliing labourmL Thei^ were violent cnunpn in tlie stomaeh
and retention of urine for twentj^-fnur liourH^ and then coma. The jwtieut Uugereil
on jet another three days, aborted, and dieebf
*- Brii. Med. Joum., Feb, 27 » 1S78, p, 272; see also li^^., Fob. I87£u
t Joum, tUChim, MM.^ May 1&30*
142 POISONS: THEIR EFFECTS AND DETECTION. [§ 156-159.
Dr. Schaaf * has recorded three cases of poisoning— one of which was fatal. A
woman gave about half a teaspoonful of a camphor solution to each of her three
children, the age« being respectively 5 and 3 years, and 15 months. The symptoms
noted were pallor of the face, a burning pain in the throat, thirst, vomiting, purging,
convulsions, and afterwards coma. The youngest child died in seven hours ; the
others recovered. The smallest dose known to have produced violent symptoms in
an adult |)erson is 1 *3 gmi. (20 grains) ; the largest dose known to have been re-
covered from is 10 '4 grms. (160 grains), t
§ 156. Pofit-mortem Appearances. —The bodies of animals or persons dying from
poisoning by camphor, smell strongly of the substance. The mucous membrane of
the stomach has been found inflamed, but there seem to be no characteristic lesions.
§ 157. Separation of Camphor from the Contents of the Stomach. —The identi-
fication of camphor would probably in no case present any difficulty. It may be
readily dissolved out from organic fluids by chloroform. If dissolved in fixed oils,
enough for the pur{)oscs of identification may be obtained by simple di.stillation. It
is precipitated from its alcoholic solution by the addition of water.
III.— Alcohols.
1. ETHYLIC ALCOHOL.
§ 158. The chemical properties of ordinary alcohol are fully de-
scribed, with the appropriate tests, in " Foods," pp. 379-398, and the
reader is also referred to the same volume for the composition and
strength of the various alcoholic drinks.
Statistics. — If we were to include in one list the deaths indirectly
due to chronic, as well as acute poisoning by alcohol, it would stand
first of all poisons in order of frequency, but the taking of doses so large
as to cause death in a few hours is rare. The deaths from alcohol are
included by the English Registrar-General under two heads, viz., those
returned as dying from delh-ium tremens^ and those certified as due
directly to intemperance.
From 1875 to 1903 the deaths registered as due to intemperance
have varied from a minimum of 1269 up to 3638, the maximum occur-
ring in 1900. The curve on the opposite page clearly shows the alcoholic
death-rate per million living during the'period. Alcoholic deaths, with
a few intermissions, increased from 1879 to 1900, and since that year
have declined.
During the ten years ending 1903, 82 deaths (56 males and 26
females) were ascribed, under the head of "accident or negligence,"
directly to alcohol.
§ 159. Criminal or Accidental Alcoholic Poisoning.— Suicide by
alcohol, in the common acceptation of the term, is rare, and murder
♦ Journ. dr. Chim. M6d., 1850, p. 507.
t Taylor on Poisons^ 3rd ed., 661.
^^P^l 159] ITHTLTC ALCOHOL. ^^^^^^^■^143
V still rarer, though not unknown. Tn the ten years ending 1903, only
^^ft DEATHS PER MILLION LIVINU FROM ALCOHOL FROM 1875-1001
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?ath8 from alcohol (3 males and 2 females) nre recorded as suicidal,
tiapa the mo&t common cause of ffital acute poi^ouing Ly alcohol is
J
144 POISONS: THEIR EFFECTS AND DETECTION. [§ l6o, l6l.
either a foolish wager, by which a man bets that he can drink so many
glasses of spirits without bad effect ; or else the drugging of a person
already drunk by his companions in a sportive spirit.
§ 160. Fatal Dose.— It is difficult to say what would be likely to
prove a lethal dose of alcohol, for a great deal depends, without doubt,
on the dilution of the spirit, since the mere local action of strong
alcohol on the mucous membranes of the stomach, etc., is severe (one
may almost say corrosive), and would aid the more remote effects. In
Maschka's case,* a boy of 9 years and a girl of 5 died from about
2^ ounces of spirit of 67 per cent, strength, or 48*2 c.c. (1*7 oz.) of
absolute alcohol.
In a case related by Taylor, a child, 7 years old, died from some
quantity of brandy, probably about 113*4 c.c. (4 ozs.), which would be
equal to at least 56*7 c.c. (2 ozs.) of absolute alcohol. From other cases
in which the quantity of absolute alcohol can be, with some approxi-
mation to the truth, valued, it is evident that, for any child below 10
or 12, quantities of from 28-3 to 56-6 c.c. (1-2 ozs.) of absolute
alcohol contained in brandy, gin, etc., would be a highly dangerous and
probably fatal dose ; while the toxic dose for adults is somewhere
between 71'8-141*7 c.c. (2*5-5 ozs.).
§ 161. Symptoms. — In the cases of rapid poisoning by a large dose
of alcohol, which alone concern us, the preliminary, and too familiar
excitement of the drunkard, may be hardly observable ; but the second
stage, that of depression, rapidly sets in ; the unhappy victim sinks
down to the ground helpless, the face pale, the eyes injected and
staring, the pupils dilated, acting sluggishly to light, and the skin re-
markably cold. Frantzel t found, in a case in which the patient survived,
• Recorded by Maschka (OiUaehten der Prager Facultdt^ iv. 239 ; see also
Masohka's Handbucfi der gericht. Medieifif Band ii. p. 384). The following is a
brief summary : — Franz. Z., 9 years old, and Caroline Z., 6 years old, were })oisoned
by their stepfather with spirit of 67 per cent, strength taken in small quantities
by each— at first by persuasion, and the remainder administered by force. About
one-eighth of a pint is said to have been given to each child. Both vomited some-
what, then lying down, stertorous breathing at once came on, and they quickly
died. The autopsy, three days after death, showed dilatation of the pupils ; rigor
mortis present in the boy, not in the girl ; and the membranes of the brain filled
with dark fluid blood. The smell of alcohol was perceptible on opening the chest ;
the mucous membrane of the bronchial tubes and gullet was normal, both lungs
oedematous, the fine tubes gorged with a bloody frothy fluid, and the mucous mem-
brane of the whole intestinal canal was reddened. The stomach was not, unfortu-
nately, examined, being reserved for chemical analysis. The heart was healthy ; the
pericardium contained some straw-coloured fluid. Chemical analysis gave an entirely
negative result, which must have been from insufficient material having been sub-
mitted to the analyst, for it is hard to see how the vapours of alcohol could have been
detected by the smell, and yet have evaded chemical processes.
t Teinperaturemiedrigung dureh AlcoholirUoxkcUion, ChariU Jnn^Uen, i. 871.
§ .62.]
ETHYLIC AIX30H0L.
145
a temperature of only 24'6'' in the rectum, and in that of another
person who diedj a temperature of 23*8^ The mucous membranes arc
of a peculiar dusky blue ; the pulse, wbich afc tii^t is quick, «oon becomes
glow and small ; the respiration is also slowed^ intermittent, and
gtertorous ; there is complete loss of conscIousueBS and motion ; the
breath smclla strongly of the alcoholic drink, and if the coma continues
there may be vomitiug and involuntary passing of excreta. Death
ultimately ocoura through paralyBis of the respiratory centres. Con-
vuUtous in iidulU are rare, in cliildreu fre<|nenti Death has more than
once been immediately caused, not by the poison, but by accidents de-
pendeut upon loss of oonsciouaness. Thus food Inis been sucked into the
air- tubes, or the person has fallen, so that the face vim burieil in water,
ordure, or mud ; here suflbcation has been induced by mechanical cansea.
A remarkable course not known with any other narcotic is that in
which the symptoms remit, the person wakes up, as it were, moves about
and does one or more rational acts, and then suddenly dies. In this
case alao^ the death is not directly due to alcohol, but indirectly — the
alcohol having develojied cede ma, imeumouia, or other aflection of the
Inngm, which causes the sudden termination when the first effect of the
poison has gone oC The time thnt may elapse from the commence-
juent of coma till death varies from a few minutea to days ; death baa
occurred after a quarter of an hour, half an hour, and an hour. It
has also been prolan j^ed to three, four, and sii days, during the whole
of whioh the couia has con tinned. The average period may, however,
be put at ftott) six to ten hoMUs.
§ 162. PoBt-mortem Appearances.— Cadaveric rigidity hists toler-
ably long> Csisper has seen it Btill existing niue days after death, and
Seidel * seven days (in February), Putrefaction is retarded in those
cases in which a very large dose has been taken, but this is not a very
noticeable or constant characteristic. The pupils are mostly dilated.
The smell of alcohol shouhl be sought for ; sometimes it is only
present in caaes where but a short time has elapsed between the taking
of the poison and death ; putrefaotiott may also conceid it, but under
favourable circumstances, espeoiully if the weather is cold, the alcoholic
smell may remain a long time. Alcohol may cause the most iu tense
reduess and congestion of the stomach. The most inflamed stomach 1
(A, W. B.)ever saw, short of inflammation by the corrosive poisons, wan
that of a sailor, vvho died suddenly after a twenty-four lionrs' drinking
bout : all the organs of the body were fairly healthy, the man had suffered
from no disease ; analysis could detect no poison but alcohol ; and the
history of the case, moreover, proved clearly that it was a pure case of
alcoholic poisoning,
' Sejdd, Mnwhkft's iTaiMurh, Bd, iL p. S80.
146 POISONS: THEIR EFFECTS AND DETECTION. [§ 163.
In a case related by Taylor, in which a child drank 4 ozs. of brandy
and died, the mucous membrane of the stomach presented patches of
intense redness, and in several places was thickened and softened, some
portions being actually detached and hanging loose, and there were
evident signs of extravasations of blood. The effect may not be con-
fined to the stomach, but extend to the duodenum and even to the
whole intestinal canal. The blood is generally dark and fluid, and
usually the contents of the skull are markedly hyperaemic, the pia very
full of blood, the sinuses and plexus gorged ; occasionally, the brain
substance shows signs of unusual congestion ; serum is often found in
the ventricles. The great veins of the neck, the lungs, and the right
side of the heart are very often found full of blood, and the left side
empty. (Edema of the lungs also occurs with tolerable frequency.
The great veins of the abdomen are also filled with blood, and if the
coma has been prolonged, the bladder will be distended with urine. A
rare phenomenon has also been noticed — namely, the occurrence of
blebs on the extremities, etc., just as if the part affected had been burnt
or scalded. Lastly, with the changes directly due to the fatal dose may
be included all those degenerations met with in the chronic drinker,
provided the case had a history of previous intemperance.
§ 163. Excretion of Alcohol. — Alcohol, in the diluted form, is
quickly absorbed by the blood-vessels of the stomach, etc., and circulates
in the blood ; but what becomes of it afterwards is by no means settled.
There can be little doubt that the lungs are the main channels
through which it is eliminated ; with persons given up to habits of
intemperance, the breath has constantly a very peculiar ethereal odour,
probably dependent upon some highly volatile oxidised product of
alcohol.
Alcohol is eliminated in small proportion only by the kidneys.
Thudichum, in an experiment* by which 4000 grms. of absolute
alcohol were consumed by thirty-three men, could only find in the
collected urine 10 grms. of alcohol. The numerous experiments by
Dupr^ also establish the same truth, that but a fraction of the total
alcohol absorbed is excreted by the kidneys. According to Lallemand,
Perrin, and Duroy, the content of the brain in alcohol is more than
that of the other organs. One of us (A. W. B.) has found also that
the brain after death has a wonderful attraction for alcohol, and yields
it up at a water-heat very slowly and with difiiculty. In one experiment,
in which a finely divided portion of brain, which had been soaking in
alcohol for many weeks, was submitted to a steam-heat of 100°, twenty-
four hours* consecutive heating failed to expel every trace of spirit.
* See Thudichum '8 Pathology of the Urine ^ London, 1877, in which both his
own and Dr. Dupre*8 experiments are summarised.
§ i64-]
ETRTLIC ALCOHOL.
147
It IS probable tbat true alcohol Htes of the cbemical conBtituenta of
the braiu are formed. In the case of vegetable colloidal bodies, such,
for example, as the pulp of cherrieaj a similar attraction has beeu
observed, the fruit condensing, as it were, the alcohol in its owti tiesueH,
and the outer liquid being of lesa alcoholic strength than that which
can be expressed from the steeped cherries. Alcohol is also excreted
by the sweat, and minuto fractions have been found in the fieccs,
§ 164. Toxicological Betectioii of Alcohol (see "Foofla,'* pp.
382-384),^ — The living cells of the bo<lj prodtice minute quantities of
alcohol, aa also some of the bacteria normally inhabiting the small
intestine produce small quantities of alcoliol, and it is often fotmd in
tmces in putrefying fluids, Hence^ mere qualitatiye proofs of the
preeeuce of alcohol are insufficient on which to base an opinion as to
whether alcohol had been taken dttring life or not, and it will be
necessary to estimate the quantity accurately by some of the processes
detailed in ** Foods," p. 385 ei »eq. In those cases in which alcohol
is found in quantity in the stomach, there can, of coulee, be no diffi-
culty ; in others, the whole of the alcohol may have been abeorbedj and
chemical evidence, unless extremely definite, must be supplemented
by other facts.
Alcohols may in many inatancea be identified by converting them
into the dinitro-benzoate eaters.
The following directions for ethyl alcohol are given by Mul liken *
for the preparation of ethjl 3r5 dinitro-benzoate, and are applicable to
the series generally, with a few obvious modifications, provided the
alcohol is pure and contains no more than 10 per cent* water*
Heat together gently over a small ftame 015 gruK 3:5 dinitro-
benzoic acid and 0*29 grm, phosphorus pentachlorida. When Bigns of
chemical action appear, the lieat is removed for a few seconds. The
heat is then reapplied, and the liquefietl mixture boiled for exactly one
minute. The product is poured out on to a watch-glass and allowed
to solidify. The liquid phosphorus oxychloridc, with which the mass
is impregnated, is got rid of by rubbing the latter between two pieces
of porous tile. The powder is placed in a dry teat tulie, and four drops
of alcohol are allowed to fall on it (with propyl or butyl alcohols six drops
are aildcfl instead of four^ because the alcohol must be in excess), the tube
is at once stoppered, and the lower pi^rt immersed in water at 75'-85*.
The tube is shaken gently and warmed in this way for ton minutes.
When the mixture is oold, any hard lumps of ester which may have
formed are cmshed with a stirring rod, and in the case of ethyl dinitro
benssoate boiletl gently with 15 c.c. of methyl alcohol until all in
dissolved.
* A Mdhofl/iff the Idtnii^^ati&tt of Pure Orffonie C&mpo>undM^ New York, 1004.
148 POISONS: THEIR EFFECTS AND DETECTION. [§ 165-168.
(With most other esters, instead of methyl alcohol as a solvent,
ethyl alcohol is used.)
If the solution is not clear it must be filtered hot. The final
crystals are recrystallised from boiling methyl alcohol, washed with the
same solvent, spread out on a porous tube to dry, and the melting-
point determined.
Methyl 3 : 5 dinitro-benzoate melts at
. 107-5»
Ethyl ., „ . .
. 92', 93'
Isobutyl „ „
83'-88-5'
Propyl „ „ . .
73"
Butyl „ M . .
64'
2. AMYLIC ALCOHOL.
§ 165. Amylio Alcohol— i^orwiwte, CsHuHO.— There is more than one amylic
alcohol, according to theory ; eight isomers are possible, and seven are known. The
amylic alcohols differ in certain physical properties, primary amylic alcohol boiling
at 137', and iso-amyl alcohol at 131*6'. The latter has a specific gravity of *8148,
and is the variety produced by fermentation and present in fusel oil.
§ 166. The experiments of Eulenberg * on rabbits, Cross t on pigeons, Rabutcau^:
on frogs, and Furst on rabbits, with those of Sir B. W. Richardson § on various
animals, have shown it to be a powerful poison, more especially if breathed in a
state of vapour.
Richardson, as the result of his investigations, considers that amyl alcohol
when breathed sets up quite a peculiar class of symptoms which last for many hours,
and are of such a character that it might be thought impossible for the animal to
recover, although they have not been known to prove fatal. There is muscular
paralysis with paroxysms of tremulous convulsions ; the spasms are excited by
touching the animal, breathing upon it, or otherwise subjecting it to trifling
excitation.
§ 167. Hitherto, neither the impure fusel oil, nor the purer chemical preparation,
has had any toxicological importance. Should it be necessary at any time to recover
small quantities from organic liquids, the easiest way is to shake the liquid up with
chloroform, which readily dissolves amylic alcohol, and on evaporation leaves it in a
state pure enough to be identified. Amyl alcohol is identified by the following
tests : — (1) its physical properties ; (2) if warmed with twice its volume of strong
sulphuric acid, a rose or red colour is produced ; (3) heated with an acetate and
strong sulphuric acid, amyl acetate^ which has the odour of the jargonelle }>ear, is
fonned ; (4) heated with sulphuric acid and potassic dichromate, valeric aldehyde is
first produced, and then valeric acid is formed ; the latter has a most peculiar and
strong odour.
§ 168. Amyl Nitrite, Iso-amyl Ester Nitrite (CjHnNOa).— Boiling-point 97* to
99', specific gravity '877. Amyl nitrite is a limpid, and, generally, slightly yellow
* Oeicerbe Hygiene^ 1876, p. 440.
t De V Alcohol Amylique et Methyl sur VOrganisme (Th^e)^ Strasburg, 1868.
X "Ueber die Wirkung des Aethyl, Butyl u. Amyl Alcohols," L* Union, Nos.
90, 91, 1870. Schmidt's Jahrb., Bd. cxlix. p. 263.
§ Trans. Brit. Association, 1864, 1866, and 1866. Also, Brit, and Foreign
Med, Chir. Rev,, Jan. 7, 1867, p. 247.
§ 169, i7ol
KTHEB,
149
liquid ; it hoj! a pixiuliar ai^d ulmrafituristic odour. On hwiting with JilcohoUc [lotaib,
the produata arc nitrite of potash and anrtylic alcohol ; the amy lie alcohol amy be
diHtilled oft' and ideii tilled. The prwwiict' of a tiitriU. iti the alkaline solution is i-cadily
shown bj the colour produced, by adding n few dropB of a uolution ofmota'pheuytetie-
lUaiuiuo,
Sir B. W, Richstxlaon and others have investigiated the action of amy 1 nitrito* m
well a» that of tliu ftcotati3 and iodide ; tboy aU act in a similar mauner, the nitrite
being mofit potent. After atisarption, the elFectB of atnyl nitrito are cj^jiecially taacn
on the heart and uirtmlation i the heart acta violeotlyi there h first dilatatjoti of the
iiapillaries, then tluH h followed hy dimmlahed aotion of tho heart &nd oontmctiou
of t!ie caplUatioa.
Accord i[ig to Richardson, it suspends tlie animation of frngs, No other anb-
stance known will thmi Hu^^Mjud a fro|^*s animation for 80 long a time without ki11in|f
it. Under favouiiible circumstances, the animal will remain ap[iarent1y df>ad for
many lUysj and yet re<JOV©r* Warra*hlooded animals may lie thrown hy junyl
nitrite into a cataleptic <^mdition. It is not an aowsthetic, and hy itsi use cooitciouH*
uess m not dfistroyi3dj unless a condition apjvroochinjj death he lirat produccfi When
Vtm oceura there is rrtrcly riMJoyery, the auinial iwsses into actual de^th.
FoBt^mortem Appearattcet.— If Eidniiniaterod quickly, the lungs atjd all the other
orgiins ar« found blanched and free from hlotid, the right aide of the heart goi^gisd
with blood, the left empty, the brain being free from congestion. If administered
lalowly^ the brain is found congested, aud there is blood both on the left and right
sides of the heart.
I V< -Ether.
§ 169. Ether, Ethylic Ether, Ethyl Oxide, {C^H^J/J.—Et hylic ether
in a highly mobile liquid of peculiar |>euetraiting odour and sweetish,
pungeat taste. It ia perfectly colon rJess, atid evaporates so rapidly^
that when applied in the form of bpray to the skin, the latter becomes
frozeOy and is thus deprived of aensibiUty.
Pure ether has a deneity of 713, its boiliiig-pDjnt is 35*, but coiii-
tnercial Bampleis, which often contain water (J part of water is soluble in
35 of ether), may have a higher gravity, and also a higher boiling-point.
The readiest way to know whether an ether is anhydrous or not, h to
tshake it up with a little carbon di^ulphidc. If it i:^ hydrouSi the
mixbure is milky. Methylated ether is largely used iu commerce ; its
disagreeable odour is due to contamination by methylated compounds ;
otherwise the ether made from methylated spirit is ethyliu ether, for
me thy lie ether is a gas which esoapea during the process. Hence tlie
term ** methylated '* ether is misleading, for it contains no methyl ic
ether, but is essentially a somewhat impure ethylic ether.
g 170. Ether as a Poison,— Ether has but Uttle todeological im-
portance. There are a few cases of death from its use as an anesthetic,
and a few cases of suicide. Ether is used hy some people as a stimulant^
but ether drinkers arc uncommon. It causes an intoxication very
similar to that of alcohol, but of Ijrit^f duration. In a case of chronic
150 POISONS: THEIR EFFECTS AND DETECTION. [§ 171-173.
ether-taking recorded by Martin,* in which a woman took daily doses
of ether for the purpose of allaying a gastric trouble, the patient suflFered
from shivering or trembling of the hands and feet, muscular weakness,
cramp in the calves of the legs, pain in the breast and back, inter-
mittent headaches, palpitation, singing in the ears, vomitings, and
wakefulness ; the ether being discontinued, the patient recovered. In
one of Orfila's experiments, half an ounce of ether was administered to a
dog. The animal died insensible in three hours. The mucous membrane
of the stomach was found highly inflamed, the inflammation extending
somewhat into the duodenum ; the rest of the canal was healthy. The
lungs were gorged with fluid blood.
§ 171. Fatal Dose. — The fatal dose of ether, when taken as a liquid,
is not known. 4 grms. (1 '28 drms.) cause toxic symptoms, but the effect
soon passes. Buchanan has seen a brandy-drinker consume 25 grms.
(7 drms.) and yet survive. It is probable that most adults would be
killed by a fluid ounce (28-4 c.c).
§ 172. Ether as an Anaesthetic. — Ether is now much used as an
anaesthetic, and generally in conjunction with chloroform. Anaesthesia
by ether is said to compare favourably with that produced by chloroform.
In 92,000 cases of operations performed under ether, the proportion
dying from the effects of the anaesthetic was only '3 per 10,000 (Morgan),
while chloroform gives a higher number (see p. 156). The mortality in
America, again, from a mixture of chloroform and ether in 11,000 cases
is reckoned at 17 per 10,000; but this proportion is rather above some
of the calculations relative to the mortality from pure chloroform, so that
the question can hardly be considered settled. The symptoms of ether
narcosis are very similar to those produced by chloroform. The chief
point of difference appears to be its action on the heart. £ther, when
first breathed, stimulates the heart's action, and the after-depression that
follows never reaches so high a grade as with chloroform. £ther is said
to kill by paralysing the respiration, and in cases which end fatally
the breathing is seen to stop suddenly: convulsions have not been
noticed. The post-mortem appearances, as in the case of chloroform,
are not characteristic.
§ 173. Separation of Ether from Organic Fluids, etc. — Despite the
low boiling-point of ether, it is by no means easy to separate it from
organic substances so as to recover the whole of the etiier present. The
best way is to place the matters in a flask connected with an ordinary
Liebig's condenser, the tube of the latter at its farther end fitting closely
into the doubly perforated cork of a flask. Into the second perforation
is adapted an upright tube about 2 feet long, which may be of small
diameter, and must be surrounded by a freezing mixture of ice and salt.
* Comptca limulus^ 18i)8.
S 174^]
CELOHOFOBM.
151
Ths uppar end of thk tube is closed by », thistle- head funnel with
»yphon, aod in the bend of the i^^jphon a little mercury gorves a8 a vaWe,
Heat is now applied to the Haak by means of a water bath , and continued
for several bonrs ; tbe liquid which has distilled over ia then treated
with dry calcic chloride and redi a tilled exactly in the same way. To
this distillate again a similar process may be used, aubstitnting dry
potassio carbonate for the calcic chloride* It is only by operating on
thejse principles that the expert can recover in an approximate state of
anhydrous purity snob a volatile liquid. Having thus obtained it pure,
it may be identified (1) by its araolli (2) by its boiling-point, (3) by its
inflammability J and (4) by its reducing chromic acid. The latter teat
may be applied to the vapour. An asbestos fibre is soaked in a mixture
of strong snlphiiric acid and potassie dicbromate, and then placed in the
tube connected with the flaak— tbe ethereal (or alcoholic) vaptiur passing
over tbe fibre immediately reduces the cbronuc acid to cbromic oxide,
with the production of a green colour.
v.— Chloroform.
CHLOROFORM , TRICHLOROMETHANE OR METHYL CHLORIDE
(CHCJ^),
g 174. Chloroform appears to have been diaeovered independently by
Soubeyran and Liebig, about 1830. It was first employed in medicine
by Simpson, of Edinburgh, as an anicstbetic. Pure chloroform has a
dfjnaity of 1*491 at 17\ and boils at GO'S" ; but eommeroial samples have
gravities of from 1'47 to 1'49L It is a colourless liquid, strongly
refracting light ; it cannot bo ignited by itself, but, when mixed with
alcohol, burns with a smoky Bame edged with green. Its odour is
heavy, but rather pleasant ; the taste in sweet and burning.
Chloroform sinks in water, and is only slightly Moluble in that fluid
(*44 in 100 c.e,) ; it is perfectly neutral ia reaction, and very volatile.
When rubl^ed on the nklu, it should completely evaporate, leaving no
odour. Pure absolute chloroform gives an opaline mixture if mixed
with from 1 bo 5 volumes of aloobol, but with any quantity above
5 volumes the mixture is cle&r ; it mixes in all proportions with ether
Chloroform coagulatea albumen, and is an excellent solvent for most
organic bases — oampbor, caoutchouc, amber, o|)al, and all common resins.
It dissolves phoaphunis and sulphur slightly— more freely iodine and
bromine. U floats on bydric sulphate, which only attacks it at a boiling
beat
Chloroform is sometLmc^ impure from faulty manufacture or decom-
152 POISONS: THEIR EFFECTS AND DETECTION. - [§ 1 74.
position. The impurities to be sought are alcohol, methylated chloro-
form,* dichloride of ethylene (C2H4CI2), chloride of ethyl (C2H5CI),
aldehyde, chlorine, hydrochloric, hypochlorous, and traces of sulphuric
acid : there have also been found chlorinated oils. One of the best tests
for contamination by alcohol, wood spirit, or ether, is that known as
Roussin's ; dinitrosulphide of iron t is added to chloroform. If it contain
any of these impurities, it acquires a dark colour ; but if pure, remains
bright and colourless.
The presence of alcohol or ether, or both, may also be discovered by
the bichromate test, which is best applied as follows: — A few milli-
grammes of potassic bichromate are placed at the bottom of a test tube
with four or five drops of sulphuric acid, which liberates the chromic
acid ; next, a very little water is added to dissolve the chromic acid ;
and lastly, the chloroform. The whole is now shaken, and allowed to
separate. If the chloroform is pure, the mass is hardly tinged a greenish-
yellow, and no layer separates. If, however, there is anything like 5
per cent, of alcohol or ether present, the deep green of chromium
chloride appears, and there is a distinct layer at the bottom of the
tube.
Another way to detect alcohol in chloroform, and also to make an
approximate estimation of its quality, is to place 20 c.c. of chloroform
in a burette, and then add 80 c.c. of water. On shaking violently, pure
chloroform will sink to the bottom in clear globules, and the measurement
will be as nearly as possible the original quantity ; but if anything like
a percentage of alcohol be present, the chloroform is seen to be diminished
in quantity, and its surface is opalescent, the diminution being caused
by the water dissolving out the alcohol. The addition of a few drops
of potash solution destroys the meniscus, and allows of a close reading
of the volume. The supernatant water may be utilised for the detection
of other impurities, and tested for sulphuric acid by baric chloride, for
free chlorine and hypochlorous acid by starch and potassic iodide, and
for hydrochloric acid by silver nitrate. J Fuchsine, proposed by Stadeler,
is also a delicate reagent for the presence of alcohol in chloroform, the
sample becoming red in the presence of alcohol, and the tint being
proportionate to the quantity present. The most delicate test for
* Methylated chloroform is that which is prepared from methylated spirit It
is liable to more impurities than that made from pure alcohol, but, of course, its
composition is the same, and it is now manufactured from this source almost
chemically pure.
t Made by slowly adding ferric sulphate to a boiling solution of ammonic su]i)hide
and potassic nitrite, as long as the precipitate continues to redissolve, and then
filtering the solution.
t Neither an alcoholic nor an aqueous solution of silver nitrate causes the slightest
change in pure chloroform.
I I7S-' 77]
GHLOROl«t»KM,
'S3
alcohol ifi> however, the iodoform tcaat fully described in " Foods, "p. 383.*
Dichloride uf ethykne is detected hy shaking up the chloroforiii T^ith
dry potaesic earbouate, and theu adding mebaliic potassium. Thi^ does
not act ou pure eblorgform, but only in presence of ethylene diehlonde,
when the gnseoua chloretbyieno (C^H^Cl) is evolved. Etliyl*chloride is
detected by distilUug the chloroform aud collecting the hrst poitiona ol
the distillate ; it will have a distinct odour of ethyl-chloride should it
be present. Methyl compounds and empyrenmatic oils are roughly
detected by allowing the chloroform to evaporate on a cloth. If presont}
the cloth, whan the chloroform has evaporated, will have a pcenliar,
disagreeable odour. Aldehyde is recognised by its reducmg action on
argentic nitrate; the mineral acids by the reddening of litmus- paper,
and the appropriate teBt«. Hypochlorous acid first reddens, and then
bleaches, litmus- paper.
Dr, Dott (Fharm. Jourru^ 1894, p. 629) gives the following tests: —
Specific gravity^ 1 '490 to 1 495* On allowing \ fluid drm» to evaporate
from a clean Burface, no foreign odour is perceptible at any stage of the
evaporation. When 1 fluid drm. is agitated with an equal volume of
solution of silver nitratej no precipitate or turbidity is produced after
standing for five minutes. On shaking up the chloroform with half its
volume of distilled water, the water should not redden litmus-paper.
When shaken with an equal volume of sulphuric acid} little or no colour
should be imparted to the acid.
g 175, The ordinai'y method of manufacturing chloroform is by
distilling alcohol with chlorinated lime; but another mode is now much
in use — via., the decomposition of chloral hydrate. By distilling it
with a weak alkali, this process yields such a piu*e chloroform, that, for
medicinal purposes, it should supersede every other.
1. AS A LIQUID.
§ 176. Poisonous EfFectfi of Chloroform— Statistics. ^Falck findss
recorded in medical literature 27 cases of poisoning by chloroform
having been swallowed — of these 15 were men, 0 were women ^ and
3 children. Eighteen of the cases were sujuidalj and 10 of the 16
died ; the remainder took the liquid by mistrike.
g 177. Local Action of Chloroform.— When applied to the skin or
mucous membranes in such a way that the lluid cannot evapomte — as,
* An atUmipt lias boen mftde hj Bosiioii to estimate tbe aniouut of akohol by
th« specific gmvity. He fouud that a cliloruform of \*4^ih i^mvityt mixed with 5
percent, of alcohol, gave a specific gravity of 1*4772 i 10 i>er ocnt,, 1/J6C>2 ; 20 per
ceut,| 1*4*2^2 ; aud 25 j>er c^uL^ 1'4090, It would, therefore, aoejii that overy jwr*
c^t&gie of alcohol lowera the gravity by '0034.
154 POISONS: THEIR EFFECTS AND DETECTION. [§ 1 78, 1 79.
for example, by means of a cloth steeped in chloroform laid on the bare
skin, and covered over with some impervious material — there is a
burning sensation, which soon ceases, and leaves the part anaesthetised,
while the skin, at the same time, is reddened, and sometimes even
blistered.
§ 178. Chloroform added to blood, or passed through it in the state
of vapour, causes it to assume a peculiar brownish colour owing to
destruction of the red corpuscles and solution of the hemoglobin in
the plasma. The change does not require the presence of atmospheric
air, but takes place equally in an atmosphere of hydrogen. It has been
shown by Schmiedeberg that the chloroform enters in some way into a
state of combination with the blood corpuscles, for the entire quantity
cannot be recovered by distillation; whereas the plasma, similarly
treated, yields the entire quantity which has in the first place been
added. Schmiedeberg also asserts that the oxygen is in firmer com-
bination with the chloroformised blood than usual, as shown by ita slow
extraction by stannous oxide. Muscle, exposed to chloroform liquid by
arterial injection, quickly loses excitability and becomes rigid. Nerves
are first stimulated, and then their fimction for the time is annihilated ;
but on evaporation of the chloroform^ the function is restored.
§ 179. General Effects of the Liquid. — However poisonous in a
state of vapour, chloroform cannot be considered an extremely active
poison when taken into the stomach as a liquid, for enormous quantities,
relatively, have been drunk without fatal effect. Thus, there is the case
recorded by Taylor, in which a man, who had swallowed 11 34 grms.
(4 ozs.), walked a considerable distance after taking the dose. He
subsequently fell into a state of coma, with dilated pupils, stertorous
breathing, and imperceptible pulse. These symptoms were followed by
convulsions, but the patient recovered in five days.
In a case related by Burkart,* a woman desired to kill herself with
chloroform, and procured for that purpose 50 grms. (a little less than
one ounce and a half) ; she drank some of it, but the burning taste and
the sense of heat in the mouth, throat, and stomach, prevented her from
taking the whole at once. After a few moments, the pain passing off,
she essayed to drink the remainder, and did swallow the greater portion
of it, but was again prevented by the suffering it caused. Finally, she
poured what remained on a cloth, and placing it over her face, soon
sank into a deep narcosis. She was found lying on the bed very pale,
with blue lips, and foaming a little at the mouth ; the head was rigidly
bent backwards, the extremities were lax ; the eyes were turned upwards
and inwards, the pupils dilated and inactive ; the face and extremities
were cold, the body somewhat warmer ; there was no pulse at the wrist,
* VicrUljahrsschr, fur ger. Med.^ 187G.
§ iSo, 181.]
CELOBOFOBM.
15s
the carotids beat feebly ; tbe breathing was deep and rattling, and after
five or six iiifipirations ceased. By the aid of artificial respiration, etc,
sbe recovered in an hour.
A still krger doac has been recovered from in the caee of a young
iiiatij aged 23,^ who had swallowed no Ic^ than T5 grm^i. (2 '6 ossb»)
of chloroform J Ijiit yet, in a few hours, awoke from tbe stupor. He
complaitied of a burning pain iu tbe stomach ; on tbe followitig day he
Buffered from vomiting, and on the third day symptoniB of janudioe
appeared — a feature which has been several timca noticed aa an eflect
of chloroform.
On the other band, even small doses have been known to destroy
life. In a cmG related by Taylor, a boy, aged 4, ts wallowed 3-5 grms,
(I drm,) of chloroform and died in three hours, notwitbstaurling that
every ertbrt was used for bis recovery.
§ ISO. The smallest dose tbat has proved fatal to an adult is 15 grms.
{a little over 4 drms.).
From twenty-two cases in which the quantity taken hiid been ascer*
tained with aome degree of accnracy, Fiilck draws the following con-
oluBions : — In eight of tbe ca^es the dose was between 4 and 30 grms*,
and one dcatli resulted from 15 grms* As for the other fourteen
persons, the 4 uses varied from 35 to 380 grms,, and eight of these
patients died — two after 40* two after 45, one after 60, 90, 120, and
180 grms, respectively, Hence, under conditions favouring the action
of the poison, 15 grms. (4%3 drms.) may be fatal to an adults wlille doses
of 40 grms, (ITS drros,) and upwards will almost certainly kill.
§ 181. Symptoms. — The symptoms can he well gathered from the
eas^ quoted. They commence shortly after the taking of the poison ;
and, indeed} the local action of the liquid immediately causes first a
burning sensation, followed by numbness.
Often after a few minnt««, precisely as when the vapour is adminm-
tered, a peculiar, excited condition supervenes, accompanied, it may be,
by delirium. The next stage is narcosis^ and the patietit lies with pale
face and livid lips, ytc, as described at p. 154 ; the end of tbe scene is
often preceded by convnlsions. Sometimes, however, consciousness
returns, and the irritation of the mucous membranes of tbe gastro-
intestinal canal is shown by bloody vomiting and bloody stools, with
coneiderable pain and general suffering. In tbis way, a person may
linger several days after the ingestion of the poison. In a ease observed
by Fomeroy, the fatal malady was prolonged for eight days. Among
those who recover, a common sequela^ i\^ before mentioned, is jaundice.
A third form of symptoms has been occasional ly observed, viz, :—
The person awakes from the coma, the breathing and pulse become
* MrU, M4d. Itnifit.. 1879.
IS6 POISONS: THEIR EFFECTS AND DETECTION. [§ 1 82, 1 83.
again natural, and all danger seems to have passed, when suddenly,
after a longer or shorter time, without warning, a state of general
depression and collapse supervenes, and death occurs.
§ 182. Post-mortem Appearances. — The post-mortem appearances
from a fatal dose of liquid chloroform mainly resolve themselves into
redness of the mucous membrane of the stomach, though occasionally,
as in Pomeroy's case, there may be an ulceration. In a case recorded
by Hoffman,* a woman, aged 30, drank 35 to 40 grms. of chloroform
and died within the hour. Almost the whole of the chloroform taken
was found in the stomach, as a heavy fluid, coloured green, through the
bile. The epithelium of the pharynx, epiglottis, and gullet was of a
dirty colour, partly detached, whitened, softened, and easily stripped off.
The mucous membrane of the stomach was much altered in colour and
consistence, and, with the duodenum, was covered with a tenacious grey
slime. There was no ecchymosis.
2. THE VAPOUR OF CHLOROFORM.
§ 183. Statistics. — Accidents occur far more frequently in the use
of chloroform vapour for anaesthetic purposes than in the use of the
liquid.
Most of the cases of death through chloroform vapour are those
caused accidentally in surgical and medical practice. A smaller
number are suicidal, while for criminal purposes its use is extremely
infrequent.
The percentage of deaths caused by chloroform administered during
operations is unaccountably different in different yeai-s, times, and places.
The diversity of opinion on the subject is partly (though not entirely)
explicable^ by the degrees of purity in the anaesthetic administered, the
different modes of administration, the varying lengths of time of the
ansBsthesia, and the varying severity of the operations.
During the Crimean war, according to Baudens and Quesnoy,
30,000 operations were done under chloroform, but only one death
occurred attributable to the anaesthetic. Sansomf puts the average
mortality at '75 per 10,000, Nussbaum at r3, Richardson at 2 '8, J
Morgan § at 3*4. In the American war of secession, in 11,000
operations, there were 7 deaths — that is, 6*3 per 10,000, the highest
number on a large scale which appears to be on record. In the ten
years ending 1903, 830 deaths are attributed to chloroform in Eng-
land and Wales — viz., 520 males, 292 females, from use as a general
* Lehrlmch der ger. Medicin, 2te Aufl.
t Chloroform: Us Action^ etc, London, 1865.
t Med. Times and OazcUe, 1870. § Med, See, of Firffinia, 1872.
§ iH. rSs ]
CHLOROFORM.
TS7
anEestbetic ; 17 (9 mftles, 8 femalofi) from suicide ; and a solitary case of
murder*
§ 184. Suicidal and Griimiial Foiaomng by GblorofoniL^ — Suicidal
poisoning by chloroform will generally be indicated by the surrounding
circuuiatances ; and in no case hitherto reported haii there been any
difficulty or obscurity as to whether the narcosis was self-induced or
not. An iuterestitig case is related by Scbaueostein,^ in which a
physician resolved to commit suicide by chloroform, a commencing
amaurosis having preyed upon his mind, and hia choice having been
determined by witnessing an accidental death by this agent. He
accordingly plugged hiu nostrila, fitted on to the face an appropriate
mask, and fai^tened it by strips of adhesive plaster. In such an
instance, there could be no doubt of the suicidal intent, and the
question of accident would be entirely out of the (piestion,
A dentist tu Potsdam, f in a state of great mental depression from
embarrassed circumstances, killed bis wife, himself, and two children by
chloroform. Such crimes are fortunately very rare.
There is a vulgar idea that it is possible, by holding a cloth saturated
with chloroform to the mouth of a e lee phi g person (or one, indeed, per-
fee fcly awake), to produce 8ii^We?i inaensibility ; but such an occurrence
I i» against all experimental and clinical evidence. It is true that a
nervous person mighty under such circumstanceSi faint and become
insensible by mere nervous shook; but a true sudden narcoeis is
impossible.
Dolheau has made some interesting experiments in order to ascer-
tain whether, under any circumstances, a sleeping person might be
aniesthoti^ed. The main result appears to answer the question in the
afhrmative, at least with certain persons; hut even with thef^e, it can
only be done by uwiug the greatest skill and care, first allowing the
sleeper to breathe very dilute chloroform vapour, and then griulually
, e]£hibitiug stronger doses, and tnklng the cloth or inhaler away on the
; slightest symptom of approaching wakefulness. In 75 per cent, of the
a, however, the individuals awoke almost immediately on being
exposed to the vapour. This cautiotis and scientific narcosis, then, Is
not likely to be used by the criminal class, or, if used, to bo successful.
§185, Physiological Hffects* ^Chloroform is a protoplasmic poison.
.Aooordiiig to Jumelle, plants can even be narcotise^l, ceasing to
■ftasimilate and no longer being sensitive to the stimulus of tight.
Isolated animal cells, like leucocytes, lose through chloroform vapour
their power of spontaneous movement^ and many bacteria ceaae to
multiply if in contact with chloroform water. According to Binx,
* Mii**chka, HctJiMit^h (ier firrirhth>h. Mtdiein, p. ?87. Tiibingen^ 18fl2.
t CftBper, Httmibuch d^ (feK Mai,
158 POISONS: THEIR EFPKCTS AND DETECTION. [§ 1 86.
chloroform narcosis in man is to be explained through its producing a
weak coagulation of the cerebral ganglion cells. As already mentioned,
chloroform has an affinity for the red blood corpuscles. Chloroform
stimulates the peripheral ends of the nerves of sensation, so that it
causes irritation of the skin or mucous membranes when locally applied.
Flourens considers that chloroform first afiects the cerebrum, then the
cerebellum, and finally the spinal cord ; the action is at first stimulating,
afterwards paralysing. Most anaesthetics diminish equally the ex-
citability of the grey and the white nervous substance of the brain,
and this is the case with chloroform, ether, and morphine ; but
apparently this is not the case with chloral hydrate, which only
diminishes the conductivity of the cortical substance of the brain, and
leaves the grey substance intact. Corresponding to the cerebral para-
lysis, the blood-pressure sinks, and the heart beats slower and weaker.*
The Hyderabad Commission made 735 researches on dogs and monkeys,
and found that in fatal narcosis, so far as these animals are concerned,
the respiration ceased before the heart, and this may be considered the
normal mode of death ; but it is probably going too far to say that it is
the exclusive form of death in man, for there have been published cases
in which the heart failed first.
§ 186. Symptoms. — There is but little outward difference between
man and animals in regard to the symptoms caused by breathing
chloroform ; in the former we have the advantage that the sensations
preceding narcosis can be described by the individual.
The acti(m of chloroform is usually divided into three more or less
distinct stages. In the^r«^ there is a "drunken" condition, changes
in the sense of smell and taste, and it may be hallucinations of vision
and hearing ; there are also often curious creeping sensations about the
skin, and sometimes excessive muscular action, causing violent struggles.
Epileptiform convulsions are seen occasionally, and delirium is almost
always present. The face during this stage is generally flushed,
covered with perspiration, and the pupils contracted. The first stage
may last from one minute to several, and passes into the second stotje,
or that of depression. Spontaneous movements cease, sensibility to all
external stimuli vanishes, the patient falls into a deep sleep, the con-
sciousness is entirely lost, and reflex movements are more and more
annihilated. The temperature is less than normal, the respirations are
slow, and the pulse is full and slow. The pupils in this stage are
usually dilated, all the muscles are relaxed, and the limbs can be bent
about in any direction. If now the inhalation of chloroform is inter-
mitted, the patient wakes within a period which is usually from twenty
to forty minutes, but may be several hours, after the last inhalation.
• KoherVs I^hrbtu^h der Intoxicatione7u
1 187, I8SJ
CHLOROFORM,
159
The ihird stoife is that of panilysis ; the pulse becomes irregular, the
reapirations superficial, there is a cyanotic colouring of the lips and skiu,
while the pupils become widely dilated. Death follows qnickly through
pamlysis of the re&pimtory ceutrcj the re^pimtioua first ceasing, then
the pulse ; iu a few caaoSf the heart ceases first to beat,
According to Sanaom's factft,* in 1 00 cfises of death bj chloroform
44*6 per cent, occurred before the full narcosis had been attained, that
is la the first atage^ 34*7 during the second stage, and 20^6 shortly a ft-er.
So, also, Kappeler has recorded that in 101 cases of death from chloro-
form, 47'7 per cent, occurred before the full eftiict, and 52'2 during the
full eifecL This con firms the dictum of Billrothi that in all stages of
anaesthesia by chloroform, death may occtm The quanfitt/ of chlorcjfonm,
which, when inhalefi in a given time, will prodnoe death, is unknown;
for all depends upon the greater or less admixture of air, and [probably
on other conditions. It has been laid down, that the inhalation of
chloroform should be so managed as to ensure that the air breathed shall
never contain more than 3*9 per cent, of chloroform. Fifteen drops have
caused death ; but Taylor, on the other hand, records a case of tetanus,
treated at Guy's Hospital, in which no less a quantity than 700 grms.
(22 '5 ozs,) was inhaled in twenty-four hours. Frequent breathing of
chloroform in no way renders the individual safe fi*om fatal accident,
A lady t having repeatedly taken chloroform, was antesthetised by the
same sgent merely for the purpose of having a tooth extracted. A lion t
G grma. (1*5 dmi,) were poured on a cloth, and after nine to ten inspira-
tions, dangerous symptoms began— rattling breathing and convulsive
movements — and, despite all remedies, she died.
g 187. Chronic chloroform poisoning is not unknown. It leads to
various ailments, and seems to have been in one or two instances the
cause of insanity.
Buchner records the ease of an opium-eater, who afterwards tcxik to
chloroform ; he suffered from periodic mania. In a remarkable ease
related by Meric, the patient^ who had also tirst been a morphine- eater,
took 350 grms* of chloroform in five days l>y inhalation ; as often as he
woke he would chloroform himself again to sleep. In this case^ there
was also mental disturbance, and instances in which chlorofonm produced
marked mental al>erration are recorded by Btibm J and by Vigla.g
^ 188, Post-mortem Appearances.— The lemons found on aeetion
are neither peculiar to, nor characteristic of, chloroform poisoning. It
has been noted that bubbles of gas are, from time to time^ to be
observed after death in the blood of those poisoned by chloroform, but
it is doubtful whether the bubbles are not merely those to be found in
' Op, mi.
+ Efiin. Mtii, JmrfL, 1856,
l6o POISONS: THEIR EFFECTS AND DETECTION. [§ 1 89.
any other corpse — in 189 cases, only eighteen times were these gas-
bubbles observed,* so that, even if they are characteristic, the chances
in a given case that they will not be seen are greater than the reverse.
The smell of chloroform may be present, but has been noticed very
seldom.
§ 189. The detection and estimation of chloroform from organic
substances is not difficult, its low boiling-point causing it to distil readily.
Accordingly (whatever may be the ultimate modifications, as suggested
by different experimenters), the first step is to bring the substances,
unless fluid, into a pulp with water, and submit this pulp to distillation
by the heat of a water-bath. If the liquid operated upon possesses no
particular odour, the chloroform may in this way be recognised in the
distillate, which, if necessary, may be redistilled in the same manner,
so as to concentrate the volatile matters in a small compass.
There are four chief tests for the identification of chloroform : —
(1) The final distillate is tested with a little aniline, and an alcoholic
solution of soda or potash lye; either immediately, or upon gently
warming the liquid, there is a peculiar and penetrating odour of phenyl-
carbylamine, CgH^NC ; it is produced by the following reaction : —
CHClg + 3K0H + CoHQNH2->CeH5NC + 3KC1 + 3H2O.
Chloral, trichloracetic acid, bromoform and iodoform also give the same
reaction ; on the other hand, ethylidene chloride does not yield under
these circumstances any carbylamine (isonitrile).
(2) Chloroform reduces Fehling's alkaline copper solution, when
applied to a distillate, thus excluding a host of more fixed bodies which
have the same reaction; it is a very excellent test, and may be made
quantitative. The reaction is as follows : —
CHCI3 + 5KH0 + 2CuO = CU2O + KgCOj + 3KC1 + SBfi ;
thus, every 100 parts of cuprous oxide equals 83*75 of chloroform.
(3) The fluid to be tested (which, if acid, should be neutralised) is
distilled in a slow current of hydrogen, and the vapour conducted
through a short bit of red-hot combustion tube containing platinum
gauze. Under these circumstances, the chloroform is decomposed and
hydrochloric acid formed; hence, the issuing vapour has an acid re-
action to test paper, and if led into a solution of silver nitrate, gives the
usual precipitate of argentic chloride. Every 100 parts of silver chloride
equal 27'758 of chloroform.
(4) The fluid is mixed with a little thymol and potash ; if chloro-
form be present, a reddish- violet colour is developed, becoming more
distinct on the application of heat.f
* SchauenBtein (op. cit, ).
t S. Vidaliin Deutxh-Amerikan, ApotK-Zeitung^ vol. iij., Aug. 15, 1882.
1 190, I9I']
CHLORAL,
161
§ 100. For the quantitatiYe estimation of chloroform the method
recomraended by Schraiedeherg * is, however^ the best. A combustion
tube of 24 to 26 cm. longj and 10 to 12 mm. in diameter, open at both
ends, 18 furnished at the one end with a plug of asbestos, while the
middle part^ to within 5-6 cm, of the other end, ia filled with pieceB of
caustic lime, from tiie iize of a lentil to that of half a pea. The lime
must be pure, and i^ uiade by heating a carlx^nate which has been pre-
cipitated from ealcic nitrate* The other end of the tube is closed by a
cork, carrying a silver tube, 16-18 cm, long, and 4 mm. thick* The
end containing the asbestos plug is fitted by a cork to a glass tube.
The combustion tube thus prepared is placed in the ordinary combustion
furnace ; the fiask containing the chloroform is adapted, and the dis-
tillation sluwly proceeded with* It is best to add a tube, bent at right
angles and going to the bottom of the flask, to draw air continuously
through the apparatus. During the whole process^ the tube containing
the lime is kept at a red heat* The chloroform is decomposed, and the
chlorine combines with the lime. The resulting calcic chloride, mixed
with much unchanged lime, is, at the end of the operation, cooled, dis-
solved in dilute nitric acid, and precipitated with silver nitrate* Any
silver chloride ia collected and weighed and calculated into chloroform* t
VL— ChloraL
§ 10L Chloral Hydrate (C^KCt^O, H^O) is made by mixing equivalent
quantities of anhydrous chloral | and water. The purest chloral is in
the form of small, granular^ sugar-like crystals. When leas pure, the
crystals are larger^ These melt into a clear fluid at from 48* to 49',
and the melted mass sol id ifiea again at 48*9^ Chloral boils at 97 '6*;
it i« not very soluble in cold chloroform, requiring four times its weight.
The only substance with which chloral hydrate may well be confused ia
chloral alcoholate (C^H^ClgOj), but chloral alcoholate melts at a lower
temperature (45°}j and hoik at a higher (llS'd'^); it is easily soluble
* Ucber dk quanlUiUi^ B^dimffmnQ da Chltmtfffrms im BhtU, In&iig. Dissert.,
Dorp&t, 1866.
t 3. Virkli li4fi niAde the ingenious ^ggeatian of developing liydrogen in tbe
u^Qal wa)% by mofttis of einc And sulphurio acid, in the liqaid Buiipoeod to coatain
chlomfonn, to ignite the hydrogen , &s io Matah'a test, when it bauea froiD the tube,
&Qd thou to hold In the tliime a clean copp«r wire. Sine« uny chloroform b burnt up
in the hydtogon Bame to hydroehlofio »cid« the chloride of copper immediately
volatilises nnd colours the flAme green.
t Anhydrotu cWornl (CjHClaO) is an oily hqnid, of apedfic gravity l'fi02 at 18" ;
it boils at ^1*T. It is obtain^ by the pTolouged action of chlorine on absolute
Alcohol.
II
1 62 POISONS: THEIR EFFECTS AND DETECTION. [§ 1 92, 1 93.
in cold chloroform, and inflames readily, whereas chloral scarcely
bums.
Chloral hydrate completely volatilises, and can be distilled in a
vacuum without change. If, however, boiled in air, it undergoes slow
decomposition, the first portions of the distillate being overhydrated, the
last underhydrated ; the boiling-point, therefore, undergoes a continuous
rise. The amount of hydration of a commercial sample is of practical
importance ; if too much water is present, the chloral deliquesces, espe-
cially in warm weather ; if too little, it may become acid, and in part
insoluble from the formation of metarchloral (C^HgClgOj). Chloral
hydrate, by the action of the volatile or fixed alkalies, is decomposed, an
alkaline formate and chloroform resulting thus —
CjHa30,H20 + NaH0->NaCH02 + H^O + CHCI3.
Trichlor-acetic acid is decomposed in a similar manner.
Statistics. — Chloral caused, during the ten years ending 1903, in
England and Wales, 96 deaths — viz., 82 (66 males, 16 females) acci-
dentally, and 14 (12 males, 2 females) from suicide.
§ 192. Detection. — It is, of course, obvious that after splitting up
chloral into chloroform, the latter can be detected by distillation and
applying the tests given at p. 160 and seq. Chloral hydrate is soluble
in one and a half times its weight of water; the solution should be
perfectly neutral to litmus. It is also soluble in ether, in alcohol, and
in carbon disulphide. It may be extracted from its solution by shaking
out with ether. There should be no cloudiness when a solution is tested
with silver nitrate in the cold ; if, however, to a boiling solution nitrate
of silver and a little ammonia are added, there is a mirror of reduced
silver.
§ 193. The assay of chloral hydrate in solutions is best effected by
distilling the solution with slaked lime; the distillate is received in
water contained in a graduated tube kept at a low temperature. The
chloroform sinks to the bottom, and is directly read off; the number of
c.c. multiplied by 2*064 equals the weight of the chloral hydrate
present.
Another method, accurate but only applicable to the fairly pure sub-
stance, is to dissolve I to 2 grms. in water, remove any free acid by
baric carbonate j and then treat the liquid thus purified by a known
volume of standard soda. The soda is now titrated back, using litmus
as an indicator ; each c.c. of normal alkali neutralised by the sample
corresponds to 0*1655 grm. of chloral hydrate. Small quantities . of
chloral hydrate may be conveniently recovered from complex liquids by
shaking them up with ether, and removing the ethereal layer. A con-
venient tube for this purpose suitable for either liquids which like ether
§ t94^]
CHLOBAL.
163
^^=^
float to the top, or like chloroform eink to the bottom, Ib repreaented in
the accompanying illustration. A is a mercury r^ervoir connected with
a graduated tube T ; a two-way 8to|M;ock S permita liquids to be drawn
in through the tliistle^head Funnel or expelled by the sido tube ; when
chloroform ia used it enii be removed through a lower two-way stopcock
(J, by the tube d. The ether may be allowed to evaporate spontaneously ;
but there ia in this way much I088 of chloral Tlte best method of
estimating minute quanti-
ties is to alkali. ^e the liquid,
and alowly distil the vapour f^ i
through a red-hot combus-
tion tube charged with pure
limo, as in the process de-
scribed at p, 16L A dilute
solution of chloral may also
he treated with a zitic-
copper couple ; the tiaacent
hydrogen bi-eaks the mole-
cule up, and the resulting
chloride may be titrated,
as in water analyi^es, by
silver nitrate and potassic g i h^T
chromate.
55 194. Effects Of
Chloral Hydrata on Ani-
malE. — Kxperiiuenta on
animals have taught irs all
that is known of the physio-
logical action of chloral.
It has been shown that the
drug influences very con-
siderably the circulation,
at first exciting the heart's
actionj and then paralysing the automatic centre. The heart, as in
animals poisoned by atropine, stops in diaatole, and the blood -pressure
sinks in proportion to the progreasive paralysia of the cardiac centre.
At the same time, the respiration is slowed and finally ceases, while
the heart continues to beat» The body temperature of the warm-
blooded animals is very remarkably depressed, according to Falok, even
to 7'6*. Vomiting has been rather frequently observed with dogs and
eats, even when the drug htia l>een takt'ii into the svstem by subcutnneous
injection,
The secretion of milk, according to Rtihrig, is also diminished, lieflex
l64 POISONS: THKIR KFFKCTS AND DETECTION. [§ I95, I96.
aotions through small doses are intensified ; through large, much
diminished. •025-'05 grm. (*4-*7 grain), injected subcutaneously into
frogs, causes a slowing of the respiration, a diminution of reflex excita-
bility, and lastly, its complete cessation; this condition lasts several
hours ; at length the animal returns to its normal state. If the dose is
raised to '1 grm. (1*5 grain) after the cessation of reflex movements, the
heart is paralysed — a paralysis not due to any central action of the
vagus, but to a direct action on the cardiac ganglia. Rabbits of the
ordinary weight of 2 kilos, are fully narcotised by the subcutaneous
injection of 1 grm. ; the sleep is very profound, and lasts several hours ;
the animal wakes up spontaneously, and is apparently none the worse.
If 2 grms. are administered, the narcotic effects, rapidly developed, are
much prolonged. There is a i*emarkable diminution of temperature, and
the animal dies, the respiration ceasing without convulsion or other sign.
Moderate-sized dogs require 6 grms. for a full narcosis, and the symptoms
are similar ; they also wake after many hours, in apparent good health.*
§ 195. Liebreich considered that the action of chloral was due to
its being broken up by the alkali of the blood, and the system being thus
brought into a state precisely similar to its condition when anaesthetised
by chloroform vapour. This view has, however, been proved to be
erroneous. Chloral hydrate can, it is true, be decomposed in some degree
by the blood at 40° ; but the action must be prolonged for several hours.
A 1 per cent, solution of alkali does not decompose chloral at a blood-heat
in the time within which chloral acts in the body ; and since narcotic
effects are commonly observed when, in the fatty group, hydrogen has
been displaced by chlorine, it is more probable that chloral hydrate is
absorbed and circulates in the blood as such, and is not broken up into
chloroform and an alkaline formate.
§ 196. Effects of Ohloral Hydrate on Man.— Since the year 1869,
in which chloral was Brst introduced to medicine, it has been the cause
of a number of accidental and other cases of poisoning. In nearly all
the cases the poison was taken by the mouth, but in one instance the
patient died in three hours, after having injected into the rectum 5*86
grms. of chloral hydrate. There is also on record a case in which, for
the purpose of producing surgical ansesthesia, 6 grms. of chloral were
injected into the veins ; the man died in as many minutes.!
* C. Ph. Falck has divided the Bymptoms into — (1) preliminary hypnotic ; (2) an
adynamic state ; and (8) a comatose condition.
t This dangerous practice was introduced by M. Ore. In a case of traumatic
tetanus, in which M. Ore injected into the veins 9 grms. of chloral in 10 grms. of
water, there was profound insensibility, lasting eleven hours, during which time a
painful operation on the thumb was performed. The next day 10 grms. were in-
jected, when the insensibility lasted eight hours ; and 9 grms. were injected on each
of the two following days. The man recovered. In another case, Ore anaesthetised
1 197.]
CHLORAL.
165
% I dl. Fatal Bose. — It b iD^poasibla to atate with any exactiieBs the
preoise quantity of chloral whi^h may eauee death. Children bear It
better^ in proportionj thau adulta, wliile old persona (eapeoially tliose
with weak hearts, and those inclined to apoplexy) are likely to be strongly
affected by very small doses. A dose of *19 grnu (3 gmins) has been
fatal to a child a year old in ten hours. On the other hand, according
to Bouchat^s observations gu lOjOOO children^ he eonsidei'S that the full
therapt^utic etiect of chloral can be obtained safely with them in the
following ratio :^ —
Ghildi^ij at' i to 3 yeAts, dmG 1 to 1'5 gi'ia. (15 '4 to 23 i gmiuu)
3 ,, 5 .. n 2 „ 3 „ (30-8 „ 46'3 ,, )
B,, 7 M » 3„ 4 „ (4e^3 ,, 617 ,, )
—these quaDtitiea being diseolved in 100 L'.c, of wAtor.
These doses are certainly too high, and it would be dangerous to take
them a!^ a guide, ninco death has occurred in a child, aged 5, from a dose
of 3 grms, (46*3 grainii)* Medical men in Enghnid consider 2(_» grains a
very full dose for a child of 4 years old, and 50 for an adnlt, while a
case is recorded in wtiieh a dose of 1*9 grm, (30 graiufi) proved fatal in
thirty-five hours to a young lady aged 20. On the other hand^ we iind
a case * in which, to a patient *?* uttering from epileptic mania, a dose of
31*1 grms* {I'l oz,) of chloral hydrate was administered ; she sank into a
deep sleep in five minutes. Subcutaneous injections of itrychnine were
appliedj and after sleeping for forty-eight hoiirs, there was recovery. On
the third day a vivid scarlatinal rash appeiired, followed by desquamation.
The examples quoted — the fatal dose of 19 grm*, and recovery from 31
grms. — are the two ejttremes for adults. From other e^iises, it appears
tolerably plain that most peojile would recover, especially with appropriate
treatment, from a single dose under 8 grms., but anything above that
(pjantity taken at one time would be very dangerous, and doses of 10
grms. and above, ahnost always fatal. If, however, K ynus, were taken in
divided doses during the twenty-four hours, it could (according to Sir
U. W. Richardson) be done with safety. The time fit>m the taking of the
poison till death varies considerably, and is ui part dependent on the doso.
In seven cases of lethal poisoning, three persona who took the small
doses of V2b, 2*5, and 1'95 grms. respectively, lived from eight to ten
hours ; two, taking 4 and 5 grms. respectively, died very shortly after
the administration of the chloral. In a sixth case, related by Brown, in
iijmi«?disiti'ly a fifttioiit by |ilrtngijig the sul)cutiitje<mfl m^ndlo of his syring«j into tUe
TAihiil vein, und injcctid 10 giin^, uf'chloml liydr^ta with SO of water. The patient
beoftme insenaiblt' Hpforf^ the wht>lo quantity wia injected with ** uru- tmintMiU^ rap-
pelkmimlU du cadnvre/* Ou fi Dishing the oi>eimtioii, the [iati«Dt waji nitised imme*
diately by tho ^ppltcittiori uf an eleolriQ earreut, on^ pole on the left side of the neck,
the othiT oti the epij^trinm, Joum^ d€ Fharm* d tk OhiffkiCf t* 10| p. SI 4.
* Chicago Mttiicat Mmfieii\ IB^2.
1 66 POISONS: THEIR KFFKCTS AND DETECTION. [§ I98, I99.
which 3*12 grms. had been taken, the patient lived an hour; and in
another, after a dose of 5 grms., recorded by Jolly, death took place
within a quarter of an hour,
§ 198. Symptoms. — With moderate doses there are practically no
symptoms, save a drowsiness coming on imperceptibly, and followed by
heavy sleep. With doses up to 2 grms. (30*8 grains), the hypnotic state
is perfectly under the command of the will, and if the person chooses to
walk about or engage in any occupation, he can ward off sleep ; but with
those doses which lead to danger, the narcosis is completely uncontrol-
lable, the appearance of the sleeper is often strikingly like that of a
drunken person. There is great diminution of temperature conunoncing
in from five to twenty minutes after taking the dose — occasionally sleep
is preceded by a delirious state. During the deep slumber the face is
much flushed, and in a few cases the sleep passes directly into death
without any marked change. In others, symptoms of collapse appear,
and the patient sinks through exhaustion.
With some persons doses, which, in themselves, are insufficient to
cause death, yet have a peculiar effect on the mental faculties. A case
of great medico-legal interest is described by the patient himself. Dr.
Manjot.* He took in three doses, hourly, 12 grms. of chloral hydrate.
After the first dose the pain, for which he had recourse to chloral,
vanished ; but Manjot, although he had all the appearance of being per-
fectly conscious, yet had not the slightest knowledge of what he was
doing or speaking. He took the other two doses, and sank into a deep
sleep which lasted twelve hours. He then awoke and answered ques-
tions with difficulty, but could not move ; he lay for the next twelve
hours in a half slumber, and the following night slept soundly — to wake
up recovered.
§ 199. The treatment of acute chloral poisoning which has been most
successful is that by strychnine injections, and the application of
warmth to counteract the loss of temperature which is so constant a
phenomenon. As an illustration of the treatment by strychnine, an
interesting case recorded by Levinstein t naay be quoted.
A man, 35 years old, took at one dose, for the purpose of suicide,
24 grms. of chloral hydrate. In half an hour afterwards he was
found in a deep sleep, with flushed face, swollen veins, and a pulse 160
in the minute. After a further half hour, the congestion of the head
was still more striking ; the temperature was 39*5' ; the pulse hard and
bounding 92 ; the breathing laboured, at times intermittent.
Artificial respiration was at once commenced, but, in spite of this, in
about another half-hour the face became deadly pale, the temperature
sank to 32*9**. The pupils contracted and the pulse was scarcely to be
* Oca. des Hop,, 1876. t Fiertdjahrsachr, f. gcr, Med,, Bd. xx., 1874.
I 2oa]
CHLORAL.
167
felt; 3 Dig I'm s. (04 gram) of strycLmine were now injected suVjcutane*
ousiy; this caused tetaiiiu convukions in the upper part of the body
and trismus. The heart'ti aution again became soniewbat Btronger, the
temperature rose to 33'^'^ and the pupils dilated ; but i^oon foUowed,
again, depression of the heart's action^ and the respiration could only be
kept going by faradisation » Two mgrnis. ('03 grain) of strychnine
were onoe more injected, and the heart's action improved. During the
succeeding six hours the respiration bad to be aaaiested by faradisation.
The temperature gradually rose to 36*5*' ; ten hours after taking the
dose the patient lay in a deep sleep, breathing spontaneously and
reacting to external atimnli with a temperature of 38 ■5". Eighteen
hours from the conimeucementj the respiration again became irregular,
and the galvanic current was anew applied* The last application
aroused the sleeper, be took some milk and again slept ; after twenty-
seven hours be could be awakened by calling, etc., but had not full con-
aciousness ; he again took some milk and sank to sleep. It was not
until thirty-two hours had elapsed from the ingestion of the poison that
be awoke tjpontaneously ; there were no a Iter- effects.
g 200. Chronic Poisomng by Chloral Hydrate,— An enormous num*
ber of people Viabittially take chloral hydrate. The history of the habit
is usually that some physician ha;:^ given tbem a chloral prescription for
neuralgia, for losa of sleep, or other cause, and hnding that they can
conjure sleep, oblivion, and less (it may be) of suffering whenever they
choose, they go on repeating it from day to day until it becomes a
necessity of their existence, A dangerous fiicility to chloral-drinking h
the existence of patent medicines, advertised as sleep- producers, and
containing chloral as the acttve ingredient. A lady^ aged 35, died in
1876, at Exeter, from an overdose of " Hunter's solution of chloral, or
sedative draught and sleep producer,'' Its strength was stated at the
iuquesst to be :25 grains to the drachm (41*6 per cent.),*
The evil results of this chloral-drinking are especially to be looked
for in the mental faculties, and the aUenists have had sinee 1869 a new
insanity-prod nchig factor. In the asylums may usually be found
several cases of njelanchoUa and mania referred rightly (or wrongly) to
cbloral-drmking* Symptoms other than cerebral are chilliness of the
body, inclination to fainthig, clonic convulsions, luid a want of co-ordina-
tion of the nmacles of the lower extremities. In a case recorded by
Husband,! a Uidy, after twelve days' treatment by chloml hydrate, in
doBoa of from 1 to 2 gnus, (15-4 to 30 'S grains), tiufl:ered from a scar-
latina4ike rae^b, which was followed by desquamation. Among the
insane, it has also been noticed that its nso has been followed by nettle-
raah and petechite (Keimei and others).
l68 POISONS: THKIR EFFECTS AND DETECTION. [§ 20I, 202.
§ 201. Excretion of Ohloral. — Chloral hydrate is separated in the
urine partly as urochloral acid (CgH^^ClsO^). Butylchloral is separated
as urobutylchloral acid (CiQHjjClaOy). Urochloral acid is crystalline,
soluble in water, in alcohol, and in ether, reduces copper from Fehling's
solution, and rotates a ray of polarised light to the left. Urochloral
acid, on boiling with either dilute sulphuric or hydrochloric acid, splits
up into trichlorethyl alcohol and glycuronic acid —
CgHiiCljO^ + H2O -> C2H3CI3O + CeHjoO^.
Trichloralcohol is an oily fluid (boiling-point 150'-152**); it yields by
oxidation trichloracetic acid.
Urobutylchloral acid gives, on treatment with mineral acids, trichlor-
butyl alcohol and glycuronic acid.
To separate urochloral acid from the urine the following process has
been found successful : —
The urine is evaporated to a syrup at the heat of the water-bath,
and then strongly acidulated with sulphuric acid and repeatedly shaken
out in a separating tube with a mixture of 3 vols, of ether and 1 vol. of
alcohol. The ether-alcohol is separated and distilled off, the acid resi-
due is neutralised with KHO, or potassic carbonate, and evaporated ;
the dry mass is then taken up with 90 per cent, alcohol, the filtrate
precipitated with ether, and the precipitate washed with ether and
absolute alcohol.
Next the precipitate is boiled with absolute alcohol and filtered hot.
On cooling, the potassium salt of urochloral acid separates out in tufts
of silky needles. The crystals are dried over sulphuric acid and again
washed several times with absolute, alcohol and ether to remove
impurities.
To obtain the free acid, the potassium salt is dissolved in a little
water and acidulated with hydrochloric acid ; the liquid is then shaken
out in a separating tube, with a mixture of 8 vols, of ether and 1 of
alcohol. The ether-alcohol is distilled off, the residue treated with
moist silver oxide imtil no farther separation of silver chloride occurs,
the silver chloride is separated by filtration, the soluble silver salt decom-
posed by SHg, and the filtrate carefully evaporated to a syrup ; after a
few hours, the acid crystallises in stars of needles.
Urobutylchloral acid can be obtained in quite a similar way.^
§ 202. Separation of Ohloral from Organic Matters.— ^It will be
most convenient to place the organic fluid or pulped-up solid, mixed
with water, in a retort, to acidify with tartaric acid, and to distil.
Chloral hydrate distils over from a liquid acidified with tartaric
* V. Mering u. Musculus, Ber,f viii. 662 ; v. Mering, ibid., xv, 1019 ; E. Kulz,
Ber., XV. 1538.
§ 202.]
CHtXtRAL.
169
acid ; to obtaiu tbe whole oi thi^ uEilomi requires distillation in a
vacuum almost to dryness.
The distillation will, uule^ there is alBo mme partly decomposed
chloral, uot smell of chloroform, and yet give chloroform reactions.
To identify it, to the distillate should he added a little burnt
magnesia, and the distillate thus tresited boiled for half an hour in a
Haak connected with an inverted condenser ] in thin way the chloral
hydmte is changed into chloroform * and magnesium formate —
2CCl3CH(OH)2 + MgO -* 2CHCla + (HCOO)aMg+ H.A
The fluid m»y now be tested for formic acid : it will give a blii^jk pre-
cipitate with solution of silver nitnite^ —
(HC00)2Mg 4- iAgNOg = 4Ag + Mg{N03)3 + 2CO2 + 3HN0^.
It will give a white precipitate of calomel wh^n treated with mercuric
chloride solution —
(HCOO)aig + iHgCl^ - 2Hg^Cl2 + MgCl, + 211U + 2CU2.
Chloml (or chloroform), when boiled with resorcinol and the liquid
made atrongly alkaline with NaHO, gives a red colour, which disappears
on acidifying and is regtored by alkalies. If, on the other hand, there
is an excess of resorcinol and only a very small quantity of HaUO used,
the product shows a yellowish -green tluoreseence; ^ of a milligramme
of chloral hydrate gives this reaction distinctly when boiled with 50
mgrms, of resorcinol and 5 drops of a normal solution of sodium
hydrate.t
Dr* Frank Ogston J has recommended sulphide of ammouinm to be
added to any liquid as a test for chloraU The contents of the stomach
are Eltered or submitted to dialysis^ and the te&l applied directi If
chloral ie present, there is firat an or^uige yellow colour ; on standing,
the fluid becomes more and more brown^ then troubled, an amor[thous
precipitate falls to the bottom, and a peculiar odour is developed.
With 10 mgrms* of uhloiul in 1 c.c. of water, there is an evident pre-
cipitate, and the odour can readily be perceived ; with 1 mgrm, dissolved
in 1 CO, of water, there is an orange-yellow colour^ and also the odour,
but no precipitate ; with '1 nigrm, in 1 c.c. of water, there is a weak,
pale, straw-yellow colour, which can S(*Arcely be called characteristic.
The only substance giving in neutral solutions the same reactions is
• Kiin>eubergor(j?<rcA. Pharjn,* ooxxxviii,, l&OO) attttes th»t when oKlorofonii ia
diiitilled with an lUkali mmp r>l it is dn^Pt^m^ioiscMl, giving carliun monmide &nd xi
ehlorlde. The c^rboii monc»3cide nmy be estimated by mu^na gf ^HillMlitim nbloridr*
One part of metallLe (HilladiiuQ = 112'S [H^rts of GhloroftjiTD,
t C» SchwftTX, Pknritt, £eif,f xxxiiu 410,
t VitrteljahrfAckri/if, g^khU. Jlmfit^n, 187ft| Ikl. xxx. HfL 1» 8. 'M^,
I70 POISONS: THKIR EFFECTS AND DETECTION. [§ 2O3-207.
autimony ; but, on the addition of a few drops of acid, the antimony
falls as an orange-yellow precipitate, while, if chloral alone is present,
there is a light white precipitate of sulphur.
VIL— Minor AnsBsthetics and Narcotics.
§ 203. When chlorine acts upon marsh-gas, the hydrogen can be displaced atom
by atom ; and from the original methane (CH4) can be successively obtained chloro-
methane or methyl chloride (CH3CI), dichloromethane, or methene dichloride,
methylene dichloride (GH2CI3), trichloromethane, or chloroform (CHGls), already
described, and carbon tetrachloride (CCI4). All these are, more or less, capable of
producing anaesthesia ; but none of them, save chloroform, are of any toxicological
importance.
Metheue dichloride, recommended by Sir B. W. Richardson as an anaesthetic, has
come somewhat into use. It is a colourless, very volatile liquid, of specitic gravity
1*360, and boiling at 41^ It burns with a smoky flame, and dissolves iodine with a
brown colour.
§ 204. Pentane (CjHja). — There are three isomers of pentanc ; that which is
used as an ansesthetie is normal (lentane, CHg - CH.^ - CUj - CHg - CH3 ; its boiling •
imut is 37-38.'* It is one of the constituents of petroleum ether.
Under the name of ' ' Pental " it is used in certain hospitals extensively, for
instance, at the Kaiser Friederich's Children's Hospital, Berlin.* It is stated to
have no action on the heart.
One death t has been recorded from its use : — A lad, aged 14, was put under
|)entul for the purpose of having two molars painlessly extracted. He was only a
minute or two insensible, and 4-5 grms. of pental was the quantity stated to have
been inhaled. The boy s|)at out after the operation, then suddenly fainted and died.
The post-mortem showed odenia of the lungs ; the right side of the heart was empty.
The organs of the body smelted strongly of pental.
§ 205. Aldehyde (Acetaldehyde), C2H4O or CH. - C^ , a fluid obtained by the
^H
carefol oxidation of alcohol (boiling-point, 20*8''), is in large doses toxic ; in smaller,
it acts as a narcotic.
Metaldehyde {(li^lfi>2)2, obtained by treating acetaldehyde at a low temperature
with hydrochloric acid. It occurs in the form of ])risms, which sublime at about
112**; it is also ]K)isonous.
§ 206. Paraldehyde (CnHiaO,) is a colourless fluid, boiling at 124** ; specific gravity
'998 at 15^ By the action of cold it may be obtained in crystals, the melting-
point of which is 10 'S". It is soluble in eight i>arts of water at 13** ; in warm water
it is less soluble ; hence, on wanning a solution, it becomes turbid. Paraldehyde is
said to }>aralyse the anterior cornua of spinal cord. In two recorded cases $ of
poisoning there was unconsciousness, |)erspiration, shallow breathing, and inter-
mittent pulse.
Treatment with amyl nitrite and strychnine has proved eflective.
§207. Somoform.§— This is a mixture of ethyl chloride, 65 |)arts; methyl chloride,
* Zeit./, Kindei'heilk,, Bd. iii.-iv., 1893.
t Dr. Bremme, Vierteljahrsxhr, f, geridUliche Mediein, Bd. v., 1893.
X Lancet, Sei)t 23, 1900, 875 ; and Sept. 6, 1902.
§ Froc. Physiol, iiioc,, xxv., 1908.
§ 208.]
MINOR ANJISTHRTICB AND NABCOTIC&
I7T
SO portH i «nd clbyl bromide, 5 ports. In toxic dosus it vi^ueca death by tgttic
itopiHige ordiaphrugni while the limit utill Ik^jiIvH strongly.
§ 20B. &iilphon6B — SuIphonAl, Trioiml, TetronaL — Of these, ^ul^bouivl, trioiial»
and tetroiiiii avu in coiuniBieii, iktid much in iise as iiarcotic& The sulphon^s aro
PQigarded 1^ 11 re than e^ in wldoh the hydrogen atoms ars i^eplivced by ulkyl und
dkyl sulphojiie nuik'U's ; thuji sul phonal ia a dimethyl snl phone diethyl etliaae,
11141. I'-^S*
\(
Tirional, Tu.p. 7&°i ni a mouomethyL- ethyl sulphone-di -ethyl ethttue,
CH, SOaCjHa
\/
y \
while tetronal, tn.p. 85", ifl ii diethyl huI phone diethyl ethane,
Ikuman and Ktwit * haTe shown that there i^ a relation between narootit! power
and thii Tiuinl>et of ethyl groups, dimethyl sulplione* dimethyl ethane being wiihont
a«^d'>n« while the c«n*esiKJndijjg elhyl (tetional) comptjniid exertrhsea the strouge^it
naiTcotie action ; if a Bulphonftl methyl group 13 replaced by phenyl Cffli no nurcotic
aetioQ ia prodncsed, but if both methyS grou|jfi are replaced as in diphimyl diethyl
siiI[^CKiie methane^ C,}HsC(302QjHa)uCf,H,^, an in tense poiaon ia produDed, the fatal
dotie for cata being 0^& gnn« (ler kito.
The ottlmary i^leeping doae of ^nlpbonal for adultB ib from 10 to 'IQ giaina
(*€5 grm. - 1'3 gnu.) *, aingle oooaaional doses of this magnitude do not mxm to
apprtectably atTect the h^lth, hut if taken day after day Berioue ohanges may be
produced. A woman t aged 53, took for acme time 15 grains (1 grm. ) of aul[ihonab
At last there was marked niunta! eonfuaion, difficulty of apeech, and a jieonliar
sighing dyapncBa. The urine was tinged a de«p pink colour, stifTnesa and paralysia
of both \e^ soon developed, and death ; the pathological changes were fatty degenera-
tion of the heart| Hver^ and kidneys.
J, C. Whatley, M.K.C.S., % records a caee in which a aingle doee of 20 grains
iippaif ntly produced an attack of urticaria. If suitable treatment is at hand large
dot»es may be recovered from. A auigle womat); § aged 27, suffering from melancholia |
took 365 gruina (1^S*9 gi'm.) with suicidal intent. Twelve hours after taking the
poinon ahe wan disco vei^ profoundly comatosMJ ; there wim no corneal relic x, and the
kni^- jerks and the radial reHeiea were abaenU She waa treated by wwhing tlie
atomach out and ^ubeutaneous injeotiona of ^ grain of atiychuiiie and ^ grain of
digitalin, She cnmpletely i^ecovered in about eight days.
There are but few cases ofiioisoning by trional on recoitl. Dr. Warren Coleman ||
deacribes an interesting case in which a woman aged 35 took, dnriug seventy-two hours,
9 draelims (alMUt 32 gnns.) of trionab She wa6 at the tune suirerLug frfun deliriuui^
the result of atc4) hollo exeo^H. dhe became ftomnoleot, but was eaaily rouaetl. Hie re
was no diatnrbauce of the circulation or resipiration. The sjieech was thick and the
gatkat4ivip. There was no ljrnmto-iM>rphyttriA, Kocovery waa ultimately eomplete.
* H. Hildebrant, Aith*f* expcTi^ J\Uh* a,
t £art«^, JuJy 28, 1900.
t Lanrst, April £t, 1904.
I All'rod E. Hind, Itnntii, Jaii> J», imA^
II Med. AVctw, July 28, 1000.
Fhttn^^ Bd liii.
172 POISONS: THEIR EFFECTS AND DETECTION. [§ 209-2II.
The sulphones described above may be shaken out of a feebly alkaline solution
by ether.
Organic matters are extracted by 90 |>er cent, hot alcohol ; the liquid is cooled,
filtered and freed from alcohol by distillation ; the residual liquid is filtered while hot,
made feebly alkaline by means of KHO, and shaken out in a separating funnel by ether.
The ethei-eal solution is eva|K>rated to dryness and leaves the sulphone in the form of
white crystals. That it is a sulphone may be proved as follows : fused with sodium-
|>eroxide, an orange-red mass results. A solution in water gives with sodium nitro-
pnisside a purple colour, showing the presence of a polysulphide ; sulphur separates
when the mass is ti-eated with hydrochloric acid, and a solution of chloride of barium
precipitates barium sulphate. A melting-point should be taken ; as before stated,
sulphonal melts at 126", trional at 75"*, and tetronal at 85", all temperatures so far
apart as to admit of practical application for the purposes of identification.
§ 209. Veronal. — Diethyl-malonyl carbamide, and ethyl-butyryl carbamide,
diethyl-malonyl carbamide, and dipropyl-malonyl carbamide, all have a narcotic
action, the first being as powerful as sulphonal, and the last four times as strong.*
Diethyl-malonyl carbimide or diethyl-barbeturic acid is in commerce under the
name of veronal, and consists of small colourless transparent crystals melting at
190° C. The crystals are soluble in 145 parts of water at 20**, fi-eely soluble in alcohol
and in ether. Boiled with caustic alkali it is converted into diethyl-malonic acid,
which, melting at 120° C, at above 170° forms COg and diethyl-acetic acid.
One death (suicidal) from veronal is re^KJrted to have taken place in Cornwall in
May 1904.
Dr. G. Fernandez Clarke t records a case in which 34 granmies were taken for
several nights, causing narcosis and erythematosis, the coma alternating with
delirium.
VIIL— Bisulphide of Carbon.
§ 210. Bisulphide of carbon— carbon distUphide, carbo7i sulphide
(CSg)— is a colourless, volatile fluid, strongly refracting light. Commer-
cial samples have a most repulsive and penetrating odour, but chemi-
cally pure carbon sulphide has a smell which is not disagreeable. The
boiling-point is 47**; the specific gravity at 0" is 1*293. It is very
inflammable, burning with a blue flame, and evolving sulphur dioxide ;
is little soluble in water, but mixes easily with alcohol or ether.
Bisulphide of carbon, on account of its solvent powers for sulphur,
phosphorus, oils, resins, caoutchouc, gutta-percha, etc., is in great
request in certain industries. It is also utilised for disinfecting purposes,
the liquid being burnt in a lamp.
§ 211. Poisoning by Carbon Bisulphide. — In spite of the cheapness
and numerous applications of this liquid, poisoning is very rare. There
appears to be a case on record of attempted self-destruction by this
agent, in which a man took 2 ozs. (56*7 c.c.) of the liquid, but without
a fatal result. The symptoms in this case were pallor of the face,
wide pupils, frequent and weak pulse, lessened bodily temperature, and
* E. Fischer and von Mering {Cfiem, CeTitr,, 1903, i.).
t Lancet, Jan. 28, 1904.
§211]
BISCLPHIDE OF CARBON.
173
spasmodic conTulsions. Car ban disulphide was detected in the breath
by lewling the expired air through an alcoholic solution of triethyl-
phospblii, with which it struck a red colour* It could also be found m
the urine in the same way. An iutetiHe hurtling iu the throat, giddiness,
and Ikeadacho lasted for seTcral days.
EKpcriments ou animuk have been frequentj and it is found to be
fatal to all forms* of animal HFe. There ig, indeed, no more convenient
agent for the destrncfcion of various noxious insects, such as moths, the
weevils in biscuits, the common bug, etc., than bisulphide of carbon. It
has also been recommended for use in exterminating mice and rats.*
Different animals show various degrees of sensitiveness to the vapour ;
frogs and cats being less aftected by it than birds, rabbits, and guinea-
pigs. It is a blood poison; methfrmoglohin is formed, and there is
disintegi'ation of the red blood corpnacles. There is complete amestheaia
of the whole body, and death occurs through paralysis of the respiratory
centre, but artificial respiration fails to restore life.
Chrome I*oisoiiiug, — Of some importance is the chronic poisoning
by carbon disulphide^ occasionally met with in manufactures necessitat-
ing the daily use of large quantities for dissolving caoutchouc, etc.
When taken thus in the form of vapour daily for some time, it gives
rise to a complex series of symptoms which may be divided into two
principal st^es — viz,, a stage of excitement and one of depression. In
the first phase, there is irmre or less permanent headache, with consider-
able indigetition, and its attendant loss of appetite, nausea, etc. The
sensitiveness of the skin is also heightened, and there are curious
sensations of creeping, etc. The mind at the same time in some degree
auSars, the temper becomes irritable, and ^singing iu the ears and noises
in the head have been noticed. In one factory a workman suffered from
an acute mania, which subsided in two days upon removing him from
the noxious vapour {Ealmtherg). The sleep is disturbed by dreams^ and,
aoeording to Delpech, t there is considerable sexual excitement, but this
atatement has in no way V:>een cotiftrmed* Pains iu the limbs are a
constant phenomenon, and the French observers have noticed spasmodic
contractions of certain groups of muscles.
The stage of depression begins with a more or less pronounced anies-
thesia of the skin. This is not confined to the outer skin, hut also
affects the mucous meu^branes; patients complain that thej feel as if
the tongue were covered with a cloth. The anaesthesia is very geuerml.
In a case recorded by llernhardt, | a girl, 22 years old* who had worked
• CltMt, Chmpi, B^uL, t. kiii, 85.
t Mimoi^ 9U^ iu Aceidenii que dmeUj^ thez Its mtvri^res en tmtnitkmit dn sul-
t BmkHn. iTocAriucftrt/if, Xo. 32, 18S6.
174 POISONS: THEIR EFFECTS AND DETECTION. [§ 2I2-2l6.
six weeks in a caoutchouc factory, suffered from mental weak-
ness and digestive troubles ; there were anaesthesia and algesis of the
whole skin. In these advanced cases the mental debility is very pro-
nounced, and there is also weakness of the muscular system. Paralysis
of the lower limbs has been noted, and in one instance a man had his
right hand paralysed for two months. It seems uncertain how long a
person is likely to suffer from the effects of the vapour after he is
removed from its influence. If the first stage of poisoning onl^ is
experienced, then recovery is generally rapid; but if mental and
muscular weakness and anaesthesia of the skin have been developed, a
year has been known to elapse without any considerable improvement,
and permanent injury to the health may be feared.
§ 212. Post-mortem Appearances. — The pathological appearances
found after sudden death from disulphide of carbon are but little
different to those found after fatal chloroform breathing.
§ 213. Detection and Separation of Carbon Disulphide. — The
extreme volatility of the liquid renders it easy to separate it from
organic liquids by distillation with reduced pressure in a stream of COg.
Carbon disulphide is best identified by (1) Hof man's test, viz., passing
the vapour into an ethereal solution of triethyl-phosphin, {C2ii^)J^.
Carbon disulphide forms with triethyl-phosphin a compound which
crystallises in red scales. The crystals melt at 95** C, and have the
following formula— P(C2H5)3CS2. This will detect 0*54 mgrm. Should
the quantity of bisulphide be small, no crystals may be obtained, but
the liquid will become of a red colour. (2) CSg gives, with an alcoholic
solution of potash, a precipitate of potassic xanthate, CSgCgH^OE.
§ 214. Xanthogenic acid or ethyloxide-solphocarbonate (CSsCsHsOH) is pre-
pared by decomi)08ing potassic xanthogenate by diluted hydrochloric or sulphuric
acid. It is a colourless fluid, having an unpleasant odour, and a weakly acid and
rather bitter taste. It bums with a blue colour, and is easily decomposed at 24°,
splitting up into ethylic alcohol and hydric sulphide. It is very poisonous, and
has an anesthetic action similar to bisulphide of carbon. Its properties are probably
due to CSj being liberated within the body.
§ 215. PotaBsic xanthogenate (OSaCsHBOK) and potassic zanthamylate
(CS9C5H11OE) (the latter being prepared by the substitution of amyl alcohol for ethyl
alcohol), both on the application of a heat below that of the body, develop OS,, and
are poisonous, inducing symptoms very similar to those already detailed. Reid Hunt
states that the fatal dose of pot. xanthogenate for rodents (mice) lies between 0'4 and
0*5 grm. per kilo, of body weight ; in non-fatal doses it is antagonistic to nitrates.
IX.— The Tar Acids -Phenol— Cresol.
§ 216. Carbolic Acid. Syn. Phenol, Phenol Alcohol, Phenylic
Hydrate ; Phenic Acid ; Coal-Tar Creasote.— The formula for carbolic
acid is C^HgUO. The pure substance appears at the ordinary tempera-
§ 217.]
TITB TAR AOIDS.
I7S
tiire aa a colourless solid, cryataUinmg in loug prisms ; the fitsibilitj of the
crystals is given variously by different authors : from our own obaerva-
tioa, the pure crystals melt at 40'-4r, any lower melting-point being
due to the presence of cresylic acid or otlier impurity ; the crystals
again become solid Jibout 15'. Melted carbolic add forms a colourless
limpid tiuid, sinking in water, Ifc boils under the ordinary pressure at
182', ani distill without deconiposltion ; it is very readily and
completely distilled in a vacuum at about the temperature of 100*.
After the crystals have been exposed to the air, they absorb water,
and a hydrate is formed containing 16*07 per cent, of water. The
hydrate melts at 17*^ any greater hydration prevents the crystallisation
of the acid ; a carbolic acid, containing about 27 per cent, of water,
and probably corresponding to the formula Cy^H^jO^^H^O, is obtained by
gradually adding water to carbolic acid so long as it continues to be
dissolved. Such a hydrate dissolves in 11 '1 times its measure of water,
and contains 8 '50 per cent, of real carbolic acid. Carbolic acid does
not redden litmus, but produces a greasy stain on paper, disappearing
on exposure Co the air; it has a peculiar smellf a burning numbing
taste, and in the fluid state it strongly refracts light. Heated to a high
temperature It takes fire, and bnnis witli a sooty flame.
When an aqueous solution of carbolic ticid is shaken up with ether,
benzene, carbou disulphide, or chloroform, it is fully dissolved by the
solvent, and is thus easily separated from most solntions in which it
exista in the free state. Petroleum ether, on the other hand, only
slightly dissolves it in the cold, more on warming. Carbolic acid mixes
in all proportions with glycerin, glacial or acetic acid, and alcohol. It
coagulates albumen, the precipitate being .soluble in an excess of albumen ;
it also dissolves iodine, without changing its properties. Tt dissolves
many resins, and also sulphur, but» on hoilingi sulphuretted hydrogen is
disengaged. Indigo blue is soluble in hot carbolic acid, and may be
obtained in crystals on cooling. Carbolic acid is contained in castoreum,
a secretion derived from the beaver, but it has not yet been detected in
the vegetable kingdom. The source of carbolic acid is at present
coal-tar, from which it is obtained by a process of distillation. There
are, however, a variety of chemical actions in the course of which
carbolic acid is formed.
§ '217. The common disinfecting carbolic acid is a dark reddish
Ijquidj with a very strong odour ; at present there is very little phenol
in it ; it is mainly composed of meta- and para-cresol. It is ofliciual in
Germany, and there must contain at leiist 50 per cent, of the pure
carbolic acid. The pure crystallised carlx>lic acid is oflieinal in our own
and all the Continental pharinacopceiae- In the British Pharmacopceia^
a solution of carbolic acid in glycerin is officinal : the proportiona are 1
176 POISONS: THEIR EFFECTS AND DETECTION. [§ 2 1 8, 2 1 9.
part of carbolic acid and 4 parts of glycerin, that is, strength by measure =
20 per cent. The Pharmacopoeia Germanica has a liqtwr natH carbolici
made with 5 parts carbolic acid, 1 caustic soda, and 4 of water ; strength
in carbolic acid = 50 per cent. There is also a strongly alkaline crude
sodic carbolate in use as a preservative of wood. The Privy Council
order of July 26, 1900, declares that liquid preparation of carbolic acid
and its homologue containing more than 3 per cent, of phenols shall,
except in certain cases connected with agriculture and horticulture, be
declared poisons within the meaning of the Pharmacy Act, 1868.
There are various disinfecting fluids containing amounts of carbolic
acid, from 10 per cent, upwards. Many of these are somewhat complex
mixtures, but, as a rule, any poisonous properties they possess are mainly
due to their content of phenol or cresol. A great variety of disinfecting
powders, under various names, are also in commerce, deriving their
activity from carbolic acid. Macdougall's disinfecting powder is made by
adding a certain proportion of impure carbolic acid to a calcic sulphite,
which is prepared by passing sulphur dioxide over ignited limestone.
Calvert's carbolic acid powder is made by adding carbolic acid to
the siliceous residue obtained from the manufacture of aluminic sulphate
from shale. There are also various carbolates which, by heating or de-
composing with sulphuric acid, give olf carbolic acid.
Carbolic acid soaps are also made on a large scale — the acid is free,
and some of the soaps contain as much as 10 per cent. In the inferior
carbolic acid soaps there is little or no carbolic acid, but cresylic takes
its place. Neither the soaps nor the powders have hitherto attained
any toxicological importance, but the alkaline carbolates are very
poisonous.
§ 218. The chief uses of carbolic acid are indicated by the foregoing
enumeration of the principal preparations used in medicine and com>
merce. The bulk of the carbolic acid manufactured is for the purposes
of disinfection. It is also utilised in the preparation of certain colouring
matters or dyes, and during the last few years has had another applica-
tion in the manufacture of salicylic acid. In medicine it is administered
occasionally internally, while the antiseptic movement in surgery,
initiated by Lister, has given it great prominence in surgical operations.
§ 219. Statistics. — The tar acids, i.e, pure carbolic acid and the
impure acids sold under the name of carbolic acid, but consisting (as
stated before) mainly of cresol, are, of all powerful poisons, the most
accessible, and the most recklessly distributed. We find them at the
bedside of the sick, in back-kitchens, in stables, in public and private
closets and urinals, and, indeed, in almost aU places where there are
likely to be foul odours or decomposing matters. It is, therefore, no
wonder that poisoning by carbolic acid has, of late years, assumed large
§ 219-]
THX TAB ACIDS,
"^77
proportions. The acid has become vulgarisedj and quite as popularly
known, as the tnoet commoti household dnigs or chemicals. This
familiarity ia the growth of a very few years^ amce it was not discovered
until 1834, and does not seem to have been used l>y Lister until about
1863, It was not known to the people generally until rnuoh later. At
present it occupies the highest place in fatiility of all poisons in England.
During the ten yeara ending 1903 carbolic acid has killed 1959 people,
either accidentally or suicidally ; there are also ftve oases of murder by
carbolic acid within the same period, bringing the total up to 1904.
Falck haa collected, since the year 1S68, 87 cases of poiaoniog from
carbolic acid recorded in medical literature. In one of the cases the
individual died in nine hours from a large dose of carbolate of soda ; in
a second, violent siymptoms were induceil by breathing for three hours
carbolic acid vapour ; in the remaining 85, the poisoning was caused by
the liquid acid. Of these 85 persons, 7 had taken the poison with
suicidal intent, and of the 7, 5 died ■ 39 were poisoned through the
medicinal use of carbolic acid, 27 of the 39 by the antiseptic treatment
of wounds by carbolic acid dressings, and of these 8 terminated fatally ;
In 8 eases, symptomfl of poisoning follow*ed the rubbing or painting
of the acid on the akin for the cure of scabies, favua, or psoriasis, and
6 of these persons died. In 4 cases, carbolic acidenemata, administered
lor the purpose of dislodging ascarldes, gave rise to symptoms of
poisoning, and in one instance death followed.
The substitution of carbolic acid for medicine happened as follows ' —
Taken instevl of Tincture of Oi>iam, ,
„ ,, iDfuaioii of S&nnti, .
,, Mineral Water,
^^ ^p other Mixturea,
„ inwardly instead of applied outwardly.
12
Of these 12, S died.
Again, 10 persons took carbolic acid in mistake for various alcoholic
drinks, such as schnapps, brandy, rum, or beer, and 9 of the 10 suc-
cumbed ; 1 7 persons drank carbolic acid simply '* by mistake," and of
these 13 died, Thu8, of the whole 85 cases, no less than 51 ended
fatally — nearly 60 per cent.
It must be always borne in mind that, with regard to statistics gener-
ally, the term ** carbolic acid'' ia not used by coroners, juries, or
medical men ia a strictly chemical sense, the term being made to include
disinfecting fluids which are almost wholly composed of the cresols^ and
contain scarcely any phenol. In this article, with regard to symptoms
and pathological appearances, it is only occasionally possible to state
12
178 POIflONS: THRIU RFFRCTH AND PRTKCTION. [§ 220, 221.
whethor tho ptiro nuHlicinal crjHUlliuo phouol or n nuxttirc of Ur-ncidH
wan tho oauso of |K)iHoning.
§ 220. Fatal Doao.— Tho ininiuntni faUl doMo for mU, i\ogH, aiui
rabbitis appoani to \h> loiw than *5 gnu. por kilograiuni(\ Kalck haaput
tlto minimum lothal dono for man at 15 grmn. (231*5 grainv), which
would bo abo\it *2 |>or kilo., l)aaiug hid ontimato on tho following roaaon^
ing. In 33 oaaon ho had a fairly oxnct rooord of tlio amount of acid
taken, and out of tho 33, he noloctA only thoiio oaaon which arc of uho
for tho dcoiRion of the quontion. Among luhiltn, in 5 oaaoii the doae
waa 30 grma., and all tho 5 caaen terminated by death, in timoH
varying from flvo minuteH to an hour and a half. Wy other ft adulU
a doso of 15 grmA. wan taken; of the 5, 3 men and a woman die<1,
in timea varying from forty-live minuted to thirty houra, while 1 woman
reoovon^d. Donen of 11*5, 10*8, and 9 grnw. were taken by different
men, and reeovere<l from ; on the other hand, a Huicido who t<x)k one
and a half toneiuionful (al)o\it G grmH.) of the concentrated acid,
diod in fifty miniitCH. Donen of *3 to 3 grms. have caused nympt^^nm of
poinoning, h\it the {mticntd rocovertHl, while higher doncd than 15 grma.
in 12 caNem, with only one exception, cauHcd death. Hence, it may W
oonnidered t-olerably well eatabliRhed, that 15 grmn. (231*5 grniuH) may
bo takon an repreaenting the minimum lethal done.
The largoHt doae from which a i)orHon appeam to have recovered in
prolmbly that given in a cane recorded by Davidnon, in which 150 grmii.
of crude carbolic acid had been taken. It numt, however, be remembered
that, aa this waa the impure acid, only half of it would be really carlHilic
aoid. The Gorman Pharmacopeia prcHcriben aa a maxinnun doMc *()5
grm. (*8 grain) of the cryiitAllised acid, and a dnily maximum qtiantit.y
given in dividwl doHCH of '15 grm. (2\3 graiuH).
§ 221. EflfectB on Animals.— (-arliolic acid Ik (mlHonoud to both
animal and vegetable life.
Infuaoria.- C)no part of the acid in 10,000 part.« of water rapidly
kills ciliated animalculea — tho movomentH become nluggiMh, the aarciKle
8ubHt4^ncc darker, and the cilia in a little time ciuiMe moving.
Pish. — One part of the acid in 7000 of water kilU tlace, minnowa,
roach, and gold fluh. In thin amount of dihition the effect in not ap-
parent innnodiately ; but, at tho end of a few houra, the movementa
of the flah become Hhigginh, they frec^uently rine to the nurfaco t-o
breathe, and at tho end of twenty >four houra are found dead. QuantiticH
of carUdic add, «uch aa I part in 100,000 of water, appear to affect
the health of fUh, and nmder them more liable to l>e attacked by tho
fungus growth which in no dostruotive to llahdifo in certain years.
Frogs. — If "Ol to '02 grm. of oarlmlic acid l>o disdolvod in a litre
of water in which a frog is placed, there in almost immediately signs of
§ 222.]
THE TAR ACIDS.
179
uneasiness in the animal, showing that pain from local contact is
experienced; a sleepy condition follows, with exaltation of reflex
sensibility ; convulsions succeed, p^enerally, though not always ; then
reflex sensibility is diminished, ultimately vanishes, and death occurs ;
the muscles and nerves still respond to the electric current, and the heart
beats, but slowly and weakly, for a little after the respiration has ceased.
^ 222. Warm-blooded Animalfl — For a rabbit of the average weight
of 2 kilos., -15 grm. is an active dose, and '3 a lethal dose (that is '15
per kilo.). The sleepy condition of the frog is not noticed, and the chief
symptoms are clonic convulsions with dilatation of the pupils, the
convulsions passing into death, without a noticeable paralytic stage.
The symptoms observed in poisoned dogs are almost precisely similar,
the dose, according to body weight, being the same. It has, however,
been noticed that with doses large enough to produce convulsions, a
weak condition has supervened, causing death in several days. There
appears to be no cumulative action, since equal toxic doses can be
given to animals for some time, and the last dose has no greater effect
than the first or intermediate ones. The pathological appearances met
with in animals poisoned by the minimum lethal doses referred to are
not characteristic; but there is a remarkable retardation of putrefaction.
Meili * has studied the relative lethal effects on rabbits of phenol
and the cresols. Meta-cresol he found less poisonous than phenol, the
deadly dose being 0*5 grm. per kilo. ; phenol, less poisonous than ortho-
and para-cresol ; and the latter most poisonous of all.
Karl TollenSjt experimenting on cats, mice, and frogs, gave the follow-
ing results : —
FATAL DOSE IN GRMS. PER KILOGRAMME OF BODY WEIGHT.
• Diaaertetion. IVerne, 1891.
t Arehiv,/, experiment. Path, u, Fhamu, Bd. lii. S. 239.
Cats.
Mice.
Froga.
Phenol
0-09
0-35
010
Para-cresol, ... ...
0-08
0-1 ,5
0-15
Ortho. „
0-09
0-35
0-20
Meta- „
0-12
0-45
0 25
Carbolate of soda reckoned in weielit of phenol, .
Cresolate of soda in terms of cresoT —
0-35
0-10
Paracresol,
0-15
0-15 1
Ortho- „
0-35
0-20
Meta- ...
0-45
0-25
L Crude cresol, .....
0-35
0-20
11. „ n
0-25
0-20!
m. „ ,
0-20
0.20'
I. Liq. cpesol saponis in terms of cresol, .
0-30
0-15
!'• f» >» »» »» • •
0-25
0-15 1
III. „ ,. M „ . .
0-20
015
l80 POISONS: THKIR EFFECTS AND DETECTION. [§ 223.
§ 223. Sjonptoms in Man, external application. — A 5 per cent,
solution of carbolic acid, applied to the skin, causes a peculiar numbness,
followed, it may be, by irritation. Young subjects, and those with
sensitive skins, sometimes exhibit a pustular eruption, and concentrated
solutions cause more or less destruction of the skin. Lemaire * describes
the action of carbolic acid on the skin as causing a slight inflammation,
with desquamation of the epithelium, followed by a very permanent
brown stain ; but this he alone has observed. Applied to the mucous
membrane, carbolic acid turns the epithelial covering white ; the
epithelium, however, is soon thrown off, and the place rapidly heals ;
there is the same numbing, aconite-like feeling before noticed. The
vapour of carbolic acid causes redness of the conjunctivae, and irritation
of the air-passages. If the application is continued, the mucous mem-
brane swells, whitens, and pours out an abundant secretion.
Dr. Whitelock, of Greenock, has related two instances in which
children were treated with carbolic acid lotion (strength 2^ per cent.) as
an application to the scalp for ringworm ; in both, symptoms of poisoning
occurred — in the one, the symptoms at once appeared; in the other,
they were delayed some days. In order to satisfy his mind, the
experiment was repeated twice, and each time gastric and urinary
troubles followed.
Nussbaum, of Munich, records a case f in which symptoms were
induced by the forcible injection of a solution of carbolic acid into the
cavity of an abscess.
Macphail t gives two cases of poisoning by carbolic acid from
external use. In the one, a large tumour had been removed from a
woman aged 30, and the wound covered with gauze steeped in a solution
of carbolic acid, in glycerin, strength 10 per cent. ; subsequently, there
was high fever, with diminished sulphates in the urine, which smelt
strongly of carbolic acid, and was very dark. On substituting boracic
acid, none of these troubles were observed. The second case was that
of a servant suffering from axillary abscess ; the wound was syringed
out with carbolic acid solution, of strength 2J per cent., when effects
were produced similar to those in the first case. It was noted that in
both these cases the pulse was slowed. J. A. Raubenheimer {Lancet^
April 18, 1003) describes the case of a child aged 6, prepared for
operation on genu valgum of both sides, by the nurse, who wrapped the
legs from the ankles to the groin with towels impregnated with carbolic
acid (1 : 40); in an hour the patient was sleepy, in two hours unconscious,
• Lemaire, Jul., De VAeidepheniquet Paris, 1864.
t LeUfaden zur antisepiiseher Wundhehandlung, 141.
t "Carbolic Acid Poisoning (Surgical)," by S. Rutherford Macphail, M.B., Ed.
Med. JauTTiul cccxiv., Aug. 1881, p. 134.
§ 223,]
THE TAB AQWB.
l8l
cyanosodj and almoet puJseleas. In six hours the urine showed carboluria,
which persisted for the next twentj-five hours; the patient, under treat-
ment, recovered. Scattered throughout Hurgical and medical literature,
there are inatiy other cases recorded, though not all bo clear m tlioae
cited- Several cases are also on record in which poisonoua By raptoms (and
even death) have reb^ulted from the application of carbolic acid lotion m
a remedy for acabies or itch,
A eurgeoii prescribed fo? two joiners who suffered from scabieu a
lutioUj which was intended to contain 30 grnis, of carbolic acid in !2iO
c,c. of water * but the actual contenta of the tiaske were afterwai^s from
analysis estimated by HoppeSeyler to be 33*26 grms.* and the quantity
uKed by ea^^h to be equal to 13 37 giratj. {206 grains) of carbolic aoid,
Une of the men died ; the survivor described his own symptoms as
follows I — He and his companion stood in front of the fire, and rubbed
the lotion in ; he rubbed it into his legs, breast, and the front |mrt of
his body ; the other purts were mutually rubbed, Whilst rubbing his
right arm, and drying it before the fire, he felt a burning sensaliou, a
tightne^ and giddiness, and mentioned his sensations to his companion,
who laughed. This condition laisted from live to seven minutes^ but he
did not remember whether his companion complained of anything, nor
did lie know what became of him^ nor how he himself came to be in bed.
He was fomid holding on to the joiner^s bench, looking with wide staring
eyes, like a drunken man, and warn delirione for half an hour. The
following night he slept nnensily and complained of headache and
hnrniug of the skin. The pulse was 68 j the appearance of the nrine,
appetite, and sense of taste were normal ; the bowels confined. He
soon recovered.
The other joiner seems to have died as suddenly as il he had taken
prnssic acid. He called to his mother, '* Ich kabe emen Hauntjh^^ and
died with pale livid face, after taking two deep, short inspimtiona»
The post-mortem examination showed the sinuses filled with nmch
fluid blood, and the vessels of the pia mater congested. Frothy, dark,
fluid blood was found in the lungs, which were hyperaimic ; the mucous
tissues of the epiglottis and air-tubes, were reddened, aud covered with
a frothy slime. Both ventricles— thi^ vense cavw and the vessels of the
spleen and kidneys — were filled witli dark fluid hlood. The muscles
were very red ; there was no special odour* Hoppe-Soyler i-ecognised
c^U'bolic acid in the blood and ditierent organs of the body,*
In another case, a child died from the outward use of a 2 per cent.
solution of carlKjlic aeid* It is described as follows t — An infant of
I weeks old suffered from vanoella, and one of the pustules became
* K. Kohkr, ^'Urtmi. MitL Cort'. BL, xMl, No, 6, April 1SF2 ; H. AWIin.
SckmuU'M Jahrb^hcr, U7i, Bel, cljuuii. a 163.
1 82 POISONS : THEIR EFFECTS AND DETECTION. [§ 224.
the centre of an er3r8ipelatoim inflammation. To this place a 2 per cent*
solution of carbolic acid was applied by means of a compress steeped in
the acid ; the following morning the temperature rose from SB'S" (97*7*
F.) to 37° (98'6** F.), and poisonous symptoms appeared. The urine
was coloured dark. There were sweats, vomitings, and contracted
pupils, spasmodic twitchings of the eyelids and eyes, with strabismus,
slow respiration, and, lastly, inability to swallow. Under the influence
of stimulating remedies the condition temporarily improved, but the
child died twenty-three and a half hours after the first application. An
examination showed that the vessels of the brain and the tissue of the
lungs were abnormally full of blood. The liver was softer than natural,
and exhibited a notable yellowishness in the centre of the acini. Some-
what similar appearances were noticed in the kidneys, the microscopic
examination of which showed the tubuli coniorti enlarged and filled with
fatty globules. In several places the epithelium was denuded, in other
places swollen, and with the nuclei very visible.
In an American case,* death followed the application of carbolic
acid to a wound. A boy had been bitten by a dog, and to the wound,
at 1 o'clock in the afternoon, a lotion, consisting of nine parts of
carbolic acid and one of glycerin, was applied. At 7 o'clock in the
evening the child was unconscious, and died at 1 o'clock the following
day.
§ 224. Internal Administration.— Carbolic acid may be taken into
the system, not alone by the mouth, but by the lungs, as in breathing
carbolic acid spray or carbolic acid vapour. It is also absorbed by the
skin when outwardly applied, or in the dressing or the spraying of
wounds with carbolic acid. Lastly, the ordinary poisonous effects have
been produced by absorption from the bowel, when administered as an
enema. When swallowed undiluted, and in a concentrated form, the
symptoms may be those of early collapse, and speedy death. Hence,
the course is very similar to that witnessed in poisoning by the mineral
acids.
If lethal, but not excessive doses of the diluted acid are taken, the
symptoms are — a burning in the mouth and throat, a peculiarly unpleasant
persistent taste, and vomiting. There is faintness with pallor of the
face, which is covered by a clammy sweat, and the patient soon becomes
unconscious, the pulse small and thready, and the pupils sluggish to
light. The respiration is profoundly affected ; there is dyspnoea, and the
breathing becomes shallow. Death occurs from paralysis of the respira-
tory apparatus, and the heart is observed to beat, for a little after the
respiration has ceased. All these symptoms may occur from the applica
tion of the acid to the skin or to mucous membranes, and have been
Anurican JuumcU of F\ar7naGy, vol. li., 4lh Ser. ; vol. iz., p. 67, 1879.
§ 22 S> 22d]
THE TAB AClDa
183
noticed wlieu solutioiia of but moderate strength have been uaed — t.g.
there are easeg in gynBecological prnctice in which the mucous membrane
(perhaps eroded) of the uterus ha& been irrigated with carbolio acid
injections. Thus, Kiiater * relates a case in which, four daja after con-
finement, the uterus was washed out with a 2 per centp solution of
carbolic acid vvithout evil results. Afterwards a 5 per cent, solution was
tisedi but it at onue caused violent symptoms of pi>Jsonitig — the face
became livid^ clonic convulsions came uu, and at first loss of conscious-
ness, which after an hour returned. The patient died on the ninth day*
There was intense diphtheria of the uterus and vagina. Several other
dmilar cases (although not attended with such marked or fatal elfeotA)
ate on record *t
§ 225. The symptoms of carbolic acid poisoning admit of considerable
variation from those already described. The condition is occasionally
that of deep coma. The convulsions may be general, or may affect only
certain groups of muscleSp Convubive twitchings of tbe face alone,
and also muscular twitchings only of the legs, have been noticed. In all
cases, however, a marked change occurs in tbe urine. Subissi % has
noted the occurrence of abortion, both in tbe pig and the mare, as a
result of carbolic acid, but this effect baa not hitherto been recorded iu
the human subject.
It has been experimentally siiowu by Ktieter, that previous loss of
blood, or the presence of septic fever, renders animals more sensitive
to carbolic acid. It fa also said that children are more sensitive than
adults*
Tbe course of carbolic acid poisoning is very rapid. In 35 oases
L^ollected by Falck, in which the period from tbe taking of the poison to
the moment of death was accurately noted, the course was as follows ; —
12 patients died within the first hour, and in the second hour 3; so that
within two hours 15 died. Between the third and the twelfth hour, 10
died ; between the thirteentb and the twenty4ourth hour, 7 died ; and
between the twenty^fifth and the airtietb hour, only 3 died. Therefore,
slightly over 71 per cent, died within twelve hours, and 91 '4 per cent.
within the twenty-four hours,
§ 226. Changes in the XJriiie, — The urine of patients who have
absorbed in any way carbolic acid is dark in colour, and may smell
♦ QttiimlhlaUf. Qfnakol^ie, >i. 14, 1873.
f A pmetitioiier m Cabutta injected iitto the bow^l of a boyi aged 5^ an ^nema of
diluted c^bdic acid, wliichj aoeordlDg ta hU own Htnttiiaent, was 1 p&n in 60, and
the whole quantity it?iireaented 144 gmioa of the sioid. The ohild became insensible
a few ininutea after the ojieration^ «xd died within foar hoars. There waa jjo poet-
mortara exatninAtion ; the body amelt stroogly of c»rbolic acid, — £aft^(^ May 10^
1883.
X VArchiviQ detla Fettrinaria /lal>, xi., 1B74.
1 84 POISONS: THEIR EFFECTS AND DETECTION. [§ 226.
strongly of the acid. It is now established — chiefly by the experiments
and observations of Baumann * — that carbolic acid, when introduced into
the body, is mainly eliminated in the form of phenyl-sulphuric acid,
CgHgHSO^, or more strictly speaking as potassic phenyl - sulphate,
CgH5KS04, a substance which is not precipitated by chloride of barium
until it has been decomposed by boiling with a mineral acid. Cresol is
similarly excreted as cresol sulphuric acid, CgH^CHgHSO^ oiiiho-, meta-,
or para-, according to the kind of cresol injected ; a portion may also
appear as hydro-tolu-chinone-sulphuric acid. Hence it is that, with doses
of phenol or cresol continually increasing, the amount of sulphates natur-
ally in the urine (as estimated by simply acidifying with hydrochloric
acid, and precipitating in the cold with chloride of barium) continually
decreases, and may at last vanish, for all the sulphuric acid present is
united with the phenol. On the other hand, the precipitate obtained by
prolonged boiling of the strongly acidified urine, after filtering ofi* any
BaSO^ thrown down in the cold, is ever increasing.
Thus, a dog voided urine which contained in 100 c.c, *262 grm. of
precipitable sulphuric acid, and *006 of organically-combined sulphuric
acid; his back was now painted with carbolic acid, and the normal
proportions were reversed, the precipitable sulphuric acid became
*004 grm., while the organically-combined was '190 in 100 c.c. In
addition to phenyl-sulphuric acid, it is now sufficiently established!
that hydroquinone (CeH^QTj) (paradi hydroxy 1 phenol) and pyro-cate-
chin (CgH^QTr) (orthodihydroxyl phenol) are constant products of a
portion of the phenol. The hydroquinone appears in the urine, in the
first place, as the corresponding ether-sulphuric acid, which is colourless ;
but a portion of it is set free, and this free hydroquinone (especially in
alkaline urine) is quickly oxidised to a brownish product, and hence the
peculiar colour of the urine. Out of dark coloured carbolic acid urine the
hydroquinone and its products of decomposition can be obtained by shak-
ing with ether; on separation of the ether, an extract is obtained,
reducing alkaline silver solution, and developing quinone on warming
with ferric chloride.
To separate pyro-catechin, 200 c.c. of urine may be evaporated to an
extract, the extract treated with strong alcohol, the alcoholic liquid
evaporated, and the extract then treated with ether. On separation and
evaporation of the ether a yellowish mass is left, from which the pyro-
oatechin may be extracted by washing with a small quantity of water.
• PflUger's Archiv, xiii., 1876, 289.
t E. Baumann and C. Preuss, Ztittchrift f. phys. ChemU, iii 156 ; Anleitung zur
Ham-Analyse, W. F. Lobisch, Leipzig, 1881, pp. 142, 160 ; Schmiedeberg. Chem,
Centrhl, (3), 13, 698.
§ 227, 228.]
THE TAR ACIDS.
tss
This BoItitioD will reduce silver uolutton in the ooldj ^ii\ if t treated with
a few drops of ferric cUbrid© solution, show a marked gr^en colour,
changing on being alkalized by a eolation of sodio hydnxmrboDate to
violet, and then on being acidified by acetic acid, changing back ftgain to
green. According to Thudichutn^* the urine of men and dogs, after the
ingestion of eaibolic acid, eontalnH a blue pigment.
§ 227. The Action of Ci^bolic Add coneidered physiologici^y, —
Beaearches on animals have elucidated, in a great measure, the mode in
which carbolic acid acts, and the general sequence of effects, but there is
still much to be learnt,
E. KUster f haa shown that the temperature of dogs, when doses of
carbolic acid in soiution are injected isubcutaneonsly, or into the veins, is
immediately, or very sioon after tbc operation^ raised. With small and
moderate doses, this eft'ect is but alight — from half to a whole degree —
on the day after the injection the temperature sinks below the normal
point, and only slowly becomes again natural. With doaea that arc juat
lethal, tjrst a rise and then a rapid h inking of temperature are observed ;
but with those excesaive doaes which speedily kill, the tempemturo at
once sinks without a preliminary rise. The action on the heart ia not
very marked, bnt there is always a slowing of the cardiac pulsations ;
according to Hoppe-Seyler the arteries are relaxed. The respiration is
much quickened ; this acceleration is due to an excitement of the vagus
centre, since Salkowaky has shown that section of the vagus produces a
retardation of the respiratory wave^ Direct application of the acid to
muaclea or nerves quickly destroys their excitability without a previous
stage of excitement. The main cause of the lethal action of carbolic acid
— putting ou one side those cases in which it may kill by ita local corro*
sive action — appears to be paralysis of the respiratoiy nervous centres.
The convidsioua arise from the apinal cord* On the cessation of the
convulsions, the superticial nature of the breathing asaists other chunges
by preventing the due oxidation of the blood.
g 228. Carbolic acid is separated from the body in the forms already
mentioned, a small portion ia abo excreted by the skin. Salkowsky
states that, with rabbits, he has also found oxalic acid in the urine
m an oxidation product. According to the researches of Binneudijk, *
the separation of carbolic acid by the urine commences very quickly
after its ingestion j and, under favourable circumstances, it may be com-
pletely excreted within from twelve to sixteen hours. It must bo
remembered that normally a small ainouut of phenol may be present in
the animal body, as the result of the digestion of albuminous substances
* On Ih^FiUhvlvgyqfihe Urin^, Lotid., 1877» p. 198.
t Archie/, khn,. Chiruf^, Bd. xxii Si 1S8» W9.
t J&wnai d« Pkarm&ck U d« CkimUf 4 Ser. T, xxx., 1880.
1 86 POISONS: THEIR EFFECTS AND DETECTION. [§ 229.
or of their putrefaction. The amount excreted by healthy men when
feeding on mixed diet, Engel,^ by experiment, estimates to be in the
twenty-four hours 15 mgrms.
§ 229. Post-mortem Appearances. — No fact is better ascertained
from experiments on animals than the following: — That with lethal
doses of carbolic acid, administered by subcutaneous injection, or intro-
duced by the veins, no appearances may be found after death which
can be called at all characteristic. Further, in the cases in which death
has occurred from the outward application of the acid for the cure of
scabies, etc., no lesion was ascertained after death which could — apart
from the history of the case and chemical evidence — with any confidence
be ascribed to a poison.
On the other hand, when somewhat large doses of the acid are taken
by the mouth, very coarse and appreciable changes are produced in the
upper portion of the alimentary tract. There may be brownish,
wrinkled spots on the cheek or lips ; the mucous membrane of the mouth,
throat, and gullet is often white, and if the acid was concentrated,
eroded. The stomach is sometimes thickened, contracted, and blanched,'
a condition well shown in a pathological preparation (ix. 206, 43 /) in
St. George's Hospital. The mucous membrane, indeed, may be quite as
much destroyed as if a mineral acid had been taken. Thus, in Guy's
Hospital museum (1799^^), there is preserved the stomach of a child
who died from taking accidentally carbolic acid. It looks like a piece
of paper, and is very white, with fawn-coloured spots; the rugae are
absent, and the mucous membrane seems to have entirely vanished.
Not unfrequently the stomach exhibits white spots with roundish edges.
The duodenum and upper part of the small intestine is often affected (see
a preparation in St. Bartholomew's Museum, 1949, e), and the action
is not always limited to the first part of the intestine.
The respiratory passages are often inflamed, and the lungs in-
filtrated and congested. As death takes place from an asphyxiated
condition, the veins of the head and brain, and the blood-vessels of the
liver, kidney, and spleen, are gorged with blood, and the right side of
the heart distended, while the left is empty. On the other hand, a
person may die of sudden nervous shock from the ingestion of a large
quantity of the acid, and in such a case the post-mortem appearances
will not then exhibit precisely the characters just detailed. Putrefaction
is retarded according to the dose, and there is often a smell of carbolic
acid.f If any urine is contained in the bladder, it will probably be
dark, and present the characters of carbolic urine, detailed at p. 183.
• AniKU, de Chimie et de Physique, 5 Ser. T. xx. p. 280, 1880.
t In order to detect this odour, it is well to open the head first, lest the putre-
faction of the internal viscera be so great as to made the odour.
§250, 23 J,]
THl TAB ACIDS.
187
Tests for Carbolic Acid.
S 230. 1. The Pinewood Test,— Certain piuewood given a beautiful
blue coluur when uiubteucd firt^t wltb carbolic acid, aud afterwards with
h^^drochlorie acid, aud exposed Lo th^ light. SSome species <jf pine give
a blue eolour with hydroehluric acid aloye, and such must uot be tuaed;
others do uot roijpond to the teat for carbolic acid. Hence it la necessary
to try the uhijjs of woud finjt, to aee how they act, and with this pre-
eautiou the test i^ very serviceable, and, m cautious hands, no error will
be nmde,
2. Ammoma and Hypochlorite Test.— If to a solution containing
even au small a quantitj as 1 part of carbolic acid in 5Q00 parts of
water, first, about a quarter of its volume of ammonia hydrate be added)
and then a small quantity of sodic hypochlorite solution^ avoiding ex-
0683, a blue colour appears ; warming quickens the reaction : the blue
is permauent, but tnrus to red with acids. If there is a smaller
quantity than the above proportion of acid, the reaction may be still
produced feebly after standing fi»r aome time,
3. Ferric Chloride. —One part of phenol in 3000 parts of water can
be detected by adding a solution of ferric chloride ; a fine violet colour
is produced. This is aim a very good test, when applied to a distillate ;
but if applied to a complex liquid, tho disturbing action of neutral salts
and other substances may be too great to make the reaction under those
circumstances of service.
4* Bromine, — The moat satisfactory test of all is treatment of the
liquid by bromine-water, A precipitate of tri-bromo-phenol {C^^^Br/))
is mpidly or slowly formed, according to the strength of the solution;
in detecting very minute quantities the precipitate must be given time to
form. According to Allen,* a solution containing but ^^^^ of carbolic
acid gave the reaction after standing twenty-four hours.
The properties uf the precii*itate are as follows : — It is crystalline^
and under the microscope ih seen to consist of hue stars of needles ; its
smell is peculiar ; it is insoluble in water aud acid liquids, hut soluble
in alkalies, ether^ and absolute alcohol; a very minute quantity of
water suiHces to precipitate it from an alcoholic solution ; it is therefore
essential to the success of tlie test that the watery liquid to be examined
is either neutral or acid In reaction.
§ 23L Tri-bromo- phenol may be used for the quantitative estimation
of carboHc acid ; 100 parts of tri-bromo-phenol are equal to 29*8 of
carbolic acid ; by the action of sodium amalgam, tri-bromo-phenol la
changed back into carbolic acid*
* QQTnjftarci^ Organic Anatytiift ^h i< 1^ '^^^-
iS8
POISONS : THBIE EFFKCT8 AND DETKCTION.
[§ 232.
That bromine-water precipitates several volatile and fixed alkaloids
from their solutions is no objection to the bromine test, for it may be
applied to a distillation product, the bases having been previously fixed
by sulphuric acid. Besides, the properties of tri-bromo-phenol are
distinct enough, and therefore there is no valid objection to the test.
It is the best hitherto discovered. There are also other reactions, such
as that Millon's reagent strikes a red — molybdic acid, in concentrated
sulphuric acid, a blue — and potassio dichromate, with sulphuric acid, a
brown colour — but to these there are objections. Again, we have the
Euchlorine test, in which the procedure is as follows : — A test tube is
taken, and concentrated hydrochloric acid is allowed to act therein upon
potassic chlorate. After the gas has been evolved for from 30 to 40
seconds, the liquid is diluted with 1^ volume of water, the gas removed
by blowing through a tube, and solution of strong ammonia poured in
so as to form a layer on the top ; after blowing out the white fumes of
ammonium chloride, a few drops of the sample to be tested are added.
In the presence of carbolic acid, a rose-red, blood-red, or red-brown tint
is produced, according to the quantity present. Carbolic acid may be
confounded with cresol or with creosote, but the distinction between pure
carbolic acid, pure cresol, and creasote is plain.
yOH
§ 232. Cresol (Oresylic Acid, Methyl-phenol), C«Hx .—There
are three cresols — ortho-, meta-, and para-. Ordinary commercial cresol
is a mixture of the three, but contains but little ortho-cresol ; the more
important properties of the pure cresols are set out in the following
table: — Pure ortho-, meta-, or para- cresol have been obtained by
synthetical methods ; they cannot be said to be in ordinary commerce.
Ortho-, .
Meta , .
Pai-a-, .
Melting-point.
31-31-6'C.
Fliiid at oitlinary
temperature.
36°
Boiling-point
Converted by fusion
with Potash into-
188 -O"
2010^
198''
Salicylic acid
(Ortho-oxv benzoic
acid).
Meta-oxybenzoic
acid.
Para-oxybenzoic acid.
Commercial cresol is at ordinary temperatures a liquid, and
cannot be obtained in a ciystalline state by freezing. Its boiling-point
is from 198' to 203**; it is almost insoluble in strong ammonia, and,
when 16 volumes are added, it then forms ciystalline scales. On the
other hand, carbolic acid is soluble in an equal volume of ammonia,
5 233-]
THK TAB ACIDS,
189
and is then precipitated by the addition of 1| Toliima of water. Creaol
is inaolubla in small quantities of pure 6 per cent, soda solution ; with
a large excesSj it ft)raia crystalline scales ; while carbolic aoid is freely
Boluble in ^mall or large quantities of alkaline solutions.
Cold petroleum spirit dissolves cresol, but 110 crystalline scales can
be separated out by a freezing mixture. Carbolic acid, on the contrary,
is but sparingly soluble in cold jjetroleura, and a solution of carbolic
acid in hot petroleum, wbeu exposed to sudden cold profiuced by a
fre^Ring mixture, separates out crystals from the upjjer layer of liquid.
Cresol is miscible with glycerin of specific gravity 1'258 in all propor-
tions ; 1 measure of glycerin mixed witli 1 measure of cre«ol is
completely precipitated by I measure of water* Carbolic acid^ under
the same circumstances, Is not precipitated. The deusity of cresol is
about 1*044* It forms with bromine a tri-bromo-c resold but this is
liqiiid at ordinary temperatures, while tri-bromo-phenol is solid* On
the other hand, it resembles carbolic acid in its reactions with ferric
chloride and with nitric and sulphuric acids.
I 233. OreMoie or Kreozote is a tenn ivpplied to the raixtiipf of cnidi> phenols
obtained from the distillation of wood -tar. It ednniiits of a tnixUire of subst&neett
of which the chief are guaiwsol m' oxycrpsul (CjHhO.^), boiling at 200"*, and oreaaol
(QiHiftCXj), boiling at 217"* ; also in small quantities phlorul (CgHioO), methyl oreaaol
(GjiHijjO-J, and other bodies. Morfton*^ English creasote is prepared from Stcjckliolm
tar, and boilt^ at about 217^} con^iating chiefly of creosol ; it h not e&sj% by mere
chemical ti^^tf^^ to dlBtingiiish creaaote from cresjlic acid* Creaso&e, in its reactiacfi
with snlpbuTJc and nitrii? acid^ bromine and gelatin, i» similar ti> carbolio and
cre^ylic acids^ and its solubility in raoat solvents is ako similar. It is^ however,
diutiiigniabed from the tar acids by Itsi insolubility in Price *s glycerin, specific gravity
1 "258, T^'liftlior 1, 2 J or 3 volnnie.^ of glycerin be emplnyi^d. But the Iwst test is
its action on an etbf real Hdlution of ijitTTi-celluloHe, Oreasote mixe.^ fre<^ly with thi
B,P« colloflinni, while eresylic acid ot dLrbolic acid at obco coagulates the latter.
With com[ilicatec] mixturea ooutaininj^' carbolic acid^ crefiol, and cre-a^totei thn only
method t>f applying these tcat^ i^ith achautiigw is to submit the mixture to fractional
distillation.
Fliickiger* testa for small qnai»titiefl of oarboUo acid in creanote^ by mixing
4 watery solution of the sample with one -fourth of ita volume of ammonia hydrate^
wetting the inside of a porcelain dish with tbia aolutioxi, ami tbnn cari fully blowing
bromine fumes on to thi.' surface. A hue blue colour appears if curbolie acid h preient,
but if the Bam 1*1 e consista of creaaote ouly^ then it is a dirty green or brown. Excess
of br':jniin*' sixjils the reactinu.t
• ylrdA. dri* Pharmame, CKiii. p» 30,
f OreaisolJ' In, \vithont doubt, jHiia«mouBt though but little is known of its action,
and very few exp'rimenta are on reconl ia vrhi&^ pure creasote bos been i^m ployed.
EuleDberg ha^ i^tudied the sym^itiimB in nbbits, by Kubmitting tliem to vaporised
oreasote — i.e, the vapour from 20 drops af creosote rlilfuHerl through a glflis nhflde
under wluch a rabbit was con lined. There was at ^mce gruat uneasiness, with a wftteiy
dieabftig^ from the eyes, and after seven 'minutes the rabbit fell on its side, and was
ilightlj ©onvtilaed. The cornea was troubled, and the eyes |rrominent ; a white slime
AofWid from the mouth ami eyes. After fifteen minutes there was narcoala, with
I90 POISONS: THKIR EFFECTS AND DETECTION. [§ 234, 235.
§ 234. Carbolic Add in Organic Fluids or in the Tissues of the
Body. — If the routine process given at page 49, where the organic
fluid is distilled in a vacuum after acidifying with tartaric acid, is
employed, phenol or cresol, if present, will certainly be found in the
distillate. If, however, a special search he made for the acids, then the
fluid must be well acidified with sulphuric acid, and distilled in the
usual way. The distillation should be continued as long as possible,
and the distillate shaken up with ether in the apparatus figured at
page 163. On separation and evaporation of the ether, the tar acids,
if present, will be left in a pure enough form to show their reactions. The
same process applies to the tissues, which, in a finely-divided state, are
boiled and distilled with dilute sulphuric acid, and the distillate treated
as just detailed.
Like most poisons, carbolic acid has a selective attraction for certain
organs, so that, unless all the organs are examined, it is by no means
indiflerent which particular portion is selected for the inquiry. Hoppe-
Seyler applied carbolic acid to the abdomen and the thighs of dogs,
and when the symptoms were at their height bled them to death, and
separately examined the parts. In one case, the blood yielded '00369
per cent. ; the brain, 0034 percent. ; the liver, 00125 ; and the kidneys,
•00423 per cent, of their weight of carbolic acid. The liver then
contains only one-third of the quantity found in an equal weight of
blood, and, therefore, the acid has no selective affinity for that organ.
On the other hand, the nerv'ous tissue, and especially the kidneys,
appear to concentrate it. P. G. Menegazzi {Uarod^ xxi., 1898), from
a poisoned rabbit, failed to extract from the tissues, etc., more than
29*2 per cent, of the phenol administered; which is not surprising,
seeing the chemical changes it is liable to undergo.
§ 235. Examination of the Urine for Phenol or Cresol. — It has
been previously stated (see p. 184) that the urine will not contain these
as such, but as compounds — viz., phenyl or cresyl sulphate of potassium.
By boiling with a mineral acid, these compounds may be broken up,
and the acids obtained, either by distillation or by extraction with ether.
To detect very minute quantities, a large quantity of the urine should
be evaporated down to a syrup, [and treated with hydrochloric acid and
lessened reflex action ; the temperature was almost normal. There was rattling
breathing, and in half an hour the animal died, tlie respiration ceasing, and
fluid blood escaping from the nose. Section after death showed the brain to be
hyi>er8emic, the mucous membranes of the air-passages to be covered with a thin
layer of fluid blood, and the lungs to be congested ; the right side of the heart was
gorged witli fluid blood.
The post-mortem ap|>earances and the symptoms generally are, therefore, closely
allied to those produced by carbolic acid. A dark colour of the urine has also been
noticed.
§ 236.]
TWK TAB ACIDS*
191
ether. On evaporating off the ether, the residue should be distilled
with dilute sulphuric acid^ and thie distillate then tested with bromine^
water, and the tri-bromo-phenol or cresol collected^ identified, and
weighed,
Tbudicbum* baa separated oiystala of potassic phenyl -sulphate
itrBfilf from the urine af patietiifj treated endermieally by carbolic iM3id|
as follows : —
The urine was evaporated to a syrup, extracted with alcohol of 90 per
cent, treated with an filcoholic solution of oxaHc acid as long as this
produced a precipitate, and then shaken with an equal volume of ether.
The mixture was next Altered, neutralised with potassic carbonate,
evaporated to a small bulk, and again taken up with alcohol. Sonie
oxalate and carbonate of potassium were separated, and oti evaporation
to a syrup, crystals of potassic phenyl-snlphate were obtained. They
gave to an analygis 4625 per cent. H^SO^, and 18*1 X — theory requiring
4^"2 of HgSO^ and 18'4 of K, Alkaline phenyl-sulphates strike a deep
purple colour with ferric chloride. To estimate the amount of phenyl-
sulphate or cresol-aulphate in the urine* the normal sulphates nmy be
separated by the addition of chloride of barium in the cold, first acidify -
iug with hydrochloric acid. On boiling the liquid a second crop of
sulphate is obtained, due to the breaking up of the compound sulphate,
and from this second weight the amount of acid can tje obtained, e.g. in
the case of phenol--C,,H;^HSO^ : BaSO^ : : 174 : 233.
§ ^6. Aaaay of DisitifiectaiitB, Gftrbolic Acid FowderB, etc. ^ For the n»say i>r
cmde t^rbolic acid, Mr. Chfirlps Lowp f uses tko following pt-ocess : — ^^A thoiwand
parti of the samplo iire distilled without any sp^cinl condeudng arrangement \ water
fiifft cornea oyer, and ia then foUow^ by &n oily tlnid Wben a hundred parts of the
Iftttor, ii measured in a graduated tub«!j have beeo collected, the receiver is changed.
The Tolume of watar ja rend off. If the oilj liquid floats on the waier, it eoatains
light oil of taT ; if it is heavier than the water^ it is regptrded as hjdrated acid, con«
taining 60 per cent, of real cArboKc acid» The next portion eon^iats of anhydrons
creaylic and car hoi ic acids^ and 025 Folum^ are distilled over : the rernaiiidi^r in the
retort cottsist^ wholly of creaylic acid and the higher homologues. The relative pro-
poftiouh of carbolic and cresyUc? acids are approximatoly determined by taking the
solidifying point, which should be between IS'S" and 24°, and having dHcertained
this temiieratnre, imitating it by making miiturea of known pro[iortionB of c&rholle
and crefiylic acids.
E. Waller t has recommended the following process i<iir the estimation of carbolic
add. It is based on the prec^ipttation of the tar ocid^ by bromine, and, of course, all
phsnok precipitated in this way will be returned as carbolic acid. The solutions
neoeisary are—
L A 0olutioii eontaining IQgrmH, of pure carbolic a^id to the litre: this serves^
aa a standard solutioHi
t Allen's Coin Hiffrfi^i Orgmvii An4df»is, vol. U
X Chtm, Nt-m^ April 1. 1S81, p, 152.
p. 311
192 POISONS : THEIR EFFECTS AND DETECTION. [§ 237.
2. A solution of bromine in water.
3. Solution of alum in dilute sulphuric acid. A litre of 10 per cent solphnric
acid is shaken with alum crystals until saturated.
The actual process is as follows : — 10 grms. of the sample are weighed out and
run into a litre flask, water added, and the mixture shaken. The flask being finally
filled up to the neck, some of the solution is now filtered through a dry filter, and
10 cc. of this filtrate is placed in a 6 or 8 ounce stoppered bottle, and SO c.c of the
alum solution added. In a similar bottle 10 ac of the standard solution of carbolic
acid are placed, and a similar quantity of alum solution is added, as in the first bottle.
The bromine- water is now run into the bottle containing the standard solution
of carbolic acid from a burette, until there is no further precipitate ; the bottle ia
stoppered and shaken after eveiy addition. Towards the end of the reaction the
precipitate forms but slowly, and when the carbolic acid is saturated, the alight
excess of bromine- water gives the solution a pale yellow tint The solution from the
sample is treated in the same way, and from the amount of bromine- water used, the
{tcrcentage of the sample is obtained by making the usual calculations. Thus, sup-
{tosing that 6 cc. of the standard required 15 c.c. of the bromine-water for precipita-
tion, and 10 cc. of the solution of the sample required 17 cc, the calculation would
bel5x2:17 = 100:a5 per cent With most samples of crude carbolic acid, the pre-
cipitate does not readily separate. It is then best to add a little of the precipitate
already obtained by testing the standard solution, which rapidly clears the liquid.
KDppe8chaar*B volumetric method is more exact, but also more elaborate,
than the one just described. Caustic normal soda is treated with bromine until
permanently yellow, and the excess of bromine is then driven off* by l>oiling. The
liquid now contains 5XaBr + NaBrOj, and on adding this to a solution containing
carbolic acid, and a sufficient quantity of hydrochloric acid to combine with the
sodium, the following reactions occur : —
(1.) 5XaBr + NaBrOj -\- 6HC1 ^ 6NaCl + 6Br + 3H9O ;
and
(2.) C6HeO + 6Br=CeHsBr30 + 8HBr.
Any excess of bromine liberated in the first reaction above that necessary for the
second, will exist in the free state, and from the amount of bromine which remains
free the quantity of car1)olic acid can be calculated, always provided the strength of
the bromine solution is first known. The volumetric part of the analysis, therefore,
merely amounts to the determination of free bromine, which is best found by causing
it to react on ]>otassium iodide, and ascertaining the amount of free iodine by titra-
tion with a standard solution of sodium thiosulphate. In other words, titrate in
this way the standard alkaline bromine solution, using as an indicator starch paste
until the blue colour disappears. Another method of indicating the end of the
reaction is by the use of striiw of paper first soaked in starch solution, and dried, and
then the same pai)ei-s moistened with zinc iodide, and again dried ; the least excess
of bromine sets free iodine, and strikes a blue colour.
Golorimetric Method of EBtimation. — A very simple and ever-ready way of
approxbnately estimating minute quantities of the phenols consists in shaking up
10 grms. of the sample with water, allowing any tar or insoluble impurities to sub-
side. Ten cc of the clear fluid are then taken, and half a cc of a 5 per cent,
solution of ferric chloride added. The colour produced is imitated by a standard
solution of carbolic acid, and a similar amount of the reagent, on the usual principles
of colorimetric analysis.
§ 287. Carbolic Acid Powders. — Siliceous carbolic acid powders are ploced in a
retort and distilled. Towards the end the heat may be raised to a]>proaching red-
ness. The distillate se]>arates into two portions — the one aqueous, the other con-
sisting of the acids— and the volume may be read off*, if the distillate be received in
§ 23S-240.]
NITRO-BBNZENE.
193
a gndUfttad reoeiyer. Carbolic Adtd {towderSj hftving lime as a basii^ may be dk-
tiiled in the a&mQ way, iiftor firai t|ec3onip4:>giDg with Bal]>hurio acid. The estimation
of the neutral tar oils in th© distillato m Baaily perforrned by shaking the duitiUate
with caustic mdn solutkiii, whicli dii^aolvfis completely the tar acids. The voIuth© of
the oila niay be directly read otf if the receiver is a gmduated ttibe, Allen* baa
suggested the addition of a known volume of {letroleuni to the distillate, which dia-
solvcm the tar oiU^ and eoiiily ^paratesi, and thus tbe volume may be more acoumtely
detenninedi a correction being of course made by subtractmg the volume of petroleqm
fitat added.
S 2S8. Carbolic Acid Soap, — A conveDient quantity of doap is carefully weighed,
and dLBSoIved In a solution of caustic soda by means of heat A Katuratjed solution
of salt is neatt addedi sufficient to precipitate entirely the aoap^ which h filtered off ;
the filtrate ia acidified with hydrocbloriR acid, and bromine -water added. The pre-
cipitated trl brotno-jihenol in fir8t melted by heat, then allowc^l to cr>ol^ and the ma^
removed from the liquid, dried, and weighed.
X.— Nitro-Benzene.
§ 239. — Nitr(>-beazeiie is the product resulting from the actioD of
strong nitric acid on benzene. Its chemical formula m CjjH^NO,^. When
pure^ it is of a pale yellow colour, of a density of 1'186, and boils at from
205' to 210\ It may be obtained In prismatic cryatals by exposure to
a temperature of Z^. Its smell is exactly the same as that from the oil
or essence of bitter almonds ; and it ii from this circiimatanca, under
the name of "essence of mirbane/' much used in the preparatioii of
perfumes and flavouring agents,
In commerce there are three kinds of nitro*benzene — the purest, with
the cbaraoters given above ; a heavier nitro- benzene, boiling at SIO"* to
220'; and a very heavy variety, boiling at 222'' to 235". The last is
specially used for the preparation of aniline, or aniline blue. Nitro*
benz^ene has been used as an adulterant of bitter almond oil, but the
detection is easy (see p. 198). Kitro-benzene waa first discovered
by Mitseherlicb in 18S4, and ite poisonous properties were first
pointed out by Casper t in 1859, Its technical iiae in perfumes, ete.,
dates from about 1848, and in the twenty-eight years intervening
between that date and 1876^ Jiibell | has collected 42 cases of poisoning
by this agent, 13 of which were fatal* One of these cases was suicidal^
the rest aeci dental.
§ 240. Effects of Poigoning by Nitro-benzene.— Nitro-benzene is a
very powerful poisoiii whether Uiken in the form of vapour or as a liquid.
The action of the vapour on animals has been studied by Eulenberg §
• Op, cit.,l |.. 310.
t Fit^fieljahrssc/iri/l far gt^r. Med. , Bd. xvi. i\ 1, 1856,
t Dk Ven/iJium^etK mil Blaumurc H, NUrQ-benml in fortnsisch^r Btskhtmg^
Erlatiget)^ 1876.
I G9vm'h$ ffifgiene, B. 607, B«rliu, IS 76*
13
194
P0I80S3: THEIR KFFKCT8 AND DETKCTION.
[§ 241.
aad others. One experiment will serve as an illustration- Fifteen
grms. of nitra-benzene were evaporated on warm gand undei* a glass
shade, into which a cat waa introduced. There was immediately ob*
served in the animal much salivatioUj and quickened and laboured
breathing. After thirty minutes' exposure, on removing the shade to
repeat the do@e of 15 gnns^i the cat for the moment escaped. On being
put back there waa again noticed the salivation and running at the eyea,
With giddineas, and repeated rising and faUing, The animal at last,
about one hour and forty minutes after the first dose, succumbed with
dyspnoea, and died with progresaive paralysis of the respiration, The
membranes of the brain were found gorged with blood, the lungs liver-
coloured, the raucous membrane of the trachea^ — to the finest subdivisions
of the bronchia — ^reddened, iutkmed, and clothed with a fine frothy
mucua. The left side of the heart was filled with thick black blood.
The bladder contained S grms. of clear urine, in which aniline was dis-
covered * There was a notable smell of bitter almonds.
§ 241. The effects of the vapour on man are somewhat difi'erent in
their details to those just described. In a remarkable case related by
Dr. IjCtheby, a man, aged 42, had spilt some nitro-benzene over his
clothes. He went about several hours breathini; an atmosphere of nitro-
benzene ; he then became drowsy, his expression wa^^ stupid, and his gait
uusteiidj, presenting all the appearances of intoxication. The stupor
suddenly deepened into coma, and the man died ; the fatal course being
altogether about nine hours — viz., four hours before coma, and five
hours of total insensibility.
An interesting case of poisoning by the vapour is recorded by Taylor.*
A woman, aged 30, tasted a liquid used for flavouring pastry, which was
afterwards chemically identified as pure nitro-benzene. She immediately
spat it out, finding that it had an acrid taste, and probably did not
awallow more than a drop. In replacing the bottle, however, she spilt
about a tables poonful^ and allowed it to remain for some minutes ; it was
a small room, and the vapour rapidly pervaded it, and caused illness in
herself as well as in a fellow -servant. She had a strange feeling of
numbness in the tongue^ and in three hours and a quarter after the
accident was seen by a medical man ; she then presented all the appear-
ances of pnissic acid poison ing. The eyes were bright and glassy, the
features pale and ghastly, the lips and nails purple as if stained with
blackberries, the skin clammy, and the pulse feeble ; but the mind was
then clear* An emetic was administered, but she suddenly became
unconscious ; the emetic acted, and brought up a fluid with an odour of
nitro-benzene. The stomach-pump was also used, but the liquid obtained
had scarcely any odour of nitro- benzene. In about eleven hours con-
• P<nm7i», Third Edition, p» m&.
1 242.]
NITRO-BENZIHE.
195
aoioitsness returned, and in about seventeen Koiirs she parti ally recovered
but oomplamed of Hashes of light aud strange colours before her eyes.
il©cx>v©i7 wm not complete for weeks. In this case the small quantity
swallowed would probably of itself have produced no symptouis, aod the
effects are to be mainly ascribed to the breathing of the vapour.
§ 24*2. The Hqntd, when swallowed ^ acts almost precisely in the same
way as the vapour, and the symptoms resemble very much those pro-
duced by prussic acid. The great distinction between pru^sio acid and
nitro-benzene poisoning is that^ in the latter, there i^ an interval between
the taking of the poison and ita eflfeuta. This is, indeed^ one of the
strangest phenomena of iiitro-bonzene potsonini^, for the personf after
taking it, may appear perfectly well for perioila varying from a quarter
of an hour to two or three hours, or even longer, and then there may be
most alarming symptom a, followed by rapid death, Poisoniog by nitro-
benzene satisfies the ideal of the dramatist^ who requires, for the pmrposcs
of his plot, poisons not acting at onoe, but with an interval sufiiciently
prolonged to admit of lengthy rhapsodies and a complicated iffhiouement.
On drinking the poison there is a burning taste in the mouth, shortly
followed by a very striking blueness or purple appearance of the Hps,
tongue, skin, nails, and even tlie conjunctivae. This curious colour of
the skiu has, in one or two instances^ been witnessed an hour before any
feeling of illness manifested itself; vomiting then comes on, the vomited
matter smelling of nitn>benzene. The skin is cold, there is great de-
pression, and the pulse is small and weak. The respiration h affected,
the breathing Ijeing alow and irregular, the breath smelling strongly of
the liquid, and the odour often persisting for days. A further stage is
that of loss of consciousness, and this comes on with all the suddenness
of a fit of apoplexy. The coma is also similar in appearance to apoplectic
eoma, but there have frequently been seen trismus and convulsions of the
extremities. The pupils are dilated and do not react to light, and reflex
sensibility is sometimes completely eitinguished. Cases vary a little tti
their main features ; in a few the blue skin and the deep sleep are the
only symptoms noted. Death, for the most part, occurs after a period of
from eight to twenty-four hour« (occasionally as soon as four or Hve
hours) after taking the poison.
From the following remarkable train of symptoms in a dogj it is
probable, indeed, that uitro- benzene, taken by a human being, might
prod nee death, after a rather prolonged period of time, by its secondary
effects : — To a half-bred greyhound * were administerecl 15 grms. of nitro-
benzene, when shortly after there were noticed nmch aalivalion, shiver-
ing, and muscular twitchings. The same dose was repeated at the end of
five, of seven, and of eight hours respectively, so that the dog altogether
196
POISONS: THEIR BFyiCTS AND DETECTION.
[§ 243-
took 60 grms., but with no other apparent symptom than the profuse
salivation. On the following daj, t1ie dog voided a tapeworm ^ vomit*
ing aupervened ; the heart*8 action was quickened, and the breathing
difficult ^ coDViilsions rollowed, and the pupik were seen to be dilated.
For eight days the dog snflfered from dyspncea, quickened pulse, shivering
of the legs or of the whole body, tetanic spasms, bloody [notions, great
thirst and debility. The temperature gmdually sank under 25", and the
animal Hnally died. The autopsy showed, as the most striking change^
the whole mucous membrane of the intestinal tract covered with a yellow
layer, which chemical analysis proved to be caused by picric acid, and in
the urine, liver, and liinga aniline waa discovered,
I 243. Fatal Dose. — ^Tt is probable, from recorded cases, that 1 grm*
(15*4 grains) would he quite sufficieut to kill an adult, and, under
favourable circumstances, less than that quantity. It would seem that
spirituous liquids especially hasten and intensify the action of nitro-
benzene, so that a drunken person, ceteris pnribtis, taking the poison with
ipirits^ would be more afTected than taking it under other conditions.
In a case related by Stevenson,* in which so small a quantity as I '74
grm. was t^ken in seven doses, spread over more than forty-eight hours,
there were yet extremely alarming symptoms, and the patient seems to
have had a narrow escape. On the other hand, a woman admitted into the
General Hospital, Vienna, took 100 grms, (about 3 J ozs.) and recovered ;
on admission she was in a highly cyanotic condition, with small pulse,
superficial respiration, smd dribbling of urine, which contained nitro*
beuF^ol, Artificial respiration was practised, and camphor injections were
adminiBtered, Under this treatment consciousness was restored, and the
patient recovered* On the fourth day the urine resembled that of a case
of cystitis (Lancet^ Jan. 16, 1894), The quantity of nit ro-benzene which
would be fatal, if breathed, is not known with any ac^curacy,
* Tkifi case is not uninteresting. Through a mUtake 111 r^cUn^ an extremely
illegihle prescription, M. S, 8., ©t, 21, w*s supphed by a druggist with the following
miiture : —
5 Benzole- Nit, 5iij,
01. ^tenth, pep., 5^
Oh Olivffi, 3)t,
gutt. xxx.^ L da.
He took on siigar eeven doacs, eiM^h of 20 minims, equalling in &I1 23 min. (or by
weight 27 '1 grains = 1 "74 grm.) ol" nitro-henzeue — vji., tlireff doR^s on the first day j
three on the second, and one on the moniing of the thiid day. The Jirst two
days he was observed to be looking pale and ill, but went on with his work until the
seventh dofie, which he took on the third day at 9 A. if. About 2 F^M. (or »ii
hours after taking the Beventh dow)^ he fell down insensible, the body }^le hlue,
and with all the symptoms already described id the taict, and usually seen in nitro-
benKefie poisoning. With suitable treatment he recovered. The next morning,
ftfom 8 OTinceB of urine some nitro^ benzene was extracted by nbaking with chloruform*
— Thos. Stevenaon, 11 D,, in fl^y*« MospUai Riports, MS., vol xxi,, lS7a.
§ 244-246.]
NITRO-BKNZENE,
§ 2i4. Pathological App^u'ances. — Tbe more obaractertstic appear-
ances seem to bo, a dark brown or even black colour of the blood, which
coagulates with diffictiUy (ao appearance of the blood that lias even been
noticed during life), venouai hjpereemia of the bruin and its membniuea,
and geDera! venous engorgement. In the stomachy when the flnid has
been Bwallowed^ the mucous membrane is somettraes reddened diffusely ,
and occasionally shows eecbymoses of a punctiform ebaraeter.
§ 245. The essetitial action of nitro-henzeue is of considerable
physiological interest. The blood is certainly in some way changed, and
gives tbe spectrum of acid h^ematin.* Filehne has found that the blood
loses, in a great degree, the power of carrying and imparting oxygen to
the tissues, and its content of carbon dioxide is also hicreased. Thus,
tbe normal amount of oxygen gas which the arterial blood of a hound
wil] give up is 17 per cent; but in the case of a dog which had been
I>oi*ioned with nitro-benEene, it sank to I per cent. During the dyspnopa
from which the dog an lib red, the carbon dioxide exhaled was greater
than the normal amount, and the arterial blood (the natural content of
which should have been 30 per cent, of this gas) only gave up 9 per
cent. Filehne seeks to explain the peculiar colour of the skin by the
condition of the blood, but the explanation is not altogether satisfactory.
Some part of the nitro-benzene, without doubt, is reduced to aniline in
the bfxly — an assertion often made, and as often contradicted — but it has
been found in too many cases to admit of question. It would also seem
from the experiment on the dog (p. 19$)^ that a conversion into picric
acid is not impossible. A yellow colour of the skin and conjunctivBB, as
if ptcrio-acid-stained, has been noticed in men suffering under slow
poisoning by nitro- benzene*
§ 346. Detection and Separation of Nitrobenzene from tbe
Animal Tissues. — It is evident from the changes which nitro-benzene
may undergo that the expert, in any case of suspected nitro- benzene
poisoning, must specially look ( 1 ) for nitro-benzene, (2) for aniline, and
(3) for picric acid. The best general method for tbe separation of nitro-
benzene is to shake up the liquid (or finely -divided solid) with light
beuzoline (petroleum ether), which readily disaolves nitro-bcnKene. On
e?apomtion of the petroleum etheri the nitro-benzene is left, perhaps
miied with fatty matters. On treating with cold water, the fats rise to
the surface, and the nitrobenzene sinks to the bottom ; so that by means
of a separating funnel, the nitro-henzene may be easily removed from
animal fats. The oily drops, or line precipitate l>elieved to be nitro-
benzene, may be dissolved in spirit and reduced to aniline by the use of
nascent hydrogen, developed from iron filings by hydrochloric acid, and
* Filehae, W,, '*Ueber div Giftwirkungeu dca KitrobpiiwK" j^A^A^/ir e»7»er,
I^thQL u, I%arm., ix. 320.
198 POISONS: THBIR EFFECTS AND DETECTION. [§ 247.
the fluid tested with bleachiug-powder ; or the aniline itself may be
recovered by alkalising the fluid, aod shaking up with ether in the
separation tube (p. 1 63) ; the ether dissolves the aniline, and leaves it,
on spontaneous evaporation, as an oily yellowish mass, which, on the
addition of a few drops of sodic hypochlorite, strikes a blue or violet-
blue — with acids, a rose-red — and with bromine, a flesh-red. It gives
alkaloidal reactions with such general reagents as platinum chloride,
picric acid, etc. Aniline itself may be extracted from the tissues and
fluids of the body by petroleum ether, but in any special search it will
be better to treat the organs as in Stas' process — that is, with strong
alcohol, acidified with sulphuric acid. After a suitable digestion in this
menstruum, filter, and then, after evaporating the alcohol, dissolve the
alcoholic extract in water; alkalise the aqueous solution, and extract
the aniline by shaking it up with light benzoline. On separating the
benzoline, the aniline will be left, and may be dissolved in feebly-acid
water, and the tests before enumerated tried.
Malpurgo* recommends the following test for nitro-benzene : — 2
drops of melted phenol, 3 drops of water, and a fragment of caustic
potash are boiled in a small porcelain dish, and to the boiling liquid the
aqueous solution to be tested is added. On prolonged boiling, if nitro-
benzene is present, a crimson ring is produced at the edges of the
liquid ; this crimson colour, on the addition of a little bleaching-powder,
turns emerald-green.
Oil of bitter almonds may be distinguished from nitro-benzcDe by
the action of manganese dioxide and sulphuric acid ; bitter almond oil
treated in this way loses its odour, nitro-benzene is imaltered. To apply
the test, the liquid must be heated on the water-bath for a little time-
XL— Dinitro-Benzol.
§ 247. Dinitro-benzol, C^jH4(N02)2 (ortho-, meta-, para-). — The ortho-
compound is produced by the action of nitric acid on benzol, aided by
heat in the absence of strong sulphuric acid to fix water. Some of the
paradinitro-benzol is at the same time produced. The meta-compound
is obtained by the action of fuming nitric acid on nitro-benzol at a boiling
temperature.
The physical properties of the three dinitro-benzols are briefly as
follows ; —
Ortho-d. is in the form of needles; m.p. 118".
Meta-d. crystallises in plates ; m.p. 90'.
* Zeit, anal, Chem., xxxii. 235.
§ 2480
DIKITRO-BBNZOL.
199
Para-d. crystrallisei, like the ortho-compoimd, in needles, but the
melting point is much higher, 171° to 172°»
JiiBt as nitro-hen^ol bj ret^ notion yields aniline, so do the nitro-
beniols on reduction jield ortho-, meta-, or para-phenylene diamitieB,
Me ta- phenyl ene diamine is an excellent test for nitrites ; and, since
the <x>mmeroial varieties of dinitro*b€naiol consist either mainly or in part
of metaHiinitro- benzol, the toxicological detection h fairly simple^ and is
based upon the conversion of the dinitro-ben^ol into meta-phenyleue-
diamine.
Bimtro-ben^l is at present largely employed in the manufacture of
eiplodyesy such as roburite, sicherheit, and others. It has produced
much illness among the workpeople in raanufacbones, and amongst
miners whose duty it has been to handle such exploBivea.
g 248* Effects of DmitTO - benzol. —Huber * finds that if dinitro-
benzol is given to frogs by the mouth in doses of from 100 to 200
mgrras*, death takes phice in a few hours. Doses of from 2*5 to 5
mgrms, cause general dalnesa, and ultiumtely complete paralysisi and
death iu from one to six days.
Rabbits are killDd by doses of 400 mgrms,, in time varying from
twenty-two hours to four days.
In a single experiment on a small dog, the weight of which was
5525 grms., the dog died in six hours after a dose of 600 mgrms.
It is therefore probable that a dose of 100 mgrms, per kilo, would
kill most warm-blooded animals.
A transient exposure to dinitro-beuzol vapours in man causes serious
symptoms ; for instance, in one of Huberts caseSi a student of chemistry
had been engaged for one hour and a half only in preparing dinitro-
bemeolj and soon afterwards his comrades remarked that his face was of
a deep blue colcmr. On admission fco lioapital^ on tlie evening of the
same day, he complained of slight headache and sleeplessneaa ; both
cheeks, the lips^ the muscles of the ear, the mucous membrane of the
lip8 and cheeks, and even the tongue, were aU of a more or less intense
bhie-grey colour. The pulse was dicrotic, 124; T. 37■2^ The next
morning the pulse was slower, and by the third day the patient had
recovered.
Excellent accounts of the ei^'ecta of dinitro-beuEol in roburite factories
have been published by Dr. Rosa t and Professor White, J of Wigan*
Mr. Simeon 8ne1l§ has also publish etl some most interesting cases of
illness, cases which have been as completely investigated as possible*
• " Bmtmgt) mr Giftwlrkaiig de« DinitrobenKala,^' A. Huber, VirahoVa Arthiv,
M cxxvLa 240, 1S91.
t M^itml Chrofikl^, 1880, 89* t Pracliiif>7^, 1880, iL 16.
g Brii. Mtd^ Jmtm.t M&ivh 8, ]S9I»
200
POISONS: THEIR EFFECTS AND DETECTION.
[§ 249.
As an example of the symptoms produced, one of Mr. Snell's oases may
be here quoted.
C. F. W., aged 38, consulted Mr. Snell for his defective sight on
April 9, 1892. He had been a mixer at a factory for the manufacture
of explosives. He was jaundiced, the conjunctiva yellow, and the lips
blue. He was short of breath, and after the day's work experienced
aching of the forearms and legs and tingling of the fingers. The urine
was black in colour, of sp. gr. 1024 ; it was examined spectroscopically
by Mr. MacMunn, who reported the black colour as due neither to
indican, nor to blood, nor bile, but to be caused by some pigment be-
longing to the aromatic series. The patient's sight had been failing
Diagram of Visual Field.
since the previous Christmas. Vision in the right eye was 7^, left -^j^ ;
both optic papillaB were somewhat pale. In each eye there was a central
scotoma for red, and contraction of the field (see diagram). The man
gradually gave up the work, and ultimately seems to have recovered.
It is, however, interesting to note that, after having left the work for
some weeks, he went back for a single day to the ** mixing," and was
taken very ill, being insensible and delirious for five hours.
§ 249. The Blood in Nitro-benzol Poisomng.— The effect on the
blood has been specially studied by Huber.* The blood of rabbits
poisoned by dinitro-benzol is of a dark chocolate colour, and the micro-
scope shows destruction of the red corpuscles ; the amount of destruction
may be gathered from the following : — the blood corpuscles of a rabbit
before the experiment numbered 5,888,000 per cubic centimetre; a day
* Op, eiL
S 2S0.1
DINITBO-BENZOL.
20J
»fter the experimeut 4,856,000; a day later 1,004,000; on the third
day the rabbit died.
In one rabbit, although the corpuscles sank to 1,416,000, yet re-
covery took place.
Dr. MacMunn * has examined specimens of blood from two of Mr.
Snell's patients [ he found a distinct departure from the normal ; the red
oorpuBcles were smaller than usual, about 5 or 6 ^ in diameter, and the
appearances were like thoae seen in pernicious aniemia- Huber, in some
of his experiments on animals, found a spectroscopic change in the
blood, viz,, certain absorption bands, one in the red between C and D,
and two in the green between D and E ; the action of reducing ag^enta
on this dinitro benzol blood, as viewed in a spectroscope provided with
a scale in which C— 48, D = 62, and E = 80*5, was as follows : —
DIuitro- Bands*
In Red.
50-62
In Green,
62-66 70-77
fter NH^SO^,
6a-55
62-60 70-77
,. NH„ /
54-&8
60-65 70^77
,. NHjS04+NH5j,
62-65
eO-65 70-77
Taking the symptoms as a whole, there has been noted :— a blue
colour of the lips, not un frequently extending over the whole face, and
even the conjuuctivee have been of a marked blue colour, giviug the
sufferer a strange livid appearance. In other cases there have been
jaundtoe, the conjnnctivse and the skin generally being yellow, the lips
blue. Ocoasionally gastric symptoms are present. Sleeplessness is
common, and not unfrequently there is some want of muscular oo*
ordiDation, and the man staggers as if drunk« In more tban one case
there has been noticed sudden delirium. There is in chronic oases always
more or less antemia, and the urine is remarkable in its colour, which
ranges from a slightly dark hue up to positive blackness. In a large
proportion of cases there is ophthalmic trouble, the characteristics of
which (according to Mr* Snell) are "failure of sight, often to a consider-
able degiee, in a more or less equal extent on the two sides ; concentric
attraction of visual field with, in many cases, a central colour scotoma i
enlargement of retinal vessels, CBpecially the veins; some blurring^
never extensive, of edges of di^c, and a varying degree of pallor of its
surface — the condition of retinal vessels spoken of being observed in
workers with the dinitrobeuzol, independently of eompluints of defective
sight Cessation of work leads to recti very."
g 250. BetectioQ of Dinitro-benzol. — ^Dinitro-ben^ol may be detected
in urine, in blood, and in fluids generally^ by the following process:^
Place tinfoil in the fluids and add h ydi-oohloric acid to strong acidity ;
• Op. «l.
202 POISONS: THEIR EFFECTS AND DETECTION. [§ 251, 252.
after allowing the hydrogen to be developed for at least an hour, make
the fluid alkaline by caustic soda, and extract with ether in a separating
tube; any metaphenylene - diamine will be contained in the ether;
remove the ether into a flask, and distil it off; dissolve the residue in
a little water.
Acidify a solution of sodium nitrite with dilute sulphuric acid ; on
adding the solution, if it contains metaphenylene-diamine, a yellow to
red colour will be produced, from the formation of Bismarck brown
(triamido-phenol).
XII.— Hydrocyanic Acid.
§ 251. Hydrocyanic Add (hydric cyanide) — specific gravity of liquid
0-7058 at IS*" C, boiling-point 26-5' (SO* F.), HCy = 27— The anhy-
drous acid is not an article of commerce^ and is only met with in the
laboratory. It is a colourless, transparent liquid, and so extremely vola-
tile that, if a drop fall on a glass plate, a portion of it freezes. It has a
very peculiar peach-blossom odour, and is intensely poisonous. It
reddens litmus freely and transiently, dissolves red oxide of mercury
freely^ forms a white precipitate of argentic cyanide when treated with
silver nitrate, and responds to the other tests described hereafter.
§ 252. Medicinal Preparations of Frussic Acid.— The B.P. acid is
a watery solution of prussic acid ; its specific gravity should be 0*997,
and it should contain 2 per cent, of the anhydrous acid ; 2 per cent, is
also the amount specified in the pharmacopoeias of Switzerland and
Norway, and in that of Borussica (VI. ed.) ; the latter ordains, however,
a spirituous solution^ and the Norwegian an addition of 1 per cent, of
concentrated sulphuric acid. The French prussic acid is ordered to be
prepared of a strength equalling 10 per cent.
The adulterations or impurities of prussic acid are hydrochloric, sul-
phuric,* and formic acids. Traces of silver may be found in the French
acid, which is prepared from cyanide of silver. Tartaric acid is also
occasionally present. Hydrochloric acid is most readily detected by
neutralising with ammonia, and evaporating to dryness in a water-bath ;
the ammonium cyanide decomposes and volatilises, leaving as a saline
residue chloride of ammonium. This may easily be identified by the
precipitate of chloride of silver, which its solution gives on testing with
silver nitrate, and the deep brown precipitate with Nessler solution.
Sulphuric acid is, of course, detected by chloride of barium ; formic acid
by boiling a small quantity with a little mercuric oxide ; if present, the
* A trace of sulphuric or hydrochloric acid should not be called an adulteration,
for it greatly assists the preservation, and therefore makes the acid of greater thera-
peutic efficiency.
I 2S30
HYDROCYANIC ACID.
203
oxide win be reduced, and metallic noercurj fall ss a grey precipitate.
Silver, tartaric acid, aud atiy other fixed impurities are detected by
evapomtiug the acid to dryness^ and eiamiDiDg any reBidue which may
be left. It may be well to give the various strengths of the acids of
uomiiierce in a tabular form : —
Per cent*
British PhannacopcEiii, Switzcrlajjdi mud Bur. (vj),
France,
VAuqiielin'B Add,
Scheele^i |,
Biner*s ,,
Kobiq net's ,,
Scbmeder*s , ,
Duflofi' ,,
Pf»rfi
Kollor'B ,,
Iti Euglish commerce, the analyst will scarcely meet with any acid
stronger than Scheele'e 5 per centt
Impure oil of bitter almonds contains hydric cyanide iu variable
quantity, from 5 per uenL up to 14 per cent. There is an officinal
preparation obtained by digeeting cherry-laurel leaves in water, and then
distilling a certain portion over. This Aqua Laum-cerasi belongs to the
old ficbool of pharmacy, and is of uncertain strength, but varies from '7
to 1 per ceuL of HCN.
§ 253, PoiEoning by FruBsic Add. — Irrespective of suicidal or
criminal poisoning, accidents from pruasic acid may occur —
L From the use of the cyanides lu the arts.
2. From the somewhat extensive distribution of the aeld, or rather
of prussic-ac id- producing substances in the vegetable kingdom.
L In the Arts.— The galvanic silvering J and gilding of metals,
photography, the colouring of black silks, the manufacture of Berlin
blue, the dyeing of woollen cloth, aud in a few other manufacturing
proceeisee, the alkalino cyanides are used, and not unfrequently fumes of
prussic acid developed.
2. In the Animal Kingdom.— One of the myriapods {Chiloiffuith4m)
contains glands at the roots of the haire, which secrete prussic acid;
when the insect is seized, the poisonous secretion is poured out from the
iKHialled /(yranfhia rejnif/naforia,
3« In the Vegetable Kingdom. — A few plants contain cyanides, and
* Strength very uncertaiii.
t Eahlbftum now \i»\M a 12 pef cent, solution,
t The prejjarAtion used for the silvering of C4}|j{)er vi^saalB is a solutioa of cj&uide
of silver In iratassic oyanid*, to wMcL m added finely powdered cli»lk, Mauipu*
Utioua with this fluid v&si]y develop hydroejanic ftcid fumcflj whlcli, in oui? caao
rekted by Martin {AerizL IttUlii^tttihlt p, 185p 1872}» w©ri poiferful enough U>
produce symptoaii of (Kiisoniug,
204 POISONS: THEIR EFFECTS AND DETECTION. [§253-
many contain amygdalin, or bodies formed on the type of amygdalin. In
the presence of emulsin (or similar principles) and water, this breaks up
into prussic acid and other compounds — an interesting reaction usually
represented thus —
CaoH^yNOii + 2H2O -> CNH + C^Ufi + 2C«Hi30^
1 equivalent of amygdalin — t.e. 457 parts — yielding 1 equivalent of
CNH or 27 parts ; in other words, 100 parts of amygdalin yield theo-
retically 5 '909 parts of prussic acid,* so that, the amount of either being
known, the other can be calculated from it.
Dunstan and Henry t have discovered three glucosides: —
** dhurrin " in the young plants of the great millet, Sorghum vulgare ;
"lotusin" in Zjoitis arahiens^ a legume indigenous to Egypt; and
" phaseo-lunatin " in the beans of the wild Phaseolus lunaivs,
Loiusifij CggHgjOjgN, is a maltose-cyan-hydrin, one molecule yielding
on hydrolysis, 1 molecule of hydric cyanide, 2 of dextrose, and 1 of
lotoflavin.
Dhurrin^ Cj^HiyOyN, yields on hydrolysis, hydric cyanide, hydroxy-
benzaldehyde, and dextrose,
Phaseo-lunatin^ Ci^Hj^OgN, may be obtained in rosettes of needle-like
crystals, m.p. 141*0*. Hydrolysis breaks the glucoside up into hydric
cyanide, acetone, and dextrose,
CioHiyOeN + H2O -> HON + C^'B.^^O^ + (CH3)2CO.
F. B. Power and F. H. Lees| have isolated from the seeds
of Gynocardaia odorata a glucoside which they name gynocardin,
CigHigOgN, on hydrolysis yielding hydric cyanide, dextrose, and an
acid.
Many cases of death occurring among cattle fed on immature
sorghum have been shown by J. C. Brunnich § to be due to " dhurrin.
Qreshoff|| has discovered an amygdalin-like glucoside in the two
tropical trees Pygeum parviflorum and P. latifolium. The same author
states that the leaves of Gyvinema laiifolium^ one of the Asclepiads,
yields to distillation benzaldehyde hydrocyanide. Both Lasia and
CyrtoapermOy plants belonging to the natural family of the Orontads,
* According to Liebig and Wohler, 17 grms. of amygdalin yield 1 of prussic acid
{i.e. 5*7 per cent.) and 8 of oil of bitter almonds. Thirty-four parts of amygdalin,
mixed with 66 of emulsin of almonds, give a fluid equalling the strength of acid of
most pharmacopoeias, viz., 2 per cent.
t Proe, Roy, Soc, Ixviii, 1901 ; IxxiL, 1908.
t Joum, Chem, Soc, Ixxxix., 1906. § Ih,, IxxxiiL, 1908.
II M. Greshoff~*'£rster Bericht iiber die Untersuchung von Pflanzenstoflen
Niederlandisch-Indiens." MiUheilungen aus dem ch$mi9ch - pharmakol4>gi8chen
Laboratan'um des botan, OarUns <Us Staates, vii, Batavia, 1890, Niederlandisch.
Dr. Greshoff^s research indicates that there are several other cyanide-yielding plants
than those mentioned in the text
S 2S4-]
HYDROCYANIC ACIB,
205
contain in theii' flowers potass ic cyanide, Pnwfiwn edulet according t<3
Greshoff^ containa so much potassic cyanide that he was able to prepare
a considerable quantity of that salt: from one sample of tbe plant. An
Indian plant (Hfjdnocar^mn inehriam) also contains a cyanide, and has
been used for the puqx>se of destroying fish. Among the TiUads,
GreshoflP found that Echinocarptis Sigun yielded hydrocyanic acid on
distillation. Even the common linseed contains a glticoside which
breaks up into Bugarj prussic acid, and a ketone.
The following plants, with many ofcherSj all yield, by appropriate treat-
ment, nvore or less pniaaic acid ; — Bitter alraonda {Amtjgdalus coTmnunw);
the Ajnt/gdaluii permca; the cherry laurel {Pnmm lauroceramm) ; the
kernels of the plum {Pninun dommtira} ; the bark, l^-vesj flowers, and
fntit of the wild service-tree {Prtmm padm) ; the kernels of the common
cherry and the apple ; the leaves of the Pmnus capHmfa ; the bark of
the Pr, mrginiana \ the flowers and kernels of the Pr, spimim ; the
leaves of the Cerasus acuta; the bark and almost all parts of the
Borbm aucuparia^ S, hyhmla^ and S. toijuinalis ; the yonng twigs of
the Craitpgus oxt/acantha ; the leaves and partly also the ttowei^
of the shrubby SpirmcBt such as Spirtt^ artmcus^ S. mrhifolia^
and 5i japonim;^ together with the roots of the bitter and sweet
Casmva.
In only a few of these, however, baa the exact amount of either
pmssic aeid or amygdalin been determined j 1 gnn. of bitter almond
pulp is about equal to 2| mgmis* of anhydroua prnssic imd. The
kernels from tlie stones of tbe cherry, according to GeiBeler, yield 3
per cent, of amygdalin ; therefore, 1 grm. equals l^T mgrm» of HON,
§ 254. The wild service-tree {Prunuit padnf^) and the cherry 4aurcl
{Prunu» laurocifvoiiis) contain, not amygdalin but a compound of
amygdalia with amygdalic acid ; to this has been given the name of
laurocerasin. It was formerly known as amorphous amygdalin ; its
formula is C^uH^^NOj^; 933 parts are equivalent to 27 of hydric cyanide
—that is, 100 parts equal to 2^89*
In the hark of the service-tree Lebmann found *7 per cent, of
laurocerasin ( = '02 HON), and in the leaves of the cherry -laurel 1'3S
percent. (=039 HCN).
Fran c is J t in a research on the prussic acid in cassava root, gives as
the mean in the sweet cassava '0168 per cent, in the bitter '0275 per
cent, the maximum in each being respectively 0238 per cent, and
*0442 per cent. The bitter-fresh cassava root has long been known as
a very dangerous poison ; but the sweet has hitherto been considered
* The bark and green parts of the PruAm atium, L, , Prunus mahaleb, L. , and
herbaeeous SpirnEm yield no pmasic acid.
t ** On Prussic Acid from Csasuva,** Anulyd, April 1877, p. 5.
206
POISONS: THEIB EFFECTS AND DETECTION.
[§ 255.
harmless, although it is evident that it also contains a considerable
quantity of prussic acid.
The kernels of the peach contain about 2*85 per cent, amygdalin
( = •17 HON); those of the plum -96 per cent. ( = -056 HON); and
apple pips '6 per cent. ( = '035 per cent. HON). A. Hubert* has
found a few milligrammes of HON in 100 grammes of the young
shoots of Rihes rulyrum ; 0*04 per cent, in the embryo of the fruit of
Eriohotrya japonica^ and from 0*01 per cent, to 0-001 per cent, in
various parts of Aquilegia vulgaris at the commencement of vegetation.
It is of great practical value to know, even approximately, the
quantity of prussic acid contained in various fruits, since it has been
adopted as a defence in criminal cases that the deceased was poisoned
by prussic acid developed in substances eaten.
§ 255. Statistics. — Poisoning by the cyanides (prussic acid or
cyanide of potassium) occupies the third place among poisons in order
of frequency in this country, and accounts for about 40 deaths
annually.
In the ten years ending 1903 there were recorded no less than 536
cases of accidental, suicidal, or homicidal poisoning by prussic acid and
potassic cyanide. The further statistical details may be gathered from
the following tables : —
DEATHS IN ENGLAND AND WALES DURING THE TEN YEARS 1894-
1908 FROM PRUSSIC ACID AND POTASSIC CYANIDE.
Prussic Acid (Accident
OR Neqlioenob).
Males, .
Females,
Total,
17
19
Cyanide of Potassium (Accident
OR Neglioenoe).
Males, SO
Females, 5
Total,
85
Prussic Acid (Suicide).
Males, 272
Females, 22
Total,
294
Potassium Cyanide (Suicide).
Males,
Females.
Total,
166
21
187
To these figures must be added 1 case of murder by prussic acid.
In order to ascertain the proportion in which the various forms of
commercial cyanides cause death, and also the proportion of accidental,
suicidal, and criminal deaths from the same cause, Falck collated
twelve years of statistics from medical literature with the following
result : —
• Bull. Soe, Chim., iiL 19, 1898,
§ 2S6.]
HYDROCYANIC ACID.
207
In 51 oases of cjanide poisonings 29 were caused by potassic cyanide,
9 hj hydric cyanide, 5 by oil of bitter almonds, 3 by peaeh atones
(these 3 were children, and are classed as '^domestic/' that is, taking
the kernels as a food), 3 by bitter almonds (1 of the 3 suicidal and
followed by death, the other 3 ** domestic"), 1 by tartario acid and
potass ic cyanide (11 suicidal case, an apothecary)^ and 1 by ferro-cyanide
of potassium and tartaric ncid« Of the 43 cases first mentioned, 21
were suicidal, 7 criminal, 8 domestic, and 7 medicinal ; the 43 jmtients
were 24 men, 14 children, and 5 women*
The cyanides are very rarely used for the purpose of murder: a
poison which has a strong smett aud a perceptible taste, and which
also kills with a rapidity only eqimlled by deadly ballet or knife wo mid s,
betrays its presence with too many circnm stances of a tragic character
to find favour in the dark and secret schemes of those who desire to
take life by poison. In 793 poisoning cases of a criminal character in
France, 4 only were by the cyanides.
llydric and potass ic cyanides were once the favonrite means of
aelf-destr notion employed by suicidal photographers, chemists, scientific
medical men, and others in positions where such means are always at
hand ; but, of late years, the popular knowledge of poisons haa
increased, and self -poisoning by the cyanides scarcely belongs to a
particular class. A fair proportion of the deaths are also due to
accident or unfortunate mistakes, and a still smaller number to the
immoderate or improper use of cyanide-containing vegetable products*
§ 256, Acddental and Criminal Foisouing by Prufisic Acid.— -^The
poison is almost always taken by the mouth into the stomach, but
occaaionally in other ways — such, for example, as in the case of the
illnstrious chemist, Schecle, who died from inhalation of the vapour ol
the acid which he himself discovered, owing to the breaking of a flask.
There is ako the case related by Tardieu, in which cyanide of potassium
was introduced under the nails ; and that mentioned by Carriere,* in
which a woman gave herself^ with suicidal intent, an enema containing
eyauide of potassium. It was been shown by experiments, in which
every care was taken to render it impossible for the fumes to be
inhaled, that hydrocyanic acid applied to the eye of warm-blooded
animals may destroy life in a few minutestt
With regard to errors in dispensing, the most tragic case on record
is that related by Arnold : J — A pharmaceutist had put in a mijctnre
* ** EmpuiiiimQemeiit pAr 1« Ojfanutv de potAfiaiimi,~gtilr]soii/* Btdht. ijin^rtU
d4 Thirap., 1860, No, SO,
t N* Grehaut, €o^n>pL rcwL St>c. MioL [9J, xi. 04, (if*.
X Antoldf A. B», ** Cu« of Paiiioning by the Cy&nicifi uf Put^smm/' Artier,
208 POISONS : THSnt EFFECTS AND DETECTION. [§ 257, 258.
for a child potassio cyanide instead of potassic chlorate, and the chOd
died after the first dose : the chemist^ however, convinced that he had
made no mistake, to show the harmlessness of the preparation, drank
some of it, and there and then died ; while Dr. Arnold himself, in-
cautioosly tasting the draught, fell insensible, and was unconscious for
six hours.
§ 257. Fatal Dose. — Notwithstanding the great number of persons
who in every civilised country fall victims to the cyanides, it is yet
somewhat doubtful what is the minimum dose likely to kill an adult
healthy man. The explanation of this uncertainty is to be sought
mainly in the varying strength of commercial prussic acid, which
varies from 1*5 (Schraeder's) to 50 per cent. (Robiquet's), and also in
the varying condition of the person taking the poison, more especially
whether the stomach be full or empty. In by far the greater number,
the dose taken has been much beyond that necessary to produce death,
but this observation is true of most poisonings.
The dictum of Taylor, that a quantity of commercial prussic acid,
equivalent to 1 English grain (65 mgrm.) of the anhydrous acid, would,
under ordinary circumstances, be sufficient to destroy adult life, has
been generally accepted by all toxicologists. The minimum lethal dose
of potassic cyanide is similarly put at 2*41 grains ('157 grm.). As to
bitter almonds, if it be considered that as a mean they contain 2*5 per
cent, of amygdalin, then it would take 45 grms., or about 80 almonds,
to produce a lethal dose for an adult ; with children less — in fact, 4 to
6 bitter almonds are said to have produced poisoning in a child.
§ 258. Action of Hydric and Potassic Cyanides on Living Organisms.
— ^Both hydric cyanide and potassio cyanide are poisonous to all living
forms, vegetable or animal, with the exception of certain fungi. The
cold-blooded animals take a larger relative dose than the warm-blooded,
and the mammalia are somewhat more sensitive to the poisonous action
of the cyanides than birds; but all are destroyed in a very similar
manner, and without any essential difference of action. The symptoms
produced by hydric and potassio cyanide are identical, and, as regards
general symptoms, what is true as to the one is also true as to the other.
There is, however, one important difference in the action of these two
substances, if the mere local action is considered, for potassic cyanide is
very alkaline, possessing even caustic properties. For instance, the
gastric mucous membrane of a woman, who had taken an excessive dose
of potassic cyanide on an empty stomach, was so inflamed and swollen,
that its state was similar to that induced by a moderate quantity of
solution of potash. On the other hand, the acid properties of hydric
cyanide are very feeble, and its effect on mucous membranes or on the
skin in no way resembles that of the mineral acids.
§ 2s8a, 259O
HYDROCYANIC ACIB,
209
It attacks the animal system hi two w&ya ; the one, a profoimd
interfetence with the ordinary metabolic changes ; the other, a paralysis
of the nervous centres. Schdnbein dbeovered that it affected the blood
corpiiacles in a peculiar way ; normal blood decomposes with great ease
hydrogen peroxide into oxygen and water. If to normal venous blood
a little peroxide of hydrogen be added, the blood at once becomes bright
red J bnt if a trace of prnsaic acid be present, it is of a dark brown
colour. The blood corpuscleB^ therefore, loJie their power of conveying
oxygen to all parts of the system, and the phenomena of asphyxia are
produced, Geppert * has proved that this in really the ease by showing,
in a aeries of researches, that, under the action of hydric cyanide, less
oxygen is taken up, and lessa carbon dioxide formed than normal, even if
the percentage of oxygen in the atmosphere breathed is artificially
increased. The deficiency of oxygen is in part due to the fact that
substances like lactic acid, the products of incomplete combustion, are
formed instead of COg.
At the same time the pT0boi>Ia8m of the tissues is pamlysed, and
unable to take up the loosely bound oxygen presented. This explains a
striking symptom which has been noticed by many observers, that is, if
hydrocyanic acid be injected into an animal, the venous blood becomes
of a bright red colour ; in warm-blooded animals this bright colour is
transitory, but in cold-blooded animals, in which the oxidation process is
slower, the blood remains bright red.
g 258a, Effect of Frussic Acid oil Lower Organisms, — In 1 to
430 dilution prussic acid annihilates the function of Dro^'-ra, In 1 per
1000 infusoria soon die, algse live longer. In a certain degree of dilution
yeast-cells are paralysed but not killed, for on removal to a nutrient
fluid, free from the acid, their activity is resumed.
§ 259, Symptoms obBerved in Aniinalg.— The main differences
between the aymptoms induced in cold-blooded and warm-blooded
animals, by a fatal dose of bydric cyanide, are as follows : —
The re,'ipiration in frogs is at first somewhat dyspnceie, then much
slowed, and at length it ceases. The heart, at first slowed, later contracts
irregularly, and at length gradually stop** ; bnt it may continue to beat
for several minutes after the respiration has ceased. But all these
progressive symptoms are without convulsion. Among warm-blooded
animals, on the contrary, convulsions are constant, and the sequence of
the symptoms appears to be — dyspncea, slowing of the pulse, giddiness,
falling down, then convulsions with expulsion of the urine and faeces ;
dilatation of the pupils, exophthalmue, and finally cessation of the pulse
and breath ing. The cotivulsions also frequently ^ms into general
• Oeppert, Ueber das fK«sffn der CJ^M-F^mJl ; mU Hner T^if, Berlin, 188© ;
S^.'AHt. au9M0chr.f. ktm^ Med., Bd. xv.
"4
2IO
POISONS: THEIR EFFECTS AND DETECTION.
[§260,
paralysis, with loss of red^x movements, weak, infrequent breathing^
irregular, quick, and very fre<iuent pulae, and cousiderablo diminution
of temperature.
The commeneement of the symptoms in animals is extremely rapid,
th© rapidity %^aryjng according to the dose and concentration of the acid.
It was formerly thought that the death from a large dose of the con-
centrated acid followed far more quickly than could be accounted for
hy the blood carrying the poison to the nervous centres ; but Blake was
among the fi r«t to point out that this doubt was not supported by facts
carefully observed, since there h always a sufficient interval between the
entry of the poison into the body and the tirat symptoms, to support the
theory that the poison b absorbed in the usual manner. Even when
Preyer injected a cubic centimetre of 60 per cent, acid into the jugular
vein of a rabbit, twenty-nine secands elapsed before the symptoms
commenced. Besides, we have direct expenments showing that the acid
— when applied to wounds in limbs» the vessels of which are tied, while
the free nervous communication is left open — only acts when the ligature
is removed. Magendie describes, in his usual graphic manner, how he
killed a dog by injecting into the jugular vein prussic acid, and ^^fhe
dog died imtmttl^, a» if druck by a cunnon baUt* but it is probable that
the interval of time wm not accumtely noted. A few seconds pass very
rapidly J and might l>e occupied even by slowly pressing the piston of
the syringe down, and in the absence of accurate measurements* it is
surprising how comparatively long intervals of time are unconsciously
shortened by the mind. In any case, this observation by Magendie has
not been confirmed by the accurate tests of the more recent experi-
menters ; and it is univerBally acknowledged that, although with strong
doses of hydric cyanide injected into the circulation — or, in other words,
introduced into the system — in the most favourable conditions for ita
speediest action, death occurs with apptilling suddenness, yet that it
takes a time sufficiently long to admit of explanation in the manner
suggested. This has forensic importance, which will he again alluded
to. Expenments on animals show that a large dose of a dilute acid
kills quite as quickly as an equivalent dose of a stronger acid^ and in
some cases it even seems to act more rapidly. If the death does not
take place within a few minutes, life may be prolonged for hours, and
even> in rare cases, days, and yet the result be death, Coullon poiaoned
a dog with prussic acid ; it lived for nineteen days, and then died ; but
this is quit^a an exceptional ciise^ and when the fatal issue is prolonged
beyond an hour, the chance of recovery is considerable,
§ 260. The length of time dogs poisoned by fatal doses survive, gener-
\l\y varies from two to fifteen minutee. The symptoms are convulsions,
isensibility of the cornea, cessation of respiration, and^ final ly, the heart
§ 261-1
HYDROCYAHTC ACID.
2Tf
Btrope — the heart contttniing to beat several m inn tea after the cessation
of the respirations.* When the doae is short of a fatal one, the
Bjmptoma are as follows : — Evident giddiness and distress ; the tongue
la protruded, the breath la taken in short, hurried g^ispa, there la saliva-
tioii, and convulsions rapidly set in, preceded, it may be, by a cry. The
couvulsioQs pass into paralysis and insensibility. After remaining in
this stiite some time, the animal again wakes up, as it were, very often
howls, and is again eonvnlsed ; finally, it sinks into H deep sleep, and
wakes up welL
Preyer noticed a striking diflTerence in tlie symptoms after section of
the vagua in animals, which varied iiecording to whether the poison was
adrainistered by the lungs, or subeutaneonsly, In the first case, if the
dose is small, the respi rut ions are dimititshed in frequency ; then this is
followed by normal breathing ; if the dose is larger, there is an increase
in the frequency of the respirations* I^stly^ if a very large quantity is
iiitrodluced into the lungs, death quickly follows, with reapiratious
diminished in frequency. On the other hand, when the poison is
injected subcutaneously, small doses have no influence on the breathing ;
but with large doses, there is an increase in the frequency of the respira*
tions, which sink again below the normal standard.
§ 261. Symptoms in Man.— When a fatal but not excessive doae of
either potasaic or hydrlc cyanide is taken, the sequence of symptoms is
as follows; — Salivation, with a feeling of constriction in the throat,
nausea, and occasionally vomiting. After a few minutes a peculiar con-
stricting pain in the chest is felt^ and the breathing is distinctly a lie ctecL
Giddiness and confusion of sight rapidly set in, and the person fails to
the gronnd in convulsions similar to those of epilepsy. The convulsions
are either genend, or attacking only certain groups of muscles ; there is
often true trismus, and the Jaws are so Ermly closed that nothing will
part them. The respiration is peculiar — the inspiration is short, the
expiration prolonged,! and between the two there is a long interval, ever
Incoming mora protracted j^s death is imminent. The skin is pale, or
blue, or gi'eyish-bhie ; the eyes are glassy and staring, with dilated
pupils ; the mouth is covered with foam, and the breath smells of the
poison ; the pulse, at first quick and small, sinks in a little while in
frequency, and at length cannot be felt. Involuntary evacuation of
fasces, urine, and semen is often obsen'ed, and occasionally there has
been vomiting, and a portion of the vomit has been aspirated into the
* H. Gr^lmttt, Qfmpi. M^^nd,, t cix, pp. 502, 603,
t In a<!iaBe quotiKl by Seidd (Moschka^s Handhneh^ p. 321), a man, 3^ y^fs of
•ge, fyur m live tninutes after swallowing 150 nigmis. anliydi^u* HCN in B[iirits, lny
•|i|iarently lif^^less, without jiuW or hreatliiug* After a few minutes was noticed an
eitmordiiuiij decip e^tfiimtiunf by trhich the riba were drawn in idmoi^t to the apiue^
Hid the chieet modf^ quits hollow^
212 POISONS: THRIB BFFECTS AND DETECTION. [§ 262.
air-passages. Finally, the convulsions pass into paralysis, abolition of
reflex sensibility, and gradual ceasing of the respiration. With large
doses these different stages may occur, but the course is so rapid that
they are merged the on^ into the other, and are undistinguishable. The
shortest time between the taking of the acid and the commencement of
the symptoms may be put at about ten seconds. If, however, a large
amount of the vapour is inhaled at once, this period may be rather
lessened. The interval of time is so short that any witnesses generally
unintentionally exaggerate, and aver that the effects were witnessed
before the swallowing of the liquid — '* As the cup was at his lips " —
" He had hardly drunk it," etc There is probably a short interval of
consciousness, then come giddiness, and, it may be, a cry for assistance ;
and lastly, there is a falling down in convulsions, and a speedy death.
Convulsions are not always present, the victim occasionally appears to
sink lifeless at once. Thus, in a case related by Hufeland, a man was
seen to swallow a quantity of acid, equivalent to 40 grains of the pure
acid — that is, about forty times more than sufficient to kill him. He
staggered a few paces, and then fell dead, without sound or convulsion.
§ 262. Tlie very short interval that may thus intervene between the
taking of a dose of prussic acid and loss of consciousness, may be utilised
by the sufferer in doing various acts, and thus this interval becomes of
immense medico-legal importance. The question is simply this : — What
can be done by a person in full possession of his faculties in ten seconds ?
We have found from experiment that, after drinking a liquid from a
bottle, the bottle may be corked, the individual can get into bed, and
arrange the bedclothes in a suitable manner ; he may also throw the
bottle away, or out of the window ; and, indeed, with practice, in that
short time a number of rapid and complicated acts may be performed.
This is borne out both by experiments on animals and by recorded
cases.
In Mr. Nunneley's numerous experiments on dogs, one of the
animals, after taking poison, *' went down three or four steps of the
stairs, saw that the door at the bottom was closed, and came back again."
A second went down, came up, and went again down the steps of a long
winding staircase, and a third retained sufficient vigour to jump over
another dog, and then leap across the top of a staircase.
In a remarkable case related by Dr. Guy,* in which a young man,
after drinking more wine than usual, was seized by a sudden impulse to
take prussic acid, and drank about 2 drachms, producing symptoms
which, had it not been for prompt treatment, would, in all probability,
have ended fatally — the interval is again noteworthy. After taking the
poison in bed, he rose, walked round the foot of a chest of drawers,
* Forensic MedieinCf 4th ed., p. 615.
§ 2630
HVDEOC¥ANIC ACID,
213
standing within a few yards of the bedside, phieed the stopper firmly
in the bottle, and then walked back to bed with the intention of getting
into it; but here a giddiness seized hiuij and be sat down on the edge,
and became insensible.
A case rehited by Taylor is still stronger* A woman, after swallowing
a fatal dose of essence of almonds, went to a well in the yard^ drew
water, and drank a oonaidet^ble quantity. Sh^ theu ascended two
flights of stairs and calked her child, again descended a flight of stair»,
fell on her bed, and died within half an hour from tbe taking of the
poiion.
Nevertheless, these cases and similar ones are ejEceptionalj and only
show what is possible, not what is usual, the rule being that after fatal
doses no voluntary act of significance — save, it may be, a cry for assist-
ance— is performed.*
Symptoms of poison in g by pruBsic acid produced from eating
substanoes containing tbe cyanide glucosides may occnr, and death
result hours after the ingestion of such substances, as illustrated by the
following interesting oases deaoribed by Dr. A, Robertson and A. J.
Wynne.t
In March 1905 a steamer brought to Rotterdam a cargo of ** kratok "
beans (Phfumilus lunalus) for the purpose of feeding cattle. A workman
(Bans) employed hi unloading took some of the beans and gave some
to a family named Van Oostende, Sunday, March 11, 12*30. Barin ate
some of the h^m^s which had been boiled ; in the evening he felt unwell,
became faint, had couvnlsious, and died about eleven hours after the meaK
The Van Oostende family, six in nnmber, four children and two adults,
partook of tbe beans about 12 noon of the same day; all became ill
three houi-s afterwards ; three of the children died, the rest recovered*
The beans had been softened by soaking in warm water and salt and bad
then been boiled ; the three children who died had no diarrhooa, those
who recovered had diarrhoea.
The unboiled beans yielded about 0-21 percent. HCN ; from the boiled
beans only tnicesof HCN could be obtained save by incubating for twenty-
four hours in neutral solution with emulsin, then 0*09 per cent, of HCN
was obtained ; from tbe intestines of the three children 3*0» 4*0,
and 6 '7 mgrms. of HCN were separated.
§ 203. Chronic poisoning by hydric cyatude is said to occur
among photographers, gilders, and those who are engaged daily in the
preparation or handling of either hydric or potasaic cyanides* The
* Dr. J, Autd, a Hyttgamn chemist, atatea thai cohalt Bitmte is an Glficacious
antidote to poisoning by either HCN or KCN* The brief intcTv&l bytw'cen the t4ikLng
of s fatnl dofla And death c&n, howovOT^ he rarely ntilised.^— i^rkr/, Jan. ttf, 1804.
214 POISONS: THEIR EFFECTS AND DETECTION. [§ 264.
symptoms are those of feeble poisoning, headache, giddiness, noises in
the ears, difficult respiration, pain over the heart, a feeling of con-
striction in the throat, loss of appetite, nausea, obstinate constipation,
full pulse, with pallor and offensive breath. Koritschoner * has made
some observations on patients who were made to breathe at intervals, .
during many weeks, prussic acid vapour, with the idea that such a
treatment would destroy the tubercle bacilli. Twenty-five per cent, of
those treated in this way suffered from redness of the pharynx, saliva-
tion, headache, nausea, vomiting, slow pulse, and even albuminuria.
§ 264. Post-mortem Appearances.! — If we for the moment leave
out of consideration any changes which may be seen in the stomach
after doses of potassic cyanide, then it may be affirmed that the
pathological changes produced by hydric and potassic cyanides mainly
coincide with those produced by suffocation. The most striking
appearance is the presence of bright red spots; these bright red
spots or patches are confined to the surface of the body, the blood
in the deeper parts being of the ordinary venous hue, unless, indeed,
an enormous dose has been taken; in that case the whole mass of
blood may be bright red ; this bright colour is due, according to
Robert, to the formation of cyanmethsemoglobin. The lungs and
right heart are full of blood, and there is a backward engorgement
produced by the pulmonic block. The veins of the neck and the
vessels of the head generally are full of blood, and, in like manner,
the liver and kidneys are congested. In the raucous membrane of
the bronchial tubes there is a bloody foam, the lungs are gorged, and
often oedematous in portions ; ecchymoses are seen in the pleura and
other serous membranes ; and everywhere, unless concealed by putre-
faction or some strong-smelling ethereal oil, there is an odour of hydric
cyanide.
Casper has rightly recommended the head to be opened and
examined first, so as to detect the odour, if present, in the brain.
The abdominal and chest cavities usually possess a putrefactive smell,
but the brain is longer conserved, so that, if this course be adopted,
there is a greater probability of detecting the odour.
The stomach in poisoning by hydric cyanide is not inflamed, but
if alcohol has been taken at the same time, or previously, there may be
more or less redness.
In poisoning by potassic cyanide, the appearances are mainly the
* Wiener klin. JVoch,, 1891.'
t Hydric cyanide has, according to C. Brame, a remarkable antiseptic action,
and if administered in sufficient quantity to animals, preserves them after death for
a month. He considers that there is some more or less definite combination with
the tissues.
§ 265-1
HYDROCYANIC ACID.
fS
same as those jimt detailed, with, it may be, the additioo of caustic
local action. There may, however^ be^ as in the case of a geiitlemati who
di*aok accidentally a cotiaidemble dose of potassic cyanide just after
a full meal, not the slighteat trace of any redueaB, still less of corrosion.
Here the contents of th© stomach protected the m neons menibranej or
possibly the larger amount of acid poured out during digestion snffi-
oiently ueutralisetl the alkali. Potasaic cyanide, in very strong soln-
tton, amy cause ereeions of the lips, and the caustic elfect may be
traced in the mouth, throat, gullet, to the stomach and duodenum ;
but this is unusual) and the local effects are, as a rnte^ conBued to the
stomach and duodenum. The mucous membrane is coloured blood-
re<i^ reacts strongly alkaline,* is swollen, and it may be even ulcerated.
The upper layers of the epithelium are also often dyed with the
eolomring- matter of the blood, which has been dissolved out by the
cyanide. This last change is a poi^t-mortem effect} and can be imitated
by digesting the m neons membrane of a healthy stomach in a solution
of cyanide. The intensity of these changes is, of course, entirely
dependent on the dose and emptiness of the stomach. If tlje dose is
BO small as just to destroy life, there may be but little redness or
swelling of the stomach, although empty at the time of taking the
poison. In those cases in ^vhieh there has been vomiting, and a part
of the vomit has l>een drawn into the air-passages » there may be also
inflanuuatery changes in the larynx. If ease nee of ahuonds has been
swallowed, the same slight inflammation tuay be seen which has been
observed with other essential oils, but no erosion, no strong alkaline
react ion J nor anything appitiachhig the effects of the caustic cyan id a
In poisoning by bitter almonds no inflammatory change in the
mucous membrime of the coats of the stomach would be anticipated,
yet in one recorded ease there seems to have been an eroded and
inflamed patch.
§ 265. Tests for Hydi-ocyanic Acid and Cyanide of Potassium.—
(1) The addition of silver nitrate to a solution containing prussic acid,
or a soluble cyanide,!, produces a precipitate of argentic cyanide. 100
parts of argentic cyanide are composed of SO '60 Ag and 19 '4 CK,
* The follawuig case came under Ihe senior author*a own obscrration : — A Rt^jut
woman, 35 jsji^rs of age, tht? wife of a French ipoli&her, draiik^ in a Kt of rtige, a aolu-
tion of cyADtde of jiotinidum* It was eatiinated that about 15 grains of the solid sub-
atAnce were swallowod, Sli<? died within aa liom» Tba face was flushed, the bf^dy not
decoin posed ; the mouth ^m^lt strongly of cyj^nide ; the stomach biul about an ounce
of bloody fluid in it, and was m a most intense state of cougpstian. There vraa com-
mencing fatty degeneration of the liwt, the kidney a were flabby, and the ca|jsulo
adherent. The 4^ont«ntd of the stomach showed cyanidti of [lotassiumj and the btood
was very fluid. The woman was known to be of inttrajMirftte hsbita.
t In the c^ae of testing in this way for the alkaliuc cyaaldes, tha solutiofi must
ecmtaiii a little h^e tiitjiu a^ii!.
2l6 POISONS: THEIR EFFECTS AND DETECTION. [§ 265.
equivalent to 20*1 HON. It is a white anhydrous precipitate, soluble
either in ammonia or in a solution of cyanide of potassium. It is
soluble in hot dilute nitric acid, but separates on cooling. A particle
of silver cyanide, moistened with strong ammonia, develops needles;
silver chloride treated similarly, octahedral crystals. It is insoluble
in water. Upon ignition it is decomposed into CN and metallic silver,
mixed with a little paracyanide of silver.
A very neat process for the identification of cyanide of silver is the
following : — Place the perfectly dry cyanide in a closed or sealed tube,
containing a few crystals of iodine. On heating slightly, iodide of
cyanogen is sublimed in beautiful needles. These crystals again may
be dissolved in a dilute solution of potash, a little ferrous sulphate
added, and hydrochloric acid, and in this way Prussian blue produced.
If the quantity to be tested is small, the vapour of the acid may be
evolved in a very short test tube, the mouth of which is closed by the
ordinary thin discs of microscopic glass, the under surface of which is
moistened with a solution of nitrate of silver; the resulting crystals
of silver cyanide are very characteristic, and readily identified by the
microscope.
(2) If, instead of silver nitrate, the disc be moistened with a solu-
tion of sulphate of iron (to which has been added a little potash), and
exposed to the vapour a short time, and then some dilute hydrochloric
acid added, the moistened surface first becomes yellow, then green, lastly,
and permanently, blue. No other blue compound of iron (with the
exception of Prussian blue) is insoluble in dilute hydrochloric acid.
(3) A third, and perhaps the most delicate of all, is the so-called
sulphur test. A yellow sulphide of ammonium, containing free sulphur,
is prepared by saturating ammonia by SHj, first suspending in the fluid
a little finely-precipitated sulphur (or an old, ill-preserved solution of
sulphide of ammonium may be used). Two watch-glasses are now taken ;
in the one the fluid containing prussic acid is put, and the second (pre-
viously moistened with the sulphide of ammonium described) is inverted
over it. The glasses are conveniently placed for a few minutes in the
water-oven ; the upper one is then removed, the moist surface evaporated
to dryness in the water-bath, a little water added, and then a small
drop of solution of chloride of iron. If hydrocyanic acid is present,
the sulphocyanide of iron will be formed of a striking blood-red colour.
(4) The reaction usually called Schonbein's, or Pagenstecher and
Schonbein's * (but long known, t and used before the publication of their
• Neues Repert, de Pharm,, zviii. 866.
t This reaction (with tincture of guaiacom and copper) has been long known.
"I remember a pharmaceutist, who attended my father's laboratory, showing me
this test in 1828 or 1829."— Mohr's Taxicologie, p. 92.
I 2660
HYDROCYANIC ACID*
217
papeT)^ coaaiBts of guaiacum paper, moistened with a very dilute tsoUitlon
of sulphate of copper (1 : 2000), This becomee blue if exposed to the
vapour of hydrocyanic acid. Unfortunately, the same reaction is pro-
duced bj ammonia, ozone, nitric acid, hypochJorous acid, iodine^ bromine,
chromate of potaeh, and other oxidiistng agents, so that its usefuluetiB is
greatly restricted,
(5) A very delicate te^t for pniaaic acid is as fdlows -^ — About one-
half centigrm* of ammonia, ferrous sulphate (or other pure ferrous
Bait), and the same quantity of uranic nitrate, are dibsolved in 50 ex- of
water^ and I c,c» of this teat liquid is placed in a porcelain dish. On
now adding a drop of a liquid containing the smallest quantity of
prussie acid, a grey-purple colour, or a distinct purple precipitate is
produced.*
(6) A hot aolution of potasslc cyanide, mixed with picric acid,
assumes a blood-red colour, due to the formation of pi cro- cyanic acid.
Free HON does not give this reaction, and therefore must first be
neutralised by an alkali.
(7) Schdnbein's Test. — To a few drops of defibrinated ox-blood are
added a few drops of the carefully-neutralised distillate supposed to
contain prussic acid, and then a little neutral peroxide of hydrogen ia
added* If tbe distillate contains no prussic actdi then tbc mixture
becomes of a bright pure red and froths strongly ; if, on the other hand,
a trace of prussic acid be present, the liquid becomes brown and does not
froth, or only slightly does so.
(8) Kobert'B Test, — A 1-4 per cent, solution of blood, to which
a trace of ferridcyanide of potassium is added, is prepared, and the
neutralised distillate added to this solution. If hydric cyanide be
present, then the liquid becomes of a bright red colour^ and, examined
speotroscopicallyt instead of the spectrum of methienioglobin, will he
seen the spectrum of cyanmethiiemoglobin. Robert proposes to examine
the blood of the poisoned, for the purpose of diagnosis, during life. A
drop of blood from a healthy person, and a drop of blood from the
patient, are examined side by side, according to tbe process just given.
(9) An extremely delicate test has been snggeeted by F, Weebuiaen
(Uiienh Cmtr.^ 1905, i. 1191). To the solution supposed to contain HCN
is added an alkaline solution of pbenolphthalin and weak copper sulphate
solution (1 : 2000) ; if HCN is present, pbenolphthalin is oxidised in the
cold to phenol phthalein and the liquid turns red ; it is said to be semsitiTe
even if 1 part of HCN is diluted up to 500,000 parts.
§ 266* Separation of Hydiic Cyanide or Potassic Gyanide from
Organic Matters, such aa the Contents of the Stomach, etc. — It is
* M. Carey Lea, Anur. Jouni, 0/ Science [S], {%. jip. 121^123 ; /. C. Society y
Fol, L p. 112, 1876.
2l8 POISONS: THEIR EFFECTS AND DETECTION. [§ 266.
very necessary, before specially searching for hydric cyanide in the
contents of the stomach, to be able to say, by careful and methodical
examination, whether there are or are not any fragments of bitter
almonds, of apples, peaches, or other substance likely to produce hydric
cyanide. If potassic cyanide has been taken, simple distillation will
always reveal its presence, because it is found partly decomposed into
hydric cyanide by the action of the gastric acids. Nevertheless, an acid
should always be added, and if, as in the routine process given at p. 51,
there is reasonable doubt for suspecting that there will be no cyanide
present, it will be best to add tartaric acid (for this organic acid will in
no way interfere with subsequent operations), and distil, as recommended,
in a vacuum. If, however, from the odour and from the history of the
case, it is pretty sure to be a case of poisoning by hydric or potassic
cyanide, then the substances, if fluid, are at once placed in a retort or
flask, and acidified with a suitable quantity of sulphuric acid, or if the
tissues or other solid matters are under examination, they are finely
divided, or pulped, and distilled, after acidifying with sulphuric acid as
before.* It may be well here, as a caution, to remark that the analyst
must not commit the unpardonable error of first producing a cyanide
by reagents acting on animal matters, and then detecting as a poison
the cyanide thus manufactured. If, for example, a healthy liver is
carbonised by nitric acid, saturated with potash, and then burnt up,
cyanide of potassium is always one of the products ; and, indeed, the
ashes of a great variety of nitrogenous organic substances may contain
cyanides — cyanides not pre-existing, but manufactured by combination.
By the action of nitric acid even on sugar,! hydric cyanide is produced.
The old method of distillation was to distil by the gentle heat of a
water-bath, receiving the distillate in a little weak potash water, and not
prolonging the process beyond a few hours. The experiments of Sokolofi*,
however, throw a grave doubt on the suitability of this simple method
for quantitative results.
N. Sokolofl*! recommends the animal substances to be treated by
water strongly acidified with hydric sulphate, and then to be distilled in
the water-bath for from two to three days ; or to be distilled for twenty-
four hours, by the aid of an oil-bath, at a high temperature. He gives
the following example of quantitative analysis by the old process of
merely distilling for a few hours, and by the new : —
Old ProceS8.~(l) Body of a hound— age, 2 years; weight, 5180
grms. ; dose administered, 57 mgrms. HON ; death in fifteen minutes.
* Domenico Ganassini {Bull, de Soc^ med, ehir. de Paria, 29) prefers in all
tartaric as the acidifying acid,
t Chemical News^ Ixviii p. 75.
X £er, d, deutach, chem. OeselUeh,, Berlin, ix. p. 1023.
§ 267.]
HYDKOCYAKIC ACID.
2ig
After five days there was foutid in the saliva 0"6 mgrm,, fitomaeh 3*2
mgrms., in the rest of the iiitestiuea 2*6 mgrnis., in the muscles 4*1, —
total, 10-5.
{2) Weight of hody, 4000 grms, ; dose given, 38 mgrma, ; death in
eleven minutes. After tifteen daya, in the saliva 0*Bi in the stomach
7'2, in the re&tt of the intefitinos 2"2, in the niuaeles ^% — total, 13*4*
Ifew Process. — Weight of body, 5700 grms. ; dose, 57 mgrms. ;
death iu tweuty-foiir uimutes» After fifteen days, in the saliva 1*1
mgrm., in the stomach 2*6, in the rest of the intestines 9*6, in the
muscles 31 '9, and in the whole, 4 -5 '2 mgrms. Duration of process^
thirteen hours.
From a second hound, weighing 6800 grms. ; dose, 67 mgmis. ; 25*1
mgrms* were separated three days after death.
From a third hound, weighing 5920 grms. ; dose, 98 mgrms, ; after
forty daysj hy distillation on a sand-bath, there were separated 2-8
mgrms. from the saliva, 4-8 from the stomach, 16*8 from the intestines,
23 "6 from the muacleSj- — total, 48 mgrma.
It would also appear that he has sepiimted 51 "2 mgrms. of anhjdrous
acid from the cor|.»sG of a dog which had been [joisoned by 57 mgrnjs, of
acid, and buried sixty days.*
From another canine corpse, three days laid in an oven, uud left
for twenty-seven days at the ordinary temijeratnre, 5'! mgrms, were
recovered out of a fatal dose of 38 mgrms.
The esthiiation was in each case performed by titrating the distillate
with argentic nitrate, the sulphur compounds having been previously
got rid of hj satumttng the distillate with XHO, and precipitating by
lead acetate.
Venturoli t has, on the contrary, got good quantitative results with-
otit distillation at all. A current of pure hydrogen gas is passed through
the lii|iitd to be tested and the gas tiiially made to bubble thro tig h silver
nitrate. He states that the whole of the hydric cyanide present is
carried over in an hour. Metallic cyanides must be decomposed by
sulphoric acid or tartaric acid. Mercury cyanide must be decomposed
with SH^ the solution acidified with tartaric acid, neutralised with
freshly precipitated calcie carbonate to fii any ferro- or ferri- cyan ides
present, and hydrogeu passed in and the issuing gases led first through
aftolntionof bismuth nitmte to remove SH.^ and then into the silver
solution.
§ 267. How long after Eeath can Ey dric or Fotaesic Cyanides be
Detected ?^Sokolofi' appears to have separated prussit* acid from the
* Without wiAhing to discrodit tlio HtuU^m^t^tB of M. Sokolofi"^ we nmy puiut out
that a loss of half a-do2en mgrtna. oiily appenrs rather extmoidiuttry.
220 POISONS : THBIK EFFECTS AND DETECTION. [§ 268, 269.
body of hounds at very long periods after death — in one case sixty days.
Dragendorflf recognised potaasic cyanide in the stomach of a hound after
it had been four weeks in his laboratory,* and in man eight days after
burial. Casper also, in his 211th case, states that more than 18 mgrms.
of anhydrous prussic acid were obtained from a corpse eight days after
death, t Dr. E. Tillner J has recognised potassic cyanide in a corpse four
months after death. Lastly, Struve § put 300 grms. of flesh, 400 of
common water, and 2*378 of KCy in a flask, and then opened the flask
after 547 days. The detection was easy, and the estimation agreed with
the amount placed there at first. So that, even in very advanced stages
of putrefaction, and at periods after death extending beyond many
months, the detection of prussic acid cannot be pronounced impossible.
§ 268. Estimation of Hydrocyaxdc Add or Potassic Cyanide. — In
all cases, the readiest method of estimating prussic acid (whether it be
in the distillate from organic substances or in aqueous solution) is to
saturate it with soda or potash, and titrate the alkaline cyanide thus
formed with nitrate of silver. The process is based on the fact that
there is first formed a soluble compound (KCy, AgCy), which the
slightest excess of silver breaks up, and the insoluble cyanide is &t once
precipitated. If grains are used, 17 grains of nitrate of silver are
dissolved in water, the solution made up to exactly 1000 grain measures,
each grain measure equalling -0054 grain of anhydrous hydrocyanic acid.
If grammes are employed, the strength of the nitrate of silver solution
should be 1*7 grm. to the litre ; each c.c. then = -0054 hydrocyanic acid,
or -01302 grm. of potassic cyanide.
Essential oil of bitter almonds may also be titrated in this way,
provided it is diluted with sufficient spirit to prevent turbidity from
separation of the essential oil. If hydrocyanic acid is determined gravi-
metrically (which is sometimes convenient, when only a single estimation
is to be made), it is precipitated as cyanide of silver, the characters of
which have been already described.
§ 269. Gase of Poisoning by Bitter Almonds.— Instances of poisoning by bitter
almonds are very rare. The following interesting case is recorded by Mskschka : —
A maid -servant, 31 years of age, after a quarrel with her lover, ate a quantity of
bitter almonds. In a few minutes she sighed, complained of being unwell and faint ;
she vomited twice, and, after about ten minutes more had elapsed, fell senseless and
was convulsed. An hour afterwards, a physician found her insensible— the eyes rolled
upwards, the thimib clenched within the shut fists, and the breathing rattling, the
pulse very slow. She died within an hour and a half from the first symptoms.
The autopsy showed the organs generally healthy, but all, save the liver, exhaling
a faint smell of bitter almonds. The right side of the heart was full of fluid dark
* Dragendorff, G., Beitr. zur gericht, Chem., p. 69.
t Casper's Prod, ffandlnich der geriehtliehen Medicin^ p. 661.
X Vierteljahr. f, gerichtl. Med., Berlin, 1881, p. 193.
§ ZcUschrift f, anal, Chemie, von Freseuius, xii. p. 4, 1873.
§ 270, 27 u]
POISONOUS OTANTDES.
221
blood, the left iv-ftK ^mp^. Botli Imip were rich in blood, whicb amelt of jtrumo
tt&id* The stomiioh waa tint inllanicd— it held 250 gmia. of & yet!»w fluid, coiitftining
white flocks smelliag of bitter almond oil. Id the most defjendent iJtirtion of the
stomach there wiw a swollen patch of mucous tnembmne^ iiartiaUy denuded of
epithelium. The mucous nieinbraiip of ttie duodenum wa» ttko swollen and slightly
red. The contents of the stomach wtsrt* acid^ and yielded, ou distillation, hydridft of
bemiolc and hydric cyanide. Residues of the almonds themselves were also found,
ftod the whole i^uivntity taken hy the w^otnan from various data was calculated to be
120Q grains of bitter almonds, equal to 4S grains of amjgtUliUi or 2 '5 grains of pum
hydric cyaiiirle.
Poisonous Cyanides other than Hydric and Potassic Cyanides*
§ '270, Tho tictiitn of Ijfutli sot/Zc atui ftntm^nic cifaniilcs ia ijrwi^iely iNimilar to that
of pfitiJi^iic [ y^iiide. With regard to ammuuic cyanide, there arc st^veral exi>eriments
by Eulenlxsrg,* h It owing that its vapour jh intensely j^ioisonous.
A weak stream of ammonic cyanide vapour waB j^asaed into glass shadeB^ tiudor
which ptgeofiswere conBtied. After a minute, symptoms of distresB commtineedj then
followed convulsions and speedy death. The post*iDortem ^gn» were similar to tho»e
produced by pmssic acid, and this sabstance was separated from the liver and lunp,
§ 271* With regard to the douhU njan itfis^ all those are poisionoufl from which hydric
cyanide can he sejjarated through dilute acids, whih? tlMtm which, like potassb ferro-
cyanide, do not admit of this decompoaitiou, may often be taken with impunity, and
are ouly ;M>i80noua under certain condidous,
Sonuonsohein records'^tbe death of a colourist^ after he hud taken a dose of potaasic
fernH?yaiiid« and then one of tartaric acid ] and Vols defioribcfi the death of a man^
who took potaaaio ferro-cyaiiide and aftenvards equal parts of nitnc and hyclrocldoric
acid^i. In th is latter case, death took place within the hour, with all the symptoms
of poisoning by hjdnc cjanide ; so that it is not eotirely true, as most text^books
declare^ that ferro^cyanide is iu no degree poisonous. Carbon dioxide will decom-
pose pota8»ic ferrO'Cyanide at 72'-74'j potass ferrous cyanide being precipitated^
KsFa/OH)(. A similar actioa takes place if forro cyanide i:3 mixed with a st>lution
of peptone mid casein, and digested at hloc»d0ieat t (from S?"" to 40^ C), so that it is
believed than when ferro cyanide is swallovfed HCN h liberatedp but the quantity
is usually so small at any given moment that no lijjury Is cauiierl t but there are
conditions in which it may kill speedily. S
Here nric; cyanide, it hsa been often said, acta preobwly like mercuric chloride
(corrosive i^niilimate), and a poiaonoua action is attributed to it not traceable to
• Qewerb^ Mt/^knr^ p» 886w t Auteurieth, Arch. Phmrm^t ccxjoeL SM^-109.
t The presence of ferm*oyanide is easilj detected. The liquid is, if necesaary^^
fdtei-ed and then acidised with hydfoehloric acid and a few droje of ferric chloride
added ; if the liquid contains ferro-cyanide, there is immediate production of Prus-
sian blue. It may happen that potuasic or sodic cyanide has been taken as well as
ferrij-cyanidu, and it wDl he neee^isary then to devise a process by which only the
pnissic acid from the sinnjlo cyanide is distilled over, Aeconling to Autenrieth, if
stMlium hydrfjcarhonat* ia added to tbe liquid in snfficiient quantity and the liquid
distilled^ tbe hydric cyanide that comes over is derivfid wholly from tJie s<tdium or
potiasium cyanide. Should mercury cyanide and ferrrj- cyanide be taken together,
thfln this proci^ss requires modification \ bicarb nat-e of sotla h added as before, and
then a few c.c- of water saturated with hydric sulphide ; under these circum-
atanci^, only the hydric cyanide derived from the mercnrj' cyanide distils over.
If the bicarbonate of soda ia omitted, the distillate contains hydric cyanide derived
ft^m the ferro-ayanidc.
222
poisons: their effects and detection.
[§ 2;r.
cynnogen ; but this m erroDeous teaching. Bernard ^ deicUrea that it is dflccim-
poaed by th^ gsstriD juice, and hydiic ^yftuidL^ aet froe ; while Pi?Ukflti puts it in
the Sftme &&n^ m ammonic iiknd i¥>tas8m cyanides. Lastly, Tolmat4Gbetf,t by dir^sct
cxjieriinent, has found its action to resemble closely that of hydtic cyaQitle.J
Silver cy&nide aetaj ac^^ording to the ex(icrimeuta of Nuujieleyi also like hydnc
cyinide, but very much weaker.
Hydrie Bulphocyanide m rery large dofiea m {Kjisonoua,
Fotaifiic Biilphocyamde, a<woitliug to Dubreiiil and Legros, g if anbcntaneoualy
injected J causes first, local paralysis of the muacks, and later^ coiivulsiona.
Cyanogen chloride (CNCl) autl also the com|K>uijd (CaNjtClj) — the one a liquid,
twill ng at 15^, the other a aolid^ which may be obtaiuod in ciyBtak— are l>ijth
pcriisonons, acting like hydrie cyanide.
Cyanogen iodide (CNl), according to Kobert, is four times weaker than prusaic
acid, but it is a poweiful jKii^on for uniccUular organisms. Tire nitriles have but
flight toxic action* Acet<j-nitiile h a good medium for bacterial growth. The lao-
nitiiles, on the conlTary, are powerful poiaoiis.
Methyl cyanide ia a liquid obtained by dLHtillatlon of a mixture of ctvkic methyl
sulphate and potaaaic cyanide. It boil a at 77", and h intensely poiaonous. Eulcu-
borg II hail made aeveral experiments on pigeon a with thin Bubatance. Due oicample
Will suffice t — A young pigeon was placed under a glasa shade, into which methyl
cyanide va{H>urf developed from calcic nicthyl sulphate aud jjotasaic cyanide, waa
admitted. The pigeon immediately beciime reatleaa, and the fceces were oxiKlleci.
In forty Escconda it waa altghtly convul^Kl, and was removed aft^er a few niinutea*
ezpocfure. The pupils were then observed not to be dilated, but the re^spiratiou had
ceased ; the legs were feebly twitching i the heart still beat, but iiTegularly ; a in ibid
white fluid dropped out of the beak, and after n'li minnteH life was extinct.
The pathological appearancei were as follows :— In the beak much watery fluid;
the membTOUcs covering the brain weakly i injected ; the plex'tts i^tiwMua §piHalis
strongly inji'cted ; in the region of the cervical verttihra a small cxtravaAtition
betwei"n the dura mater and the bone ; the liglit lung of a clear cherty*red colour,
and the left lung partly of the same colour ; the jjarenchyma presented the same hue
as the surface - on geetion of the lungs a whitiah froth exud^ from the eut surface.
In the cellular tissue of the trachea, there were extravitsations 5 mm. in di&meter ;
the mucous membrane of the air-paaeagee was pale ; the right ventricle and the left
auriele of the heart were filled witb coagulated and Uuid dark I'ed blood ; tiv^er and
kidneys nonnal ; the blood dark red atid very fluid, Iweorauig bright cherry- luil on
eJtposure to the air ; blood oorpnscles unchauijcd. Cyanogen was aepamted, and
identified from the lungs and the liver.
Gyannric acid (OaOal^sH..), one of the decora position products obtained fr^^m urea,
is ^loisonous, the symptoma and iMithologic^l efl'ects closely resembling those due t^i
hydrie cyanide. In experimeuta on animals, there )jaa been no difficulty in detecting
pruasic acid in the lungs and liver after ]x>isoning by eyanurie acid.
Reid HuntH has determined the toxto dose of many uitrdes when aubcutaneinisly
• Substatiees ToxineSj pp* 06-103.
t ^* Eiuige Bemerkungen iiber die Wirkimg von CyanquccksillHir,*' in Hoppe-
Seyler^a Med. Chirm,, Unttrsti^hungen^ 2 Heft, p, 279,
Z Mercury cyanide may l^ detected in a liquid after acidifying with tartaric acid,
and adding a few c.c, of SHg water and then distilling. 3. Lojies s^ugget^tB another
process; the liquid la acidified with tartaric acid, amnioniuni chloride added in
ej^cess, and the liquid is distilled. A double chloride of amnion ium and meix^ury la
formed, and HCN distiJa over witli the strata — J. Phm-m.^ i^xvi'u 550-553-
§ Cmnpi, Kend., t. Ixiv. p. 5fil, 18G7, |J (hw^he Bytfienc^ p. 392.
ff Arch, inter, tk Pharm. cttU Thdrapk, xih, 1904*
§ 271.]
POISONOUS CYANIDES.
223
injected into mice. The nitriles were either diaaolved in water or in diluted alcohol.
The results may be seen from the following table :—
i
|1
"1
1
an
s
w
it»
1
M
iii;
Fraasic acid *
HCN
1
ii I
27
0-005 1
: '
Aceto iiitrile .
CHjCN
41
07 140
92*2
Formal oyanhydririe
CH^01I)GK
57
0-016 3
1*42 1
Chloral cyanbjdriiit'
C0liCH(OH)CN
188^5
0-023 4*6
0-66
Benio nitrile .
CflH^CN
103
O^ie ' 36
9*6
Benzyl nitrile
U^HaCH^CN
117
0-03^2 1 6-4
1-47
Maoildic nitrile ,
C.H,CH(OH)t:N
133
0-023 1 4'e
0*93
Diothyldminoaceto nitrile
hydrochloride ,
1
^NCCjHs).^Cl
CN
H8"6
0*031
0
1-09
Dis^liylatDinoaceto nitrile
iodam^thyUte .
CHa CH,
^I
SGI
0*25
50
5^31
DiethyUminO'lactic nitrile
CN
120
0*022
4 4
0-94
Di6thylsmino-!actk! nitrile
iodo methybte ,
\ /
1 '^N(CH,)a
260
0-4
80
8*1
1
1
\l
/ON
Pbenykmitioaceto nitrile
CHa
^NHCbHa
133
0-055
n
2*25
TolykfXiitjoawto nitrik
{ortho-}
C8H<(CH3)NHCH^CNto)
116
0-091
18-2
3*30
Tolylaininoa£»to nitrile
(metaO - > <
CN
146
0-1
20*0
3*7
Dietbylamiao - phenyl-
aceto nitrile*
i^HjOB
isd
0-025
G
0-73
CN
\nC,H,o
124
0*058
lie
252
dodium nitro pmstslde .
Fe<0N)s(NO)Na5+2HO,
298
0*012
3-4
0-217
224
POISONS: THKIR KFFECTS AND DBTECTION.
[§ 272.
He ascribes the toxic properties of these nitriles to the splitting off of HON.
The different stability of the compounds, the ease with which tiiey are absorbed and
excreted, and the variations in distribution in the body, account for the differences in
toxicity that they exhibit
The same author has made exx)eriments on the antagonistic action of certain
thiosnlphates and other sulpho compounds when injected a short time before the
nitrile. The results of a few of these experiments may be seen from the following
table, the figures indicating how many fatal doses of the nitrile have been neutral-
ised by the sulpho compound.
frwicactd , , .
BCS
1
IS
n
In
Ii
S'4
=11
f
is
M
1'
III
III
Hi
L
If
^ tie
^1
i-fi
i4
0
a
S
1-4
Ac«to nttrile . . .
CH^CS
2
„,
?
0
2-e
„,
.»
U
1-3
0
CH^a)CN
la
about 3
S'6
3*3
3
lew
as
K-fi j
5
thanS
Qilof*! ty*iibjdrin«
0Cli^tOH)CK
S7
.„
u-S
tluuiS
f
X-3
1-3
i'#
1-3
«ii
BmuD Dttrllo . . .
CijH^CN
0
^**
0
^
ri
n
0
CflHoCfl^lCK
a-6
IfauE
1-7
..,
17
T
...
T
s
XT
MmndQllciiJtrtle. ,
C,HsCe(OH)CX
rB
x-t
a-E
0
!
...
£
Bt
--
XIIL— Phosphorus.
§ 272. Phosphorns. — Atomic weight 31, specific gravity 1-82 to
1*840. Phosphorus melts at from 44 •4° to 44*5* to a pale yellow oily
fluid. The boiling-point is about 290°.
The phosphorus of commerce is usually preserved under water in
the form of waxy, semi-transparent sticks ; if exposed to the air white
fumes are given off, luminous in the dark, with a peculiar onion-like
odour. On heating phosphorus it readily inflames, burning with a very
white flame.
At 0"* phosphorus is brittle ; the same quality may be imparted to
it by a mere trace of sulphur. Phosphorus may be obtained in dodeca-
hedral crystals by slowly cooling large melted masses. It may also be
obtained crystalline by evaporating a solution in bisulphide of carbon, or
hot naphtha in a current of carbon dioxide. It is but little soluble in
water. Julius Hartmann * found in some experiments that 100 grms. of
water digested with phosphorus for sixty-foiir hours at 38 '5° dissolved
'000127 grm. He also investigated the solvent action of bile, and
* Zur acuten Phosphor- Vergiftung, Dorpat, 1866.
§ Vl^
PHOSPHORUS.
225
found that 100 grms. of bile under the same conditions dissolved
■02424 grm.i and that the solubility of phosphorus rose both in water
and bile when the temperature was increased. Phoaphorus is somewhat
soluble in alcohol and ether, and ako, to some extent, in fatty and
ethereal oils ; but the best solveut is carbon disulphide*
The following is the order of solubilitj in certain menstrua, the
figures rep^resenting the numl>er of parts by weight of the advent
retjuired to dissolve one part of phosphorus : —
Cftrbon Disulphidpj . . , . . 4
Almond Oil, , . . , . .100
ConcentTated AtMstic Add,* , , , ♦ 100
Ether, .... . , 260
Alcohol, specific gravity '822, . , , .400
Glycflnn^ ,,.,,,. 5S8
Phosphorus exists in, or can be converted into, several allotropio
modifications, of which the red or amorphous phosphorus is the most
important. This is effected by heating it for some time, in the alisence
of air, from 230' to 235". It is not poisonous, t Commercial red
phosphorus does, however, contain very small quantities of unchanged
or ordinary phosphorus — according to Fresenius, from '6 per cent, down-
wards j it also contains phosphorous acid, and about 4 "6 per cent, of
other impurities, among which is graphite | and ofteu arsenic.
g 273. Phoaphuretted Hydrogen, — ^Phoaphine (PHg), mol, weight
34, specific gravity I '178, percentage composition, phosphorus 91*18,
hydrogen 8-8*2 by weight. The absolutely pure gas is not 8|)oiitaneously
inflammable, but that made by the ordinary process is so. It is a
colourless, highly poisonous gas, which does not support combustion,
but is itself combustible, burning to phosphoric acid {PHg + 20^ = PO^H^).
Extremely dangerous explosive mixtures may be made by eombining
phosphiue and air or oxygen. Phosphiue, when quite dry, bums with
a white flame, but if mixed with atjueous vapour, it is green ; hence a
hydrogen flame containing a mixture of PHy possesses a green colour.
If sulphur is heated in a stream of pbosphine, hydric sulphide and
sulphur phosphide are the products. Oxides of the metala^ Ijeated with
phosphiue^ yield phosphides with formation of water. Iodine, warmed
in phosphiue, gives white crystals of iodine phosphonium, and biniodide
of phosphorus, 5I-h4PH3= 3PIH^+ PI^. Chlorine inflames the gas,
the final result being hydrio chloride and chloride of phosphorus, PHg +
8C1 = 3CIH + PCl^. One of the moat important decompositions for
* Pliosplionis ifi veiy littb soluble in cold acetic octd^ and the eolubiUty given
is only correct when th(^ boiHng acid acts for some tiniQ ou the phosphorus.
t A hound took 200 gm;a. of red pho«phon» in tw(^lre days, and remained
beat thy. — Son neri9ch<*in *
t Schrott«r, Cliem, jVet^s, vol xxxri, p, IflS.
i
226 POISONS : THEIR EFFECTS AND DETECTION. [§ 274, 275-
our purpose is the action of phosphine on a solution of nitrate of
silver ; there is a separation of metallic silver, and nitric and phosphoric
acids are found in solution, thus — SAgNOg + PHg + 40H2=8Ag +
8HNOg+P04H8. This is, however, rather the end reaction; for, at
first, there is a separation of a black precipitate composed of phosphoiv
silver. The excess of silver can be separated by hydric chloride, and
the phosphoric acid made evident by the addition of molybdic acid in
excess.
§ 274. The medidnal preparations of phosphorus are not numerous ;
it is usually prescribed in the form of pills, made by manufacturers of
coated pills on a large scale. The pills are composed of phosphorus,
balsam of Tolu, yellow wax, and curd soap, and 3 grains equal ^ grain
of phosphorus. There is also a phosphorated oil^ containing about 1
part of phosphorus in 100; that of the French Pharmacopoeia is made
with 1 part of dried phosphorus dissolved in 50 parts of warm almond
oil ; that of the German has 1 part in 80 ; the strength of the former
is therefore 2 per cent., of the latter 1*25 per cent. The medicinal
dose of phosphorus is from y^ to ^ grain.
§ 275. Matches and Vermin Pastes. — An acquaintance with the
percentage of phosphorus in the different pastes and matches of com-
merce will be found useful. Most of the vermin-destroying pastes
contain from 1 to 2 per cent, of phosphorus.
A phosphorus paste that was fatal to a child,* and gave rise to
serious symptoms in others, was composed as follows : —
Per cent.
Phosphorus, 1*4
Flowers of sulphur, 42*2
Flour, 42-2
Sugar, 14-2
100-00
Three common receipts give the following proportions : —
Per cent.
Phosphorus, 1*6
Lard, 18*4
Sugar 18-4
Flour 61-7
100 00
Per cent
Phosphorus, 1*2
Warm water, 26*7
Rye flour, 26*7
Melted butter, 26*7
Sugar, 187
100 00
* Casper's 204th case.
§ 27$.] PHOSPHORUS. 227
Per cent.
Phosphoras, 1*6
Nntoa, 15-7
Wann water, 31-6
Flour, 81'6
Sugar, 197
100-00
A very common phosphorus paste, to be bought everywhere in
England, is sold in little pots ; the whole amount of phosphorus con-
tained in these varies from 324 to '388 grm. (5 to 6 grains), the active
constituent being a little over 4 per cent. Matches differ much in
composition. Six matchheads, which had been placed in an apple for
criminal purposes, and were submitted to Tardieu, were found to con-
tain 20 mgrms. of phosphorus — i.e. 33 grm. in 100. Mayet found
in 100 matches 55 mgrms. of phosphorus. Gonning''^ analysed ten
different kinds of phosphorus matches with the following result: —
Three Jlnglish samples contained in 100 matches 34, 33, and 32 mgrms.
of phosphorus ; a Belgian sample, 38 mgrms. ; and 5 others of unknown
origin, 12, 17, 28, 32, and 41 mgrms. respectively. Some of the pub-
lished formularies are as follows : —
(1.) Glue, 6 parts.
Phosphorus, * >, or 14*4 |>er cent.
Nitre 10 „
Red ochre, .... ^ n
Blue smalts, .... 2 „
(2.) Phosphorus, .... 9 parts, or 16 '3 per cent.
Gum, 16 „
Nitre, 14 „
Smalts 16 „
(3.) Phosphorus, .... 4 parts, or 14*4 per cent.
Glue, 6 „
Nitre, . . 10 ,,
Red lead 6 „
Smalts 2 „
(4.) Phosphorus, .... 17 parts, or 17 per cent
Glue 21 „
Nitre, 88 „
Red lead, 24 „
Phosphorus poisoning by matches is, however, becoming rare, for
those containing the ordinary variety of phosphorus are being superseded
by matches of excellent quality, which contain no phosphorus whatever,
or by matches which are manufactured with phosphorus sesquisulphide,
P^Sj ; for example, the matches made in France in the national factories
* Nederlandsch Tijdschr, voor Oeneesk., Afdl. I, 1866.
228 POISONS : THKIR KFFBCTS AND DETBCTION. [§ 2/6.
contain only the sesquisulphide, which has not the injurious qualities
of the ordinary phosphorus.
§ 276. Statistics. — The deaths for ten years ending 1903 from
phosphorus poisoning in England and Wales amount to 148 ; of these^
67 (29 males, 38 females) were due to accident, and 81 (21 males and
60 females) were suicidal.
Phosphorus as a cause of death occupies the eleventh place among
poisons ; as a cause of suicide it occupies the seventh.
A far greater number of cases of poisoning by phosphorus occur yearly
in France and Germany than in England. Phosphorus may be considered
as the favourite poison which the common people on the Continent em-
ploy for the purpose of self-destruction. It is an agent which, before the
change of manufacture, was within the reach of anyone who had two sous
in his pocket wherewith to buy a box of matches; but to the educated and
those who know the horrible and prolonged torture ensuing from a toxic
dose of phosphorus, such a means of exit from life will never be favoured.
Otto Schraube* has collected 92 cases from Meischner*s worlr,t and
added 16 which had come under his own observation, giving in all 108
cases. Seventy-one (or 65 per cent.) of these were suicidal— of the
suicides 24 were males, 47 females (12 of the latter being prostitutes);
21 of the cases were those of murder, 11 were accidental, and in 3 the
cause was not ascertained. The number of cases in successive years, and
the kind of poison used, is given as follows : —
Ntunber of Cases.
In the Tean
Fhotphonu In
Sabstance,
or as Paste.
Phosphorus
Matches.
15
1798-1850
13
2
36
1851-1860
15
21
41
1861-1864
6
85
16
1865-1867
6
11
Of the 108 cases, 18 persons recovered and 90 (or 83-3 per cent.) died.
Falck also has collected 76 cases of poisoning from various sources
during eleven years ; 55 were suicidal, 5 homicidal X (murders), and
the rest accidental. Of the latter, 2 were caused by the use of phos-
phorus as a medicine, 13 by accidents due to phosphorus being in the
house ; in 1 case phosphorus was taken intentionally to try the effects
of an antidote.§ With regard to the form in which the poison was
* SchmidVs Jahrbuch der ger, Med., BA clxxxvi S. 209-248, 1867.
t Die aeute Photphorose und einige ReJUxionen aber die acute gelbe Leber atrophie,
etc., Inaug. Diss., Leipzig, 1864.
X Dr. Dannenberg has shown by direct experiment that a poisonous dose of
phosphorus may be mtroduced into spirits or coffee, and the mixture have but little
odour or taste of phosphorus. — Schuchardt in Maschka's ffandbitch.
§ G^ry, "Ueber Terpentlnessenz als Qegenmittel gegen Phosphor," in Oaz.
Hebd. de Med., 2 ser., x. 2, 1878.
§ ^77-279}
PHOSPHORUS.
229
laket], 2 of the 76, im alrea(.ly mentioned, took it as prescribed by
physic laafc^ tht? reniaiuing 74 were divided between poiaouiugs by phos-
phorus paste (22) aud matches (52) = 70 per ceut. Of the 76 cases, 6
were children, 43 adult Diales, 13 adult females;, and 14 adults, sex not
given- Of the 75 casea, 42, or 55^3 per cent., died — a much smaller
rate of mortality thati tiiat shown by Schmube^a collectioo.
g 277. Fatal Dose. — The smallest dose on record is that mentioned
by Lobeostcin Lobel, of Jena, where a iunatic died from taking 7 "5
mgrms. ('116 grain), There are other cases clearly indicating that this
small i[uaiUity may produce dangerous E^ymptoma in a healthy adult
§ 27 H. Effectfl of Phoiphorue. — Phosphorus is exee&si\ ely poisonous,
and will destroy life, provided only that it enters the body in a line state
of division, but if taken in eoarse pieces no symptoms may follow, for
it has been proved that single lumps ot phosphorus will go the whole
length of a dog's intestinal canal without causing appreciable loss of
weightj and without destroying life.* Mage n die injected oleum phoi*-
ph4)ratum into the veins, and although the animals experimentetl on
exhaled white fumes, and not a few died asphyxiuted, yet no symptoms
of phoBphorua poisoning resulted — an observation confirmed by others—
the reason being that tlie phosphorus particles in a comparatively coarse
state of division were arrested in the capillaries of the lung, and may be
said to have been, as it werCj outside the body. On the other hand,
A, Brunner^t working in L. Hermann^ laboratory, having injected into
the veins phosphorus in such a fine emulsion that the phowphoms eould
pass the lung capilhiries^ found that there were no exhalations of white
fiimes, but that the ordinary symptonm of phosphorns poii^ouiug soon
manifested themselves. Phosphorus paste ^ by the method of manu-
facture, is in a state of extreme sulxii vision, and hence all the
phosphorus pa-stes are extremely poiaonous.
§ 279. In a few poisons there is a difference, more or less marked,
between the general symptoms produced on man^ and those noticeable
in the difterent otasses of animals ; but with phosphorus, the elfeets on
animals appear to agree fairly with those witnessed most freijuently in
man. Tardien (who h^is written perhaps the best and most complete
clinical record of pbospljorus poisoning extant) divides the cases under
three classes, and to use his own words : — ** I think it useful to establish
that poisoning by phosphorus in its course, sometimes rapid, sometimes
slow, exhibits in its symptoms three distinct forms — a common form, a
nervous form, and a ha^morrhagic form* I recognise that, in certain
cases, these three forms may succeed each other, and may only constitute
periods of poisoning ; but it is incontestable that each of them may ahow
' Revi'il, Ann. (Tll^iitie FM, (3), xii. p. 370,
l Ardt.J. d. f/j?j(* l*h}fStQkfg%4y 111. p. l.
230 POISONS: THIIR KFFBCTS AND DKrBCnON- [§ 280.
itself alooe, aud occupy the whole course of the illness produced by the
poison."* Premising that the common form is a blending of irritant^
nervous, and haemorrhagic symptoms, we adopt here in part Tardieu's
division. The name of " hsemorrhagic form " may be given to that in
which haemorrhage is the predominant feature, and the " nervous " to
that in which the brain and spinal cord are torn the first affected.
There yet remain, however, a few cases which have an entirely
anomalous course, and do not fall under any of the three classea.
From a study of 121 recorded cases of phosphorus poisoning,
the relative frequency of the different forms appears to be as follows : —
The common form 83 per cent., haemorrhagic 10 per cent., nervous 6
per cent., anomalous 1 per cent. The "anomalous" are probably
over-estimated, for the reason that cases presenting ordinary features
are not necessarily published, but others are nearly always chronicled
in detail.
§ 280. Common Form. — At the moment of swallowing, a disagree-
able taste and smell are generally experienced, and there may be
immediate and intense pain in the throat, gullet, and stomach, and
almost immediate retching and vomiting. The throat aud tongue also
may become swollen and painful ; but in a considerable number of cases
the symptoms are not at once apparent, but are delayed from one to six
hours — rarely longer. The person's breath may be phosphorescent
before he feels in any way affected, and he may go about his business
and perform a number of acts requiring both time and mental integrity.
Pain in the stomach (which, in some of the cases, takes the form of
violent cramp and vomiting) succeeds ; the matters vomited may shine
in the dark, and are often tinged with blood. Diarrhoea is sometimes
present, sometimes absent; sleeplessness for the first night or two is
very common. The pulse is variable, sometimes frequent, sometimes
slow ; the temperature in the morning is usually horn 36*0*" to 36*5% in
the evening 37' to 38".
The next symptom is jaundice, as was observed in the following
23 cases: — In 1 within twenty-four hours, in 3 within thirty-six
hours, in 3 within two days, in 11 within three days, in 1 within four
days, in 1 within five days, in 1 within nine days, in 1 within eighteen
days, and in 1 within twenty-seven days; so that in about 78 per
cent, jaundice occurred before the end of the third day. Out of 26
cases, in which the patients lived long enough for the occurrence
of jaundice, in 3 (or 11 per cent.) it was entirely absent. In 132 cases
recorded by Lewin, Meischner, and Heisler^ jaundice occurred in 65,
or about 49 per cent., but it must be remembered that in many
of these cases the individual died before it had time to develop. The
* £tude M6dicO'LegaU et Clinique 9ur V£fnpoiaonneinetU, Fkris, 1876, p. 483.
§281, 282,]
PKOSPHORUS,
231
jaundice liaving thoroughly pranoiinced itself, the sjatem may be con-
sidered ae not only under the itiflueuce of the toiic action of phosphoruSj
but sm BufFering in addition From all the nccidcuta iuctdental to the
retention of the biliary secretion in the blood ; nor h there from this
point any special ditference between phosphorus poisoning and certain
affections of the liver— such, for example, as at^ite yellow atrophy. There
IS retention of uriiie, sleeplesanesa, headache, frequent vomiting, painful
aad often invohmtary evacuations from the bowels, and oceasionally skin
aflTeetiouB, such aa urticaria or erythema. The case terminates either by
acute delirium with fever, followed by fatal eoma, or, in a few instances,
coma comeg on, and the patient passes to death in sleep without delirium.
In thiB common form there is in a few caaea^ at the end of from t^veuty-
four to thirty honri^, a remisaion of the symptoms, and a non-medical
observer uiight imagine that the patient was about to recover without
further discomfort ; Imt then jaundice supervenes^ and the course is as
described. Infants ofteu do not live long enough for the jaundiced
Btage to develop, but die within twenty*four houru, the chief symptoms
being vomiting and con v ids! on 3.
§ 281, HiemorrhagiQ Form. — The symptoms set in as just detailed,
and jaundice appeal's, but accompanied by a new and terrible traiu of
eveuts — vi»., great eU'usfon of blood. In some cases the blood has been
poured out simultaneously from the nose, mouth, bladder, kidneys, and
bowels. Among women there is excessive hscmorrhagia. The liver is
found to be swollen and p^iinful ; the bodily weakness is great. Such
cases are usually of long duration, and a person may die months after
taking the poison from weakness, anemia, and general cachexia, In
many of its phases the haemorrh^c form resembles scurvy, and, as in
scurvy J there are spots of purpura all over the body.
§282. The nervous form is less common than the two forms
just de^ribed. From the begiuning, thei'e are strange creeping
seiisations about the limbs, followed by paiuful cramps, repeated
faiu tings, and great somnolence. Jaundice^ as usual, sets in, erythe-
matous spots appear on the skin, and, about the hfth day, delirium
of an acute character breaks out, and lockjaw and convukions close
the scene.
The following are one or two brief abstracts of anonmlous cases in
which symptoms were oither wanting, or ran a course entirely different
from any of the three fomxs described : —
A woman, aged 20, took about 3 grains of phosphorus in the form
of rat-paste. She took the poison at 6 in the evening, behaved accord-
ing to her wont, and sat down and wrote a letter to the king. During
the night she vomited once, and died the next morning at 6 o'clock,
exactly twelve hours after taking the poison. There appear to have
232 POISONS : THKIK EFFECTS AND DETECTION. [§ 283-286.
been uo symptoms whatever, save the single vomiting, to which may be
added that in the course of the evening her breath had a phosphorus
odour and was luminous.''^
A girl swallowed a quantity of phosphorus paste, but there were no
marked symptoms until the fifth day, on which there was sickness and
purging. She died on the seventh day. A remarkable blueness of the
finger nails was observed a little before death, and was noticeable after-
wards.!
§ 283. SequelsB. — In several cases in which the patients have
recovered from phosphorus poisoning, there have been observed para-
lytic affections. J O. Bollinger has recorded a case in which paralysis
of the foot followed ;§ in another, published by Bettelheim,|| there were
peculiar cerebral and spinal symptoms. Most of these cases are to be
explained as disturbance or loss of function from small haemorrhages in
the nervous substance.
§ 284. Period at which the first Symptoms commence. — The time
when the symptoms commence is occasionally of importance from a
forensic point of view. Out of 28 cases in which the commencement
of evident symptoms — i.e. pain, or vomiting, or illness — is precisely
recorded, in 8 the symptoms were described as either immediate or
within a few minutes after swallowing the poison ; in 6 the symptoms
commenced within the hour ; in 3 within two hours ; in other 3 within
four hours ; and in 1 within six hours. One was delayed until the lapse
of twelve hours, 1 from sixteen to eighteen hours, 1 two, and another
five days. We may, therefore, expect that in half the cases which may
occur, the symptoms will commence within the hour^ and more than 80
per cent, within six hours.
§ 285. Period of Death.— In 129 cases death took place as follows : —
In 17 within twenty-four hours, in 30 within two days, in 103 within
seven days. Three patients lived eight days, 6 nine days, 13 ten days,
1 eleven days, 1 sixteen days, 1 seventeen days, and 1 survived eight
months. It hence follows that 79 '8 per cent, of the fatal cases die
within the week.
§ 286. Phosphorus Vapom:. — There are one or two cases on record of
acute poisoning by phosphorus in the form of vapour. The symptoms
are somewhat different from the effects produced by the finely-divided
solid, and in general terms it may be said that phosphorus vapour is
more apt to produce the rarer '* nervous " form of poisoning than the
solid phosphorus.
* Gasper's 205th case. f Tftylor on Poiscms, p. 277.
t See Gallayardin, Les Paralyses PhosphoriqtLes^ Paris, 1865.
§ Deutsches Archivf, kliru Med., Bd. vi Hit 1, S. 94, 1869.
II Wiener Med. Presse, 1868, No. 41.
I 286.]
PHOBPHORUS.
233
Bouchardat * mciitioim tlie case of a dniggiBt who, while preparing a
large quantity ^f rat-poiBoii in a cluse room, inhaled phosphorus vapour*
He fainted repeatedly, fell into a eomplete state of prostration^ and died
withm a week.
The following in teres ting case came under the observation of
Professor Magnus Hues t — A man, 39 yeare old» iiiarriodj was ad-
mitted into the Seraph in-Lazareth^ Stockholm, on the 2nd of February
1S42. He had been occupied three yeare in the manufacture of
phosphorus matches, and inhabited the room iu which the materials
were preserved. He had always been w el h conducted in every way, and
in good health, until a year previously, when a large quantity of the
material for the manufacture of the matches accidentally caught fire and
exploded. In his endeavoura to extinguish the ilames^ be breathed a
large quantity of the vapour, and he fell for a time uncoiiHcious, The
spine afterwards became so weak that he could not hold himself up, and
he lost, in a great measure, power over bis lege and arms. On admission,
his condition was as follows : — He could make a few uncertain and
staggering steps, bis knees trembled, his arms shook, and if he attempted
to grits p anything when he lay in bed, there were invohuitary twitchings
of groups of muscles. There was no pain ; the sensibility of the skin
was unchanged; be had formieation in the left arm; the spine was
neither sensitive to pressure^ nor unusually sensitive to heat (as, e^g.^ to
the application of a hot sponge) ; the organs of special sense were not
affected, but his speech was somewhat thick. He lived to 1845 in the
same condition, but the ptiralyais became worse. There does not seem
to have been any autopsy.
The effects of phosphorus vapoiir may be still further elucidated by
one of Eulenberg's t experiments on a rabbit. The vajjour of burning
phosphorus, mixed with much air, was admitted into a wooden hatch in
which a strong rabbit sat. After 5 mgrms. of phosphorus had been in
this manner consumed, the only symptoms in half an hour were
salivation, and quickened and somewhat laboured respiration. After
twenty-four hours had elapsed there was sudden indisposition, the
animal fell as if lifeless, with the hind extremities stretched out, and
intestinal movements were visible ; there was also expulsion of the urine.
These epileptiform seizures seem to have continued more or less for
twelve days, and then ceased. After fourteen days the experiment was
repeated on the same rabbit. The animal remained exposed to the
vapour for three-quarters of an hour, when the epilepsy showed itself as
before, and, indeedj almost regularly after feeding. Between the
• AnnUJiiTc de 'rii^h^p.,lB7it P^ H>S i Sobucbardt in Masuhka'sfi^awfAttcA ; bAho
Sohmidt'B Mifbrnh, Bd. U, S, 10 U IS46.
t GtwerH MjftjiffHc, p* 256.
234 POISONS : THEIR EFFECTS AND DETECTION. [§ 287, 288.
attacks the respiration was slowed. Eight weeks afterwards there was
an intense icterus, which disappeared at the end of ten weeks.
§ 287. Chronic phosphorus poisoning has frequently been noticed in
persons engaged either in the manufacture of phosphorus or in its
technical application. Some have held that the symptoms are due to
an oxidation product of phosphorus rather than to phosphorus itself ;
but in one of Eulenberg*s experiments, in which a dove was killed by
breathing phosphorus fumes evolved by phosphorus oil, phosphorus was
chemically recognised in the free state in the lungs. The most constant
and peculiar effect of breathing small quantities of phosphorus vapour
is a necrosis of the lower jaw. There is first inflammation of the
periosteum of the jaw, which proceeds to suppuration and necrosis of a
greater or smaller portion. The effects may develop with great sudden-
ness, and end fatally. Thus Foumier and Olliver^ relate the case
of a girl, 14 years old, who, after working four years in a phosphorus
manufactory, was suddenly affected with periostitis of the upper jaw,
and with intense anaemia. An eruption of purpuric spots ensued, and
she died comatose. There is now little doubt that minute doses of
phosphorus have a specific action on the bones generally, and more
especially on the bones of the jaw. Wegner t administered small daily
doses to young animals, both in the state of vapour, and as a finely-
divided solid. The condition of the bones was found to be more compact
than normal, the medullary canals being smaller than in healthy bone,
the ossification was quickened. The formation of callus in fractured
limbs was also increased.
§ 288. Changes in the Urinary Secretion. — It has been before stated
that, at a certain period of the illness, the renal secretion is scantier
than in health, the urine diminishing, according to Lebert and Wyss's J
researches, to one-half on the third, fourth, or fifth day. It frequently
contains albumen, blood, and casts. When jaundice is present, the urine
has then all the characters noticed in icterus ; leucin and ty rosin, always
present in acute yellow atrophy of the liver, have been found in small
quantity in jaundice through phosphorus; lactic acid is also present.
The urea is much diminished, and, according to Schultzen and Biess,§
may be towards death entirely absent. Lastly, it is said that there is
an exhalation of either phosphorus vapour or phosphine from such urine.
In some cases the urine is normal, e.g. in a case recorded by E. H.
Starling, M.D., and F. G. Hopkins, B.Sc. (Guy's Hospital RepoH, 1890),
in which a girl, aged 18, died on the fifth day after taking phosphorus
* Oaz. hthd. de MiiL, xxix. p. 461, 1868..
t Vircbow's ^irc^. /. paih. Anat.^ Iv. 11.
X Archiv Ginirale de M6d., «S^r., Tom. xii, 1868, p. 709.
§ AnnaUn der ChariU, Berlin.
§ 289-2(/i]
PHOSPHORUS.
235
paste, the li^er was Uliy, and there was jaundice ; but tbo untie con-
tained neither lencin nor tyrti&in^ and waa sUited t€ be generally nonuaL
§ 289. Cimx^ges in the blood during life liavc been Beveml times
observed. In a case attended by M. Komelhere of BruBseb,^ in ^hieh
a man took the p&ste from 300 matches and under treat nictit by
turpentine recovered, the blood was frequently examined, auii the
leucocytes found much increased in number. There is a curious conflict
of evidence as to whether phosphonis prevents coagulation of the blood
or not, Kasse asserted that phosphorated oil given to a dog fully
prevented coagulation ; V. 1, Liebreck t ^Iso, iu a series of reaearchra,
found the blood dark, fluid, and in perfect solution. Thiee observations
were also supported by V. Bibra and Sclmuhiirdt. | NeverthelesSi
Lebert and Wy&s found the bloodt whether in tlie veins or in ejctravaaiir
tiona, in a normal condition. Phosphorus increases the fatty con tenia of
the bloods liitter found that phosphorus mbed with starch, and given
to a dogi raised the fatty content from the normal 2 per 1000 up to
3"41 and 3*47 per 1000. Eug. Menard § saw in the blood from the
jugular and fxirUd veins, bs well as iu extravtiBations, microscopic fat
globules and fine needle-shaped crystals soluble in ether.
g *29Q, Antidote — Treatment, — After emptying the stomach by
means of emetics or by the at<jmach-pump, oil of turpentine in full
meditiinal doscs^ say 2*5 c.c* (about 40 ndu.), frequently administeredi
seems to i^et as a true antidote, and a large percentage of cases treated
early in this way recover.
g 20 L Poisonous Effects of FhoBphine (phospbu retted hydrogen).
— Eiperiraeuts ou pigeons, on rats, and other atiimals, and a few very
rare oases among men, have shown that phusphine lui^ an exeititig action
on the respiratory mucous membranes^ and a secondary action on
the nervous system, Euleuherg || exposed a pigeon to an atnuisphere
containing 1'68 per cent, of phoaphine. There was immediate unrest ;
at the end of throe minutes, quickened and laboured breathing (100 a
minute) ; after seven minutes, the bird lay p rot? t rate, with shivering of
the body and wide-open beak ; after eight minutes, there was vomiting ;
after nine minutesj slow breatluug (34 per minute) j after twelve
minutes, convulsive movcuients of the wings; and after thirteen minutea,
general eonvulsions and death.
" T«rdleu, oj>. Hi., Caae 31.
t BitfS, fU Ftntjito PhmphQYco Acutfi^ \J\imi, 1845*
t V, Bibra u, Geist, Dh Ktmikfuilcn dtr Arbcit^r in den Ffu^phm^ujidfttik
FaLnktu^ 1847. 8, &9, etc ; Honk u. v, Pfeuffer^t Z«(«eAr. / raiion, Mtd., N. ¥.,
ltd. vii„ Hft. 3, im,
% ^ufk Bjjf4fimmk^ mit ^wl^u<t ktimi§ de ^Smp^kfrnMrnm^ m^ for U
Phtmphtytts (TUeiie), Strasbourg, 1369.
II Oewerhc HyffUna^ p 278,
236 POISONS: THEIR KFFKCTS AND DBTKCTION. [§ 292.
The membranes of the brain were found strongly injected, and there
were extravasations. In the mucous membrane of the crop there was
also an extravasation. The lungs externally and throughout were of a
dirty brown-red colour; the entire heart was tilled with coagulated
blood, which was weakly acid in reaction.
In a second experiment with another pigeon, there was no striking
symptom save that of increased frequency of respiration and loss of
appetite ; at the end of four days it was found dead. There was much
congestion of the cerebral veins and vessels, the mucous membrane of
the trachea and bronchi were weakly injected, and the first showed a
thin, plastic, diphtheritic-like exudation.
Dr. Henderson's * researches on rats may also be noticed here. He
found that an atmosphere consisting entirely of phosphine killed rats
within ten minutes, an atmosphere with 1 per cent, in half an hour.
The symptoms observed were almost exactly similar to those noticed in
the first experiment on the pigeon quoted above, and the post-mortem
appearances were not dissimilar. With smaller quantities of the gas, the
first symptom was increased frequency of the respiration ; then the
animals showed signs of sufifering intense irritation of the skin, scratching
and biting at it incessantly ; afterwards they became drowsy, and assumed
a very peculiar attitude, sitting down on all-fours, with the back bent
forward, and the nose pushed backwards between the forepaws, so as to
bring the forehead against the floor of the cage. When in this position,
the rat presented the appearance of a curled-up hedgehog. Phosphine,
when injected into the rectum, is also fatal ; the animals exhale some of
the gas from the lungs, and the breath, therefore, reduces solutions of
silver nitrate, t
Brenner! has recorded the case of a man 28 years old, a phar-
maceutist, who is supposed to have suffered from illness caused by
repeated inhalations of minute quantities of phosphine. He was
engaged for two and a half years in the preparation of hypophosphites ;
his illness commenced with spots before the eyes, and inability to fix the
attention. His teeth became very brittle, and healthy as well as carious
broke ofi^ from very slight causes. Finally, a weakness of the arms and
limbs developed in the course of nine months into complete locomotor
ataxy.
§ 292. Blood takes up far more phosphine than water does. Dybs-
kowsky found that putting the coefficient of solubility of phosphine in
pure water at '1122 at 15', the coefficient for venous blood was 13, and
* Journ. Anal, and Physiol. , vol. xiii. p. 19.
t Dybskowsky, Med. Chein, Unlersuchungen aaa Hoppe-Seyler's Labor, in
TUbingeiif p. 67.
t St. PeUnhurg Med, Zeitaehr,, 4 Hft, 1866.
§ 293^]
PH08PRORUB.
257
for arterial 26*73 ; hence the richer tiie blood is in oxygen the more
pboBphine is absorbed. It seems probable that the poisonous gas reacts
on the oxyhj^moglobin of the blood, and phosphorous acid is formed.
This is supported by the fact that a waterj^ extm<?t of such blood re-
duces silver nitrate, and haa been also found feebly acid. The^dark
blood obtained from animals poisoned by phosphine, when eramined
spectroscopicallj, has been found to exhibit a band in the Tiolet,
§ 293. Post-mortem Appearances.— There are a few perfectly well
authentieated cases showing that phosphorus may canse death* and yet
no lesion be discovered afterwards. Thus, Tardieu * cites a case in
which a woman, aged 45, poisoned herself with phosphorus, and died
suddenly the seventh day after warfls. Dr, Mascarel examined the
viscera with the greatest care, but could discover absolutely no
abnormal conditions ; the only aynipt^ms during life were vomiting, and
afterwards a little indigestion. It may, however, be remarked that the
microscope does not seem to have been employed, and that probably a
close examination of the heart would have revealed some alteration of
its ultimate structure. The case qttoted by Taylor t may also be
mentionefl, in wluch a child was caught in the act of sucking phoaphonis
mat4!hes, and died ten days afterwards in convulsions. None of the
ordinary poet- mortem signs of poisoning by phosphonia were met with,
but the intestines were reddened throughout, and there were no less
thsn ten invaginations ; but the ease is altogetlier a doubtful one, and
no phosphorus may actually have been taken. It is very difficult to
give in a limited space anything like a full picture of the diffen^nt
lesions found after death from phosphorus, for they vary according aa to
whether the death is speedy or prolonged, whether the phosphorus has
been taken aa a finely*divided solid^ or in the form of vapour, etc. It
may, however, be shortly said, that the most common changes are fatty
infiltration of the liver and kidneys, fatty degeneration of the heart,
enlargement of the liver, ecchymosea in the serous membranes, in the
muscular, in the fatty^ and in the mucous tissues. When death occurs
before jaundice supervenes, there may be little in the aspect of the
corpse to raise a suspicion of poison ; but if intense jaundice has existed
during life, the yellow staining of the skin, and, it may Ijc, spots of
purpura, will suggest to the experienced pathologist the possibility of
phosphorus poisoning. In the mouth and throat there will seldom be
anything abnormah In one or two ca-^ea of rapid death among infanta,
some traces of the matches which had been sucked were found clinging
to the gums. The stomach may be healthy, but the most common
appearance is a swelling of the mucous membrane and superficial
t Msm$, Srd ^., p. 276.
238
POISONS: THEIR EFFECTS AND DKTBCTION.
[§ 293
eroaioiia Virohow,* who was the first to gbW atteution to this peculiar
grey swellmg of the intestinal mucous membrane under the name of
gasirifu fjlandularin or gmtradBnitis^ shows that it is due to a fatty
degeneration of the epithelial cells, and that it is by no means peculiar
to phosphoruB poisoning. The swelling may be seen in properly-
prepared tjeetions to have its esaeiitial seat m the glands of the niucoiis
membrane; the glands are enlarged^ their openings filled with large
cells, and each single cell is finely granular. Little centres of h®mor-
rhage, often microscopically smalU are seen, and may be the centres of
small inflammationB; their usual situation is on the summit of tlie
rugffi. Very similar changes are witnessed after deatfi from Beptica^mia^
pyaimia, diphtheria, and other diseases. The soften in j( of the stomach,
gangrene, and deep erosions, recorded by the earlier autborSi have not
been observed of late years » and probably were due to post-mortem
changes, and not to processes during life. The same changes are to be
seen in the inte!itine», and there are numerous extra\'&satious in the
puritoneum.
The liver shows of all the organs the most characteristic signs ; a
more or less advanced fatty iniiltration of its structure takes place
which was first described as caused by phosphorus by Haiifl' in 1860.t
It ia the most constant pathological evidence both in man and animal,
and seems to occur at a very early period, Munk and Ley den having
found a fatty degeneration in the liver far advanced in twenty-four
hours J after poisoning. In rats and mice poisoned with paste, this
may be seen by the naked eye twelve liours after the fati\l dose.
The liver is mostly large, but in a case§ recorded in the Laneet,
* Virchow'a^/rAm/. path. AimL, Bd. xxii. HfL 3, 39§.
t HftUfT oollected 12 caaes, and found n fi^tty livor iu II.— Wurtcmb, Med.
Ci^rrtsp. Bl,, ISSO, No. 34*
t BieaeuU Fhitsphor-Venjifiung^ Berhn, 1865.
§ This case, from tho Himikrity of the jmthologieal appearatjcea to those pro-
duced by yellow atrophy, diserves ftiUer notice : — ** Frauecii A, Cuwley, aged 20, uu
her own admtsaioiij tcxik some mt p^te on TuesdAj^ June 19th. Death ensued
eleveti dAys later. The initial itymptonis were not very iimrkeil. Nausea and
vomiting continued with modemto s*? verity (oit a U^ days and then cefli»od*
There eiiuued a ft*eliiig of depression. Towarrls the end insensibilftyi iotemSj and
somewhat profuBe metrorrba^a flnperveiied. At tbo nectxip^y the Nkin and con*
jtinctivsp were observed of a bright yellow nolour. There wan no organic dL^i^iBe aatro
of a recent nature^ fi-u^J entirely attributable to the action of the pnflon ingested*
The stomach eo II tatned abont three-quartera of a pint of dark cIaret'eoh>urMi Auidf
consiating largely of blood derived from eapillary htcjuorrhage from the mueoiia
membrane. There waa no solution of continuity of the mucous membi^ne, which
abowed traces of rt^ent irritatioij. Th« whole surface protiented a yellow icti*rio
tint, except the i^ummits of ttfjnve of the rugas, which were of a bright pink colour.
Therv was also faint wrtukliiig af tbe muoouB rnembnint?. The upji^^r part of tbe
small intestine was affectdd in much the same manner ua the siomacb. Tha
large iutcHtiue eonUined a quantity of almost colotirleas fnces. The Urer was
§ 293-]
PHOSPHORUS.
239
July 14, 1888, tli^ liver was shmnken ; it has a pale yellow (or some-
times an intense yellow) colour ; on section the cut surface presents a
mottled appearance } the serous enyelopes, especially along the course of
the vessels, exhibit eKtrarasationB of hlood. The liver itself is more
deficient in blood than in the normal condition, and the more bloodless
it is, the greater the fatty infiltration.
In the museum of the Royal College of Surgeons there is a prepara-
tion (No. 2737) of the section of a liver derived from a case of phosphorus
poisoning*
A girl ageti 18, after two days' illness, was admitted into Guy's
Hospital. She confessed to having eaten a piece of bread coated with
phosphorus paste. She had great abdominal pain, and died on the
seventh day after taking the phosphorus, A few hours before her death
she was profoundly and suddenly collapseil. The liver weighed 66 oza.
The outlines of the hepitic lobules were very distinct, each central vein
being surrounded by an opaque yellowish sione ; when fresh the (me was
more uniform^ and the section was yellowish- white in colour, A micro-
seopical examination of the hepatic cells showed them laden with fat
globules, especially in the central parts of the liven
The microscopic appearances are also characteristic. In a case of
suicidal poisoning hy phosphorus, in which death took place on the
seventh day, the liver was very carefully examiued by Dr, O, F. Goodarl^
who reported as follows : —
^* UudEr a low jH>wer tlie atraictare of the liver is still readily recognisable, Mid in
llib the BpecimfiD dithers from flUdea af tlu^e coaes of axsaio yellow Atrt}|jhj that I
hsvp in my posaessioju The hepatio t^ls are present in large tiumbers, and have
tlivir natumt trabecular arrangeiDeDtk The <M>1i)mQs are abnormally Be|Niratcd by
diktetl blood or lymph-spaoes, «id the indindu&l cellfl are cloudy and ill^dti fined*
The portal chauufsla are everywhere characterised by a crowd uf amall nuclei which
stAin with logwood deeply. The epithelium of ths rtmaller ducts in cloudy, and
blocks the tiibe^ in mauy caaeM. Under a high power (one-Bfth) it ta aeeti that the
heps tic ciells are exceedingly ill -defined m outline, and full of gnuules and eran
drops of oil. But m smay parta^ even where the cells themaelTea are bazy^ tba
ahmnkent weighing only 26 ozb., and htxth on its onter and BectioJial atirfoce
eiCACtly Fe»emblod the appearanceii produced by acute yellow atrophy^ elE€(^pt that
there were greater congestion and intertititifll hcpmoiThago in jiatches. The lobules
of the liver were in nmny places iinret?ognisable ; in others they Fitoixl iij ^Kiht
relief aa brilliaiit canary •yellow patch ea^ at-anding in strong contrast to the det'p
dark red areaa of ooDgestion and cxtravaf^ation. The gall bladder cotitampil libout
2 drafchin^s of thin grpyiah Huid, api>arfijtly all but devoid of bile. The ni-rimiy
bladder was empty ; the kidneyij ware cn1argc<l ; the cortex waa very pale and bile-
staiiied, of greater depth than natural, and of softer eousbtcnce. The splwn was
Bot enlarged, nor was It hi the leaiit dogreM.^ softened. In addition to the hk^edlng
from the uterus noticed during Ufe» there was capillary luemorrhage into the right
]ung and pleura, into the pericanlinm, and, m already mentioned^ into the stomach.
The brain wa-s healthy.''
240
POISONS : THEIR EFFECTS AND DETECTrON,
[§294.
nucleus is atiH filrly visible. It ap}>0air^ to ma that^ iii opposition t^ what otben
li*ve dfiteiibed, the nuclei of the cells hove in great nieiLsnre resisted the degenera-
tiye process. The clmtige in the mIU h uniform tbroughout each lobule, but some
!obul&<i ai-e rather more affected than others* The bltK>d'Sijacea betwoen the cells aie
empty, and the liver apj>eara i& be very blmidleas. The portal canala are uniformly
studded with small lound nuclei or cells, ^vhich ai*e in part, and might be said in
grait part, due t^i increaae of the ccmnective ti^ue or to a cirrhotic proees-j* But I
am more difi posed to fuvour the vit^w that they are due to migration from the blood-
yeaaelsj l>ecause they are so uniform in sij&e, and the hepatic cells and connective
tisaue in their neigh hourhooii are undeTjijoiiig no changes in the way of growth what-
ever, I caimot detect any fatty changes in the vessels, but some of the smaller
biliary ducta contain »me cloudy albumiuoua ma to rial ^ and their nucleation is not
dietiiict. No retained biliary pigment is visible*" *
Osear Wysa^t in the case of a woman 23 years old, who died
on the fiftti cky after taking phosphoruB, describes, in addition to the
fatty appearance of the cells, a now formation of cells lying between
the lobules and in x>art snrroutxding the gal 1-d nets and the branches of
the portal vein and hepatic artery,
Saikowsky | found in animals, which he killed a few hours after
administering to them toxic doses of phoBphorna, notable hypeni&mia
of tbe throat, intestine, liver, and kidneys— Iwth the latter organs being
larger than nauah The liver cells were swollen, and tbe nuclei very
evident, but they contained no fat, fatty drops being formed afterwards.
§ 294. Tlie kidney B exhibit alterations veiy similar and analogous to
those of the liver They arc mostly enlarged, congested, and flabby,
with extravasations under the capsule, and show microscopic changes
essentially consisting in a fatty degeneration of the epitheliunL In
cases attended with bsemorrhage, the tubuli may be here and there
filled with blood. Tbe fatty epithelium is especially seen in the con-
torted tubeSj and the walls of the vessels, both of the capsule and
of the malpighian bodies, also undergo the same fatty change. In cases
in which de^tb has occurred rapidly, the kidneys have been found almost
healthy, or a little congested only. Th^ pancreas has also been found
with its structure in part replaced by fatty elements.
Of great significance are also the fatty clnmges it) the general muscular
Bjstem, and more especially in tbe heart. The muscular fibres of the
heart quiekly lose their transverse stnsB, which are replaced by drops of
fat. Probably this change is the cause of tbe sudden death not nii-
freqnently met with in phospborus poisoning.
In the lungs, when the pbosphorns is taken in substance, there is
little ** naked-eye" change, but Perls,^^ by manometric researches, hns
* '* A Recent Case of Suicide,*' by HerWrt .1. Capon, M,D.—Lan<^, Maroh 18,
1882.
t Virchow*H Arehif*/. path, AmL, Bd. x^xxxl Hft 3, S. 432, lSd6*
X Tbid,, Bd. Jtjcxlv. Hft, ] U. 2, S, 73, 1865,
I Dfittath. Anhh^f. klin, Mi^L, vl lift 1, 8» 1, 1869.
I 295, 296,}
PHOSPHOROS,
^41
ihown that the elasticity h always decreaaecL According to experiments
ou auiraals, when the vapour is breathed, the mucous membrane iB red,
ooogested, swollen, and has an acid reaction*
In the nervoiis system no change haa been remarkedj aave ocoasiou-
ally h hemorrhagic points and extravasations.
§295. DiagnoBtie BilTereiices between Acute Yellow Atrophy of
the Liver and Fatty Liver produced by PhoBphonifl.— O. SchnUjsen
and 0* L. Rieas have collected and compared ten eases of fatty liver from
phosphorus poisoning, and four cases of acute yellow atrophy of the Hver,
and, according to tbem, the chief points of distinction are as follows !—
In phospliorus poisoning the liver is large, doughy, equally yellow, and
witli the acini well marked ; while in acute yellow atrophy the liver is
diminished in size, tough, leathery, and of a dirty yellow huCj the acini
not being well mapped out The "phosphorus" Hver, again, preeenta
tlie cells filled with large fat drops, or entirely replaced hy them ; but in
the "atrophy" liver, the cells are replaced by a finely 'nucleated detritus
and through newly-formed cellular tissue. Yellow atrophy seems to be
eBsentialiy an inflammation of the intTalobuIar connective tissue, while in
phoaphorus poisoning the cells Iwcome gorged by an infiltmtion of fat,
which presses upon the vessels and l^sens the blood supply, and the
liver, in consequence, may, after a time, waste-
There is also a chnical distinction during life, not only in the lessening
bulk of the liver in yellow atrophy, in opijosition to the increase of sJEe
in the large phosphorus liver, but also in the composition of the renal
secretion. In yellow atrophy the urine contains so much leucine and
tyros in, that the simple addition of acetic acid causes nt once a precipitate,
Schultzen and Riess also found in the urinCi in cases of yellow atrophy,
oxtjmanddk acid (CjjHgO^), but in cases of phosphorus poisoning a nitro-
genised acid, fusing at 184° to 185\
According to Maschka, grey- white, knotty^ faecal masses are found in
the intestineH in yellow atrophy, but never in cases of phosphorus poison-
ing. In the latter, it is more common to find a slight intestinal catarrh
and fluid excreta.
g 296. The Detection of Phosphortis,— The following are the chief
methods in use for the separation and detection of phosphorus :*^
L MitBcherlich's Frocess, — The essential feature of this process is
simply distillation of free phosphorus, and observation of its lununons
properties as the vapour condenses in the condensing tube. The condi-
* It hii^ bt^n i-^^commt^tided to diAsolve the phosphorus out from organic mattera
by c^rlwn db!uli>hifle. On evajioration of the Utt«r the jihoHphonis b reeogniswi
Ivy its physical properties. Such a method is of but limited application, dthongh
it luay Bometimes be found mtefnl. The soiiior autlior has succt^aa Fully employed it
hi the extmction of phosphorus from the <;rop of a fowl ; but on this occAaiou it
hupi^eaed to l>e prest-*«t in huge (juantity*
16
242 POISONS : THEIR EFFECTS AND DETECTION. [§ 296.
tioDs necessary for success are— (1) that the apparatus should be in total
darkness ; * and (2) that there should be no substance present^ such
as alcohol or ammonia, f which, distilling over with the phosphorus
vapour, could destroy its luminosity. A convenient apparatus, and one
certain to be in all laboratories, is an ordinary Florence flask, containing
the liquid to be tested, fitted to a glass Liebig's condenser, supported on
an iron sand-bath (which may, or may not, have a thin layer of sand), and
heated by a Fletcher's low temperature burner. The distillate is received
into a flask. This apparatus, if in darkness, works well ; but should the
observer wish to work in daylight, the condenser must be enclosed in
a box perfectly impervious to light, and having a hole through which
the luminosity of the tube may be seen, the head of the operator and the
box being covered with a cloth. If there be a stream of water passing
continuously through the condenser, a beautiful luminous ring of light
appears in the upper part of the tube, where it remains flxed for some
time. Should, however, the refrigeration be imperfect, the luminosity
travels slowly down the tube into the receiver. In any case, the deli-
cacy of the test is extraordinary. | If the organic liquid is alkaline, or
even neutral, there will certainly be some evolution of ammonia, which
will distil over before the phosphorus, and retard (or, if in sufficient
quantity, destroy) the luminosity. In such a case it is well, as a precau-
tion, to add enough sulphuric acid to flx the ammonia, omitting such
addition if the liquid to be operated upon is acid.
2. The Production of Fhosphine (PH3). — Any method which pro-
duces phosphine (phosphuretted hydrogen), enabling that gas to be
passed through nitrate of silver solution, may be used for the detection
of phosphorus. Thus, Sonnenschein states that he has found phos-
phorus in extraordinary small amount, mixed with various substances,
by heating with potash in a flask, and passing the phosphine into silver
nitrate, separating the excess of silver, and recognising the phosphoric
acid by the addition of molybdate of ammonia.§
The usual way is, however, to produce phosphine by means of the
action on free phosphorus of nascent hydrogen evolved on dissolving
metallic zinc in dilute sulphuric acid. Phosphine is formed by the
* Any considerable amount of phosphorescence can, however, be observed in
twilight
t Many volatile substances destroy the luminous ap^iearance of phosphorus
vapour, e.g, chlorine, hydric sulphide, sulx)hur dioxide, carbon disulphide, ether,
alcohol, petroleum, turpentine, creasote, and most essential oils. On the otlier hand,
bromine, hydrochloric acid, camphor, and carbonate of ammonia do not seem to inter-
fere much with the phosphorescence.
t Fresenius states that he and Neubauer, with 1 mgrm. of phosphorus in 200,000,
recognised the light, which lasted for half an hour. — Zeitachr, f, anal, Chem,^ i.
p. 336.
% Sonnenschein, Handhich der gerichtlichen Chtinief Berlin, 1869.
§296.]
PHOSPHOBUS.
243
action of nascent hydrogen on ^olid phosphorns, phoaphorouB acid, and
hypopho^pfiorous acid ; but no phoaphine can be formed in tVjis way by
the action of hydrogen on phosphoric acid.
Since it may happen that no free phosphorus is present, but yet the
first product {phosphorous acid) of its osidatiou, the production of pbos-
phine becomes a necessary test to make ou failure of Miti^cherlich's
test ; if no result follows the proper applit-ation of the t^o processes,
the probability h that phosphorus has not been taken.
Blgndlot and Dusart evolve hydrogen from 21 nc and dilute sulphuric
acid, and pass the gas into silver nitrate; if the gaa is pure, there in
of counse no reduction : the liquid to be tested is then added to the
hydrogen-generating liquid, and if phosphorous or hypo phosphorous acids
be present, a black precipitate of phosphor-silver will be produced. To
prove that this black precipitate is neither that produced by SH,>, nor
by antimony nor arsenic, the precipitate is collected and placed in the
apparatus to be presently described, and the spectroscopic appearances of
the phosphiue flame observed.
3. Tests dependent on the Combustion of Phosphiiie (PH,^)* — A
hydrogen flame, containing only a minute trace of piiowphorus, or of the
lower product of its oxidation, acquires a beautiful green tint^ and
peeaesses a characteristic syjedmm. In order to obtain the latter in its
best fornif the amount of phosplnne must not be too hirge, or the flame
will Ijecome whitish and livid, and the bauds lose their defined characteri
renderiiig the speetmm continuous. Again^ the orifice of the tube
whence the gas escapes must tmt be too smalt ; and the best result is
obtained when the flame is cooled,
M. Salet has proposed two excellent methods for the obsorvation of
pbosphine by the spectroscope : —
(1) He projects the phosphorus flame ou a plane vortical surface,
nmintained constantly cold by means of a thhi layer of running i^ater;
the green colour is especially produced in the neighbourhofKl of the
cool surface.
(2) At the level of the base of the flame there is an annular space,
through which a stream of cold air is continually blown u]jwanl3. Thus
cooled, the light is very pronounced^ and the band S, which is almost
invisible in the ordinary method of examination, is plaiidy seen.*
An apparatus (devised by Blond lot, and improved by Fresenius) for
the production of the phosphiue Hame in medico-legal research, is repre-
sented in the diagram on the following page: —
Several of the details of this apparatus may be modified at the con-
* CoDfiitlt Spfidres Liimiiteitsr^ jiar M. Lccoq de BoisliAudran, Puris, 1874. Bet
«koChri«tofleoTid Beiktronrs * * Abhandlung" iu Fresenim^ ZtUschr./. an^t, Chem.t
B, ii ju ia\ ami 11 iii. {k 147.
244
VOBOXS: TUUK DTKHS AXD UUtL'lVfSL
[1237.
TenieDoe of the opentor. A is a ft— J eoDtftimng solplmiir acid ; B k
partlT fiUed witli gmiizlated imc, and hjdiogai maj be developed at
pleasure ; c coDtains a solutJon of nhnte of sihrer ; ^ is a tube at vbich
the gas can be lit : e, a flask oontaining: the fluid to be tested, and pnK
vided with a tube/, at vhich also the gas ifiwihig can be ignited. Tlie
orifice should be proTided with a platmnm noode. When the hjdiogen
has displaced the air. both tubes are lit^ and the two flames, being aide
bj side, can be oompsred. Should anj phosphoros come orer fram the
zinc (a possibility which the interposed silver nitrate ooght to gnard
against), it is detected : the last flask is now gentlj wanned, and if
the flame is green, or, indeed, in anj ease, it should be examined br
the spectroscope.*
§ 297. The spectrum, when fully developed, shows one band in the
orange and yellow between C and D, but venr cloee to D, and several
bands in the green. But the bands ^ y, a, and fi are the roost
characteristic. The band S has its centre about the wave-length 599*4 ;
it is easily distinguished when the slit of the spectroscope is a little
wide, but may be invisible if Uie slit is too narrow. It is best seen by
M. iSalet's second process, and, when cooled by a brisk current of air, it
V/roadens, and may extend closer to D. The band y has a somewhat
decided lx)rrler towards £^ while it is nebulous towards D, and it is,
therefore, very difficult to say where it begins or where it ends ; its
centre may, however, he put at very near 109 of Boisbaudran's scale,
corresponding to W. L. 560*5, if the flame is free. This band is more
* F. S^rlmi hAA propoMd the nmple dipping of m platinum loop into a liquid coo-
tatuing pbcif pboric acid, and then inserting it into the tap of a hydrogen flame.
§ 29S,]
piiospaoKUs.
24S
distinct than ^j but with a htrtiug current of air the reverse it^ the case^
The middle of the importtint band a is nearly marked by FraunUofer's
line E, BulMbaudrau givey it as coincidiug with 122 of his ^jcnle W. L.
526 "3* In ordinary conditions (that is, with a free uncooled flame) this
iij the bri^hteiit and most marked of all the banda. The approximate
middle of the band jS ia W. L. 510'6 {Boiabaud raw's scale 120'00).
Lipowitz'B Sulphur Test. ^-Sulphur hm the peculiar property of
condeuiiing phosj^horas ou its aurfacc^ and of this Lipowitz proposed to
take advantage, Piecesi of yulpbur are digested some time with the
liquid under research, subaequeutly reraovedj and slightly dried. When
examined in the dark, should phogphorus be present, they gleam istrongly
if rubbed with the linger, and develop a phoBphorua odour. The test m
wanting in delicac^y, nor can it well be made quautitative; it has, how-
ever, an advantage in certsiin crises, G.fj, the detection of pbo»pborus in
an alcoholic liquid,
Scherer's test, as modified by Hager,* is a very delicate aud akuost
decisive tent* The substances to be examined are placed in a flask with
a little lead acetate (to prevent the possibility of any hydric sulphide
being evolved), aoaie ether added, and a strip of filter-paper soaked in a
solution of silver nitrate ia then suspended in the flask ; thiis in con-
veniently done by making a slit in the bottom of the cork, and in the
slit securing the paper. The closed i\mk is placed in the dark, and if
phosphorus is present, in a few minutes there is a black stain. It may
bo objected that arslne will cause a similar staining, but then arsino
could hardly bo developed under the ei re u instances given. It is
scarcely necessary to observe that the paper must be wet,
1 298. Ohemiea! Examination of the Uniie.— It may be desirable,
in auy case of suspected phosphorus [>oisouiiig, to examine the reual
secretion for leucin and tyrosin, etc, Loucin may be found as a deposit
iu the urine. Its general appearance is that of little oval or round discs,
looking like drops of fat. It can be recognised by taking up one or more
of these little bodies and placing thetn in the author's subliming cell (see
p, 259). By careful lieating it will sublime wholly on to the upper cover.
Ou now adding a little nitric acid to the sublimed leucin, and drying,
and then to the dried residue adding a droplet of a solution of sodium
hydrate, leuciti forms an oily drop. Tyroain also may occur as a sediment
of little heaps of fine needles. The best test for tyrosin is to dissolve m
hot water, and then add a drop of a solution of mercuric nitrate and
mercurouB nitrate, when a rose colour ia at once developed, tf the tyrosin
is in very minute quantity ; but if in more than traces, there is a distinct
erimson pi*ecipitate. To separate leucin and tyrosin from the urine, the
best process is as follows: — The urine is filtered from any deposit,
246 POISONS : THEIR EFFECTS AND DETECTION. [§ 299.
evaporated to a thin syrup, and decanted from the second deposit that
forms. The two deposits are mixed together and treated with dilute
ammonia, which will dissolve out any tjrosin and leave it in needles, if
the ammonia is spontaneously evaporated on a watch-glass. The urine
is then diluted and treated with neutral and basic acetates of lead, filtered,
and the lead thrown out of the filtrate by hydric sulphide. The filtrate
is evaporated to a syrup, and it then deposits leucin mixed with some
tyrosin. If, however, the syrup refuses to crystallise, it is treated with
cold absolute alcohol, and filtered ; the residue is then boiled up with
spirit of wine, which extracts leucin, and deposits it on cooling in a
crystalline form. To obtain oxymandelic acid, the mother-liquor, from
which leucin and tyrosin have been extracted, is precipitated with
absolute alcohol, filtered, and then the alcoholic solution evaporated to a
syrup. This syrup is acidified by sulphuric acid, and extracted with
ether ; the ether is filtered off and evaporated to dryness ; the dry residue
will be in the form of oily drops and crystals. The crystals are collected,
dissolved in water, and the solution precipitated by lead acetate to remove
colouring matters; after filtration it is finally precipitated by basic acetate.
On decomposition of the basic acetate, by suspending in water and
saturating with hydric sulphide, the ultimate filtrate on evaporation
deposits colourless, flexible needles of oxymandelic acid. The nitro-
genised acid which Schultzen and Riess obtained from urine in a case of
phosphorus poisoning, was found in an alcohol and ether extract — warts
of rhombic scales separating out of the syrupy residue. These scales gave
no precipitate with basic acetate, but formed a compound with silver
nitrate. The silver compound was in the form of shining white needles,
and contained 33*9 per cent, of silver; the acid was decomposed by heat,
and with lime yielded aniline. Its melting-point is given at from 184*
to 185**. The occurrence of some volatile substance in phosphorus
urine, which blackens nitrate of silver, and which is probably phosphine,
was first noticed by Selmi.* Pesci and Stroppa have confirmed Selmi's
researches. It is even given off in the cold.
§ 299. The quantitative estimation of phosphorus is best carried
out by oxidising it into phosphoric acid, and estimating as ammon.
magnesian phosphate. To effect this, the substances are distilled in an
atmosphere of 00^ into a flask with water, to which a tube containing
silver nitrate is attached ; the latter retains all phosphine, the former
solid phosphorus. If necessary, the distillate may be again distilled into
AgNOg ; and in any case the contents of the y -tube and flask are mixed,
oxidised with nitromuriatic acid, filtered from silver chloride, and the
phosphoric acid determined in the usual way.
In the case of a child poisoned by luoifer matches, Sonnenschein
* QiamaU JnUmaz, deUa Scienza Med,^ 1879. Nro. 5, p. 645.
Sjoa]
ptiospitofics.
247
estimated the free ph<>sphonifi in the followiiig wmjz — The ©on tents of
the stomach were diluted with water, a measured part filteit^, and
the phosphonc aisid estimated. The other portion waa then oxidieed
by HCl and pot&esie ehlomte, and the phosphoric acid estimated — the
di^erence being calculated as free phosphorus,
§ 300. How long can Fbogphoms be recognised after Death f—Otie
of the most important matters for eouBideration ib the time after d^itli in
which free pbospborus, or free phoepboric acids, can \m detected. Any
phosphorus changed into ammon* mag. phosphate, or into any other saltj
is for medico-legal purposes entirely lost, since the expert can only Uiko
ooguJBauce of the substance either in a free state, as phosphitiet or i\» a
free acid.
The question, again, may be asked in court — ^Does the deooni position
of animal substances rich in phosphorus develop phosphine ? The answer
to this is, that no such reaction has been observed.
A case is related * in which phosphorus was recognised^ although the
body had been buried for several weeks and then exhumed*
The expert of pharmacy of the Provincial Government Board of
Breslau has also made some experiments in this direction, which are
wortliy of note : — Four guiuea-pigs were j.)oisonedj each by 0 "023 grm.
of f^hosphoruH ; they died in a few hours, and were buried in sandy loam
soil, 0*5 metre deep. Exhumation of the first took phice four wrecks after*
The putrefying organs— heart, liver, spleen, stomach, and all the in tea*
tines — tested by Mitscberlich*s method of distillation, showed charac-
teriatic phosphorescence for nearly one hour.
The second animal was eihnmed after eight weeks in a highly putres-
cent state. Its entrails, on distiUatton, showed the phosphorescent
appearance for thiry-hve minutes*
The third animal was taken from the earth after twelve weeks, but no
free phosphorus could be detected, although there was evidonoe of the
lower form of oxidation (PO^) by Blondlot*s method.
The fourth animal was exhumed after fifteen weeksi but nfither free
phosphorus nor PO^i could be detected*!
A man, as well as a cat, was poisoned by phosphorus. On analysis,
twenty-nine days after death, negative results were alone obtainod, —
(Bonneuschein,)
It will thus be evident that there is no constant rule, and that, even
when decomposition is much advanced, an examiuation frm^ lie
successful.
t FierUfjtihraMehH/$/yr gericMlichc Mrdicin^ Smxx. 7, 187* 1
1 Ghmme, 18711
B«« also Mei^chr, f.
PART VI. -ALKALOIDS AND POISONOUS VEGETABLE PRIN-
CIPLES SEPARATED FOR THE MOST PART BY ALCO-
HOLIC SOLVENTS.
DIVISION I.— VEGETABLE ALKALOIDS.
L— General Methods of Testing* and Extracting* Alkaloids.
§ 301. General Tests for Alkaloids.— In order to ascertain wliether
an alkaloid is present or not, a method of extraction must be pursued
which, while disposing of fatty matters, salts, etc., shall dissolve as little
as possible of foreign substances — such a method, e.^., as the original
process of Stas, or one of its modern modiBcations.
If to the acid aqueous solution finally obtained by this method a
dilute solution of soda be added, drop by drop, until it is rendered
feebly alkaline, and no precipitate appear^ whatever other poisonous
plant-constituents may be present, all ordinary alkaloids * are absent.
In addition to this negative test, there are also a number of sub-
stances which give well-marked crystalline or amorphous precipitates
with alkaloids.
§ 302. These may be called " group reagents." The chief members
of the group reagents are — iodine dissolved in hydriodic acid, iodine
dissolved in potassic iodide solution, bromine dissolved in potassic
bromide solution, hydrargo-potassic iodide, bismuth-potassic iodide,
cadmic potassic iodide ; the chlorides of gold, of platinum, and mercury ;
picric acid, gallic acid, tannin, chromate of potash, bichromate of potash,
phospho-molybdic acid, phospho-tungstic acid, silico-tungstic acid, and
Frohde's reagent. It will be useful to make a few general remarks on
some of these reagents.
Iodine in hydriodic add gives either crystalline or amorphous pre-
cipitates with nearly all alkaloids ; the compound with morphine, for
* In the case of morphine tartrate, this test will not answer. See the article on
Morphine.
348
§ 303,]
VEGETABLE ALKALOIDS,
249
eiample, is in very defitiitc uecdles; with dilute Bolutioug of utropiue,
the precipitate IB iu the form of miuute dota, but the majority of the
precipitatet^ are amorphous^ and all are more or less coloured.
lodme dissolved in a solution of potassic iodide gives with alkaloids
a reddish or rod-brown precipitate, and this in perha|m a greater dilu-
tion than almost auy reagotjt. Since the testing solution may be nho
used for ascertaining the weight of the alkaloid, it iaoouveuient to make
it a decinormal one^ that is, 12 '7 grma, 1 and 60 grms. KI, dissolved in
a litre of water. When added to an aqueous solation, the precipitates
are amorphuus, but if added to an alcohotic solution, certaiti alkaloids
then form crystidline precipitates ; this^ far example, is the ease with
berberine and narceine. The aqueous solution should be either neutral
or feebly acid. The alkaloid may be recovered by the proeCBii detailed
on page 253. A solution of bromine iu potassie bromide solution &ho
gives similar precipitates to the above, but it forma insoluble compounda
with phenol, orcin, and other substances.
Mercuric potaasic iodide h prepared by decomposing mercuric
chloride with potasssic iodide iu excess. The propoitionts are 13'546
grms. of mercuric chloride and 4 9 "8 of jwjtaasic iodide, and water
sufficient to measure, when dissolved, 1 litre. The precipitates from
this reagent are white and lloccnlentj many of them become, on
standing, crystalline.
BiBmuthic potassic iodide in solution precipitates alkaloids, and the
ctjm pounds formed are of great insolubility, but it also forois eom}:iounds
with the various albuminoid bodies.
Iodised parethoxyphenyl succinimide ik another reagent which
precipitates alkaloidS| and is said to be even more sensitive than iodine
in pot iodide.
Chloride of gold forms with the alkaloids eomijomids, many of which
are crystalline, and most admit of utilisation for qimntitative determina-
tions, Cliloride of gold does not precipitate amides or ammonium com-
pounds^ and on this account its value is great. The precipitates are
yellow, and after a while are partly decomposed, when the coluur is of a
retldiah* brown,
Platinic chloride also forms precipitates with most of ttie alkaloid s,
but since it also precipitates ammonia and potasste salts, it is inferior to
gold chloride in utility,
I 303. (1) Pbosphomolybdle Aeid as a Beageut for Alkaloids. —
Preparaiiou: Molybilate of amniotua is precipitated by phospfiate of
iK>da ; and the well- washed yellow precipitate is suspended in water and
warmed with carbonate of soda, until it is entirely dissolved. This solu-
tion is evaporated to dryness, and the amnionia fully expelled by heat-
ing. If the molybdic acid is fairly reduced by this means, it is to be
250
POISONS: THEIR EFFECTS AND DETECTION.
[§ 303.
moistened by uitric acid, and the heating repeated. The now dry residue
is warmed with water, nitric acid added to strong acid reaction, and the
mixture diluted with water, so that 10 parts of the solution contain 1 of
the dry salt. The precipitates of the alkaloids are as follows : —
Aniline, .
Bright yellow, flocculent
Morphine,
ft a
Narcotine,
Brownish-yellow, „
Quinine, .
Whitish-yellow, „
Cinclionine,
H M
Codeine, .
Brownish -yellow, voluminous.
Strychnine,
White-yellow,
Brucine, .
Yelk-yellow, flocculent
Veratrine,
Blight yellow, „
Jervine, .
>» >»
Aconitine,
it a
Emetine, .
i> >»
Theine, .
Bright yellow, voluminous.
Theobromine,
II n
Solanine, .
Citron-yellow, pulverulent
Atropine,
Bright yellow, flocculent
Hyoscyamine,
II II
Colchicine,
Grange-yellow, ,,
Delphinine,
Grey-yellow, voluminous.
Borbcrine,
Dirty yellow, flocculent
Coniine, .
Bright yellow, voluminous.
Nicotine, .
»» II
Piperine, .
Brownish-yellow, flocculent
(2) Silico-Tungstic Add as a Reagent for Alkaloids.— Sodium tung-
state is boiled with freshly precipitated gelatinous silica. To the solution
is added mercurous nitrate, which precipitates the yellow mercurous
silico-tungstate. This is filtered, well washed, and decomposed by an
equivalent quantity of hydrochloric acid ; silico-tungstic acid then goes
into solution, and mercurous chloride (calomel) remains behind. The
clear filtrate is evaporated to drive oflf the excess of hydrochloric acid,
and furnishes, on &jx)ntaneous evaporation, largo, shining, colourless
octahedra of silico-tungstic acid, which effloresce in the air, melt at 36°,
and are easily soluble in water or alcohol.
This agent produces no insoluble precipitate with any metallic salt.
Caesium and rubidium salts, even in dilute solutions, are precipitated by
it ; neutral solutions of ammonium chloride give with it a white precipi-
tate, soluble with difficulty in large quantities of water. It precipitates
solutions of the salts of quinine, cinchonine, morphine, atropine, etc. ; if
in extremely dilute solution, an opalescence only is produced : for in-
stance, it has been observed that cinchonine hydrochlorate in innr^nnr'
quinia hydrochlorate in Tnr.WTF* naorp^ia hydrochlorate in y^.i^j dilution,
all gave a distinct opalescence. — Archiv der Phann,^ Nov., Dr. Richard
Gk)deffroy.
§ 304-^06.]
VECJ STABLE ALKALOlDa
251
According to Gabriel Bertmnd ( CompL ifefkf., cxxviil 742), the salts
posseBH the general formula 1 2Wo03SiOgMk + iiH^O, the morphine salt
haa the formula* of P2WoOa.8iO.,2H204C47HjoN03 + 9Hj^.O j dried ut
1 20', it still contatna 2 molecules* of water ; the sti^ychniue suit ia
similar, but retains only 1 mol of water on drying. These compounds
are insoluble in acids or cold water; for the moat part they do not
interfere with colour tests, mid on treatment with dilute alkalies^
silieium and tungsten pasi^ into solution and the alkaloid can either he
filtered oif or shaken out with appropriate solvents.
(3) Scheibler'fi Method for Alkaloids: Phospho Tungstic Add.^ —
Ordinary eommercial aodiam tungatate is digested with half its weight
of phospboric acidj specific gravity 1*13, and the whole allowed to stand
for some tlaya, when the acid separates in crystals. A solution of these
crystals will give a distinct precipitate with the moat minute quantities
of alkaloids, ^iJF/tTiyir ^^ strychnine^ and hjtfVotj ^^ quinine* The alkaloid
is liberated by digestion with tiurium hydrato (or calcium hydrate); and
if volatile, may be distilled oil'; if fixed, dissolve*! out by chloroform*
In complex mixtures, colouring mutter niay he removed by plumbic
acetate, the lead thrown out by SHg, and concentrated, so as to reuiove
the excess of SIl,^*
§ 304. Schulze's reagent its phospho-antimonic acid. It is prcfiarcd
by dropping a strong aolutjon of antimony tricldoride into a saturated
solution of scxlic {ilioHphate, The precipitation of the alkaloids is
etfected by this reagent in u sulphuric acid solution.
g 3Q(l Dragendorfif's reagent is a S4.4ution of potaas-biamuth iodide;
it ia prepared by dissolving bii^niuth iodide in a hot solution uf
potassium iodidci and theo diluting with an equal volume of iodide of
potaasium solution. On the additiou of an acid solution of an alkaloid,
a kernies-red precipitute falls down^ which is in many cases crystalline,
Marme'B reagent ia a solution of potassHmdmlum iodide. It is made
on similar principles.
PotasB-zinc iodide in solution is also made similarly. The pre
cipiUites produced in solutions of narceine and codeine are crystalline
and very characteristic.
§ 306. Coloiir Tests.— Frohde's reagmit i^ made by dissolving 1
part of sodic molybdutc io 10 parts of strong sulphurio acid ; it strikes
diistjuctive colours with many alkaloids.
Mandelln's reagent i» a solution of mcta-vanadate of ammonia in
mono- or dihyd rated sulphuric acid. The strength should be 1 part of
the salt to 200 of the acid. This reagent strikes a colour with many
alkaloids, and aids to their idontiticatiou, It is specially useful to
supplement and correct other teste* (Sec p. 58 for the spectroscopic
ftppearancea of certain of the colour tests.)
252 POISONS : THEIR EFFECTS AND DETECTION. [§ 3O7.
METHODS OF SEPARATION.
§ 307. General processes for the Separation of Alkaloidal Substances
from Organic Matters. — The processes in use are the Stas-Otto process,
the process of Kippenberger, and that of DragendorlF. The Hilger-
Kuster method, in which gypsum is used, apparently leads to poor
results, aud will therefore not be described.
The three processes are seldom used singly, but more or less in com-
bination. The Stas-Otto process consists in exhausting the organic
matters with strong alcohol. With every kilogramme of such sub-
stances as liver or other internal organs, rather more than a litre of
alcohol of 92 to 95 per cent, strength is required. The more finely
divided the organ is the better. For this purpose it is often advisable
to pass the matters through a mincing machine. The flask containing
the substances and the alcohol is placed in a water-bath and the cork
connected with a reflux condenser. The water in the bath is kept at a
boiling temperature from one to two hours. In the original Stas-Otto
process an acid, such as tartaric acid, was usually added ; but if the
substance itself, as is usually the case, has an acid reaction, and at the
end of the operation the alcohol is found acid, it is preferable not to add
acid. The alcoholic solution is filtered through a piece of muslin and
the organic matter pressed in a filter press, so as to squeeze the solution
out of the mass. It is best now to distil ofl* the alcohol, and then to
extract the watery fluid in a separating funnel by petroleum ether two
or three times, otherwise there will be much difficulty in filtration.
The petroleum ether extract contains all the fatty matter and, it may
be, some of the alkaloid dissolved in the fat. To recover this the
petroleum is distilled ofl*, a little paraffin wax added to the fatty matter
left behind, and the fatty matters washed in a separating funnel with
hot water made slightly acid by means of hydrochloric acid.
The original liquid, free from fat, is then filtered. The clear liquid
to which the washings of the fat are added is now evaporated to dryness
and treated with absolute alcohol. The absolute alcoholic extract is
filtered and evaporated to dryness. This contains all the alkaloid in an
impure state. It is, however, important to note that even when no
alkaloidal poison is present, the extract invariably contains residues
which give decided reactions with the group-alkaloidal reagents, such
as iodine and potassic iodide, phospho-tungstic acid, and so forth.
Eippenberger's Process. — In Kippenberger's process the reaction
of the final product with general alkaloidal reagents in operating
on alkaloidal free substances is much less than in the Stas-Otto
process.
Kippenberger extracts the organic substances with glycerin holding
§ 3o8.]
VliaKTABLK ALKAmiDS.
2S3
tannin in solution. To 500 grms. of gl;ycerin should be added about
100 grma. of tannin*
The extraetioii may be eondnctefl at a gentle heat^ and should be
continued for several hours. The glycerin sol ut ion ig filtered^ a process
which is facilitated by diluting the glycerin^ with this extract, as with
tlie Stas-Otto process, it is advisable to extract the fat by petroleum
ether before filtration.
It is best in practice to combine the Staa-Otto process with Kippen-
berger^a, that is to say, to apply Kippenberger*s process to the iiltiniate
alcoholic extract derived from the Staa-Otto prot^ei^s in order to get rid
of impurities*
In ettiier case the final aqueous, slightly acid solution may be
treated with either the general alfcaloiiial reagents or it may be very
carefully a Ik alised by a solution of potash ; if uo turbidity or precipitate
occursj then no ordinary alkaloid is present. Should a cloud or precipitate
occur the liquid can be made acid^ so aa to dissolve the precipitate,
and be submitted to Dragendorff s process.
Most alkaloids can also be purified by Kippenberger's* iodine method,
which is as follows :^Tho supposed idkaloid is dissolved in a little acid
water, which is then just made neutral by soda solution; it is then pre-
cipitated by a iiolution of iodine and potiissic iodide (12"7 grms* I and 60
grms. KI to the litre), the precipitate is filtered through an asbestos
filter and washed with cold water, it is then dissolved in acetone, to
the acetone ig added KaOH solution to saturate free iodine, the alkaline
solution is next acidified and mixed with water. The scarcely coloured
final solution contains the alkaloid as an acid siilt The solution is now
gently warmed in the water-bath to evaporate ofl:' the acetone, and while
still warm a few^ drops of d.n, ijolutlon of thio-sulphate added. The acid
is now over-saturated with sodic carbonate and the alkaloids shaken out
by means of an appropriate volatile solvent. A silico-tungatate of the
alkaloid may also be made, or a picrate ; in either ease on alkalising the
alkaloid is set free, and may be separated by amyl-alcohol, chloroform,
ether, according to its solubility^
g 308. Selmi'fl Process for Separating Alkaloids. — A method of
separating alkaloids from an ethereal solution haa been proposed by
Selmi.t The alcoholic extract of the viaeeni, acidified and filtered, is
evaporated at 65'' ; the residue t^iken up with water, filtered, and
decolorised by basic acetate of lead. The lead is thrown out by
sulphuvetted hydrogen ; the solution, after concentration, repeatedly
extracted with ether; and the ethereal solution saturated with dry
C0.>, which generally precipitates some of the alkaloids. The ethereal
• Zeil.f. analiftMie Chmkt ISM, 114.
f Selmi, Ga^U. Ckim, Ital, vj. l&3-ie6, and Jtrnm^ Chem, Soe,,h, 1877, 93.
254 POISONS: THKIR EFFECTS AND DETECTION. [§ 309.
solution is then poured into clean vessels, and mixed with about half
its volume of water, through which a current of COg is passed for twenty
minutes ; this may cause the precipitation of other alkaloids not thrown
down by dry COg. If the whole of the alkaloids are not obtained by
these means, the solution is dehydrated by agitation with barium oxide,
and a solution of tartaric acid in ether is added (care being taken to
avoid excess) ; this throws down any alkaloid still present. The detec-
tion of any yet remaining in the viscera is effected by mixing with
barium hydrate and a little water, and agitating with purified amylic
alcohol ; from the alcohol the alkaloidn may be subsequently extracted
by agitation with very dilute sulphuric acid.
Another ingenious method (also the suggestion of Selmi) is to treat
the organic substance with alcohol, to which a little sulphuric acid has
been added, to filter, digest with alcohol, and refilter. The filtrates are
united, evaporated down to a smaller bulk, filtered, concentrated to a
syrup, alkalised by barium hydrate, and, after the addition of freshly
ignited barium oxide and some powdered glass, exhausted with dry
ether ; the ether filtered, the filtrate digested with lead hydrate ; the
ethereal solution filtered, evaporated to dryness, and finally again taken
up with ether, which, this time, should leave on evaporation the alkaloid
almost pure.
§ 309. DragendorflTs Process.— To Dragendorff we owe an elaborate
general method of separation, since it is applicable not only to alkaloids,
but to glucosides, and other active principles derived from plants. His
process is essentially a combination of those already known, and its dis-
tinctive features are the shaking up — (1) of the acid fluid with the
solvent, thus removing colouring matters and certain non-alkaloidal
principles ; and (2) of the same fluid made alkaline.
I. The substance, in as finely-divided form as possible, is digested for
a few hours in water acidified with sulphuric acid, at a temperature of
40" to 50**, and this operation is repeated two or three times, with
filtering and pressing of the substances ; later, the extracts are united.
This treatment (if the temperature mentioned is not exceeded) does not
decompose the majority of alkaloids or other active substances ; but there
are a few (e.g, solanine and colchicine) which would be altered by it ;
and, if such are suspected, maceration at the common temperature is
necessary, with substitution of acetic for sulphuric acid.*
II. The extract is next evaporated until it begins to be of a syrupy
consistence ; the residue mixed with three to four times its volume of
alcohol, macerated for twenty-four hours at about 34°, allowed to become
* When blood is to be examined, it is better to dry it, and then powder and
extract with water acidified with dilute sulphuric acid. However, if the so-called
volatile alkaloids are suspected, this modification is to be omitted.
§309-]
draokndobff's trockss.
255
quite cool, and filtered from the foreign matters wiiich have separated,
The residue ia waRhcd witti alcohol of 70 per cent
IIL The filtrate is freed from alcohol by distillation, the watery residue
poured into a capacious tlaak, diluted (if necessary) with water^ and
filtered^ Acid as it is, it is extracted at the common temperature, with
freciTieut shakingj by freahly- rectified petroleum ether; and, after the
fluids have again separated, the petroleum ether is removed, carrying
with it certain impurities (colouring matter, etc.), which arc in this way
advantageously displaced. By thin operation ethereal oils, carbolic acid,
picric acid, etc., which have not been distilled, besides piperin^ may also
be separatefl. Tlie shaking up with petroleum ether is repeated several
times (as long as anything remains to be dissolved), and the products are
evaporated on several watch-glasses.
The fluid is next successively shaken up with benzene and chloroform,
the solvents being removed and evaponited as before, the last traces of
ehloroforiu are removed by petroleum ether, and the liquid alkalised by
ammonia is shaken up successively with petroleum ether, benseue^
chloroform, and lastly amy I alcohol*
The original process was based upon the svipposed fact that volatile
Bolventa, such as ether, petroleum ether, acetic acid, tetrachloride of
CftrboB, extracted from acid solutions, fata, glucosides^ and various non-
alkaloidal substances, while the same solution alkalised ^ave up to an
appropriate solvent alkaloidal substances — the said alkaloidal substanceg
being, with a few exceptions, almost insoluble in the volatile solvent
acting on acid solutions. This has now been shown to be only true to a
certain extents For example, Kipponberger has shown that 200 mgrms.
of strychnine dissolved in 70 c.c. of water, acidified by *2 c.c. of MCI, and
the whole shaken up with 50 c*c. of chloroform, is taken up by the
solvent to the extent of 43 to 49 per cent* ; 200 mgrms « of paimverinc
dtHsolvod with 1 CO. of HCl in 70 c,c, of water can, by repeate*! shaking
with chloroform, be entirely extracted ; and, according to the dilution
and the kind and strength of acid, a great number of the alkaloids may
be to a considerable extent shaken out of acid solutions. The reason
of this is that disaociation of the alkaloidal gait takes place under
certain conditions of dilution and acidity ; then the alkaloidal base is
soluble in the volatile aolveut, the liydrocidorideH being more eiLsily
diBSOciftted than the sulphates, and, therefore, sulphuric acid being the
more suitable to use ; the solntions must not be too dilute.
D rage n dorse's process, or modifications thereof, is seldom employed
now for the direct extraction of poisons, but ia useful for the investi-
gation of the extracts obtained by the Stns-Otto process,
Kippenberger's modification of Dragendorff* s process ia as follows i*
" ZiiL/, tmalifiischt CfmnU^ 1900, t^O.
2S6
POISONS : THEIR EFFECTS AND DETECTION.
[I3IO'
— The fiiiidj wliich Bhould be as free from mineral salts as possiblej ia
aoiditied mih milphurie acid until it contains at least 1 per cent, free
sulphunc acid ; it is warmed to 30° C, allowed to cool, and then shaken
up twice with petroleum ether (b,p. SO^-SO') in a separating fuuneL
The petroleum ether extracts fat, fatty acids, veratroiditii jervin-
xanthin b&ses, and nther matters.
The petroleum ether remaining in the fluid is completely got rid of
by evaporation in tho water-bath, cooled, and shaken up with chloroform ;
this removes from the acid solution colchicin, digital in, picrotoxin,
cantharklin, pa paver in, aconitine, narceiu, ]ervin, geisoapermin, caffeiu ;
it also extracts some delphinin, brucinei emetine, and thebaine^ and
mere tracer of narceine, strychnine, veratrine, niid cocaine.
The acid liquid may now be alkalised with weak aoda solution, and
shaken with chloroforuL The chloroform extracts sparteine, coniine,
nicotine, atropine, codeine, emetine, brucine, strychnine, veratrine,
delphinine, pilocarpine, apo morphine, hyoacyamine^ daturine, scopola-
miDe, and alkaloids generalty soluble in chloroform ; It must be
noted that in the alkaline liquid there may remain morphine, narcoUne,
papaverine, aeon i tine, and cafl'ein. To the alkaline fluid is now added a
concentrated solution of sodic bicarbonate and common salt^ the latter
in the proportion of 15 grms. per cent., and the liquid again heated
with chloroform to which 10 per cent, alcohol has been added ; this
dissolves out morphine, narceine, and strophantine.
If the shaking out process of Dragendorff m applied to quite small
quantities of fluid, say up to 50 c.c.^ derived from an alcohoMc extract,
there is seldom any practical difflculty in its e^teeution ; if^ on the other
hand, solutions containing mucus, peptones, album oses, and carbohydrates
are treated by the volatile solvents, eniulsious are obtained, difficult to
separate. Some imrtial success in separation is possible by warming the
mixture, and also by whirling the separating funnel and its contents in
a centrifugal apparatus; but unless neat, well-defined separations occur,
the process should not be used,
§310. 9«h©ibler'a ProeeM,— This ia to precipitate the phosphotnngatate of the
allcAloid, and thon to libenito the lattor by digestifig th^ prt^ipitat^ with either
hydra tfl of barium or hydrate of calcitim, diasolving it out by ehloroformj or, if
volatile, hj simple distillation. The details of Schdbler's proeesa ar*? as fgllowa : —
The organic mixture ia repeatedly rxti acted by water strongly acidifiod with
aulphurio acid ; the t^JcLmct is evaporated at 30° to the consistence of a thin aymp ;
then diluted with water^ and after seretdl hours* stundiiig^ filtered in a cool place.
To the filtered Huid phogphotmigstic acid 1^ added in "jxoess^ the pn?cipiLatfl filtei-ed,
wastjod with water to which some phospliotungatie acid solution haa bfleti added,
and, while atill moigt, nuRed into a 11a»k. Cauatic baryta or carbonate of potiish is
ftddfd to alkaline reaction, and tif^er the flank ha<i been connected with bulbs con-
talBiiig HCh it i!^ heated at lirst slowly , then more ntrongly. Ammonia and any
TCilalUe alkaloids ^r'e driven over into the Actd^ and are there fixer], and can be
§311-313-] IDKNTIFICATION OF THE ALKALOIDS.
2S7
f^xjimiued later by suit-able tu^thud!^* TUe residuct iu the tlaak h c&rafully ovaporited
to drytieas (the exci?S3 of baryta having been precipitate by CO^), and tlieti uxtrocM
by strong tilculioU On eraporatioii of the alcohol, thb alkaloid is generally sufficiently
pure to be cxamiutHl, or, if not aoj it may be obtained pui^ by re-solutioD| etc*
Scheiblei^s prot^ega cannot be used witb advantage directly on wateiy-
acid extracts of the organs, for it not only precipitates alkaloids, but
also invariably gives voluminous precipitates with ordinary flesh ex-
tracts, m that a preliminary purification from albuminous matters by
alcohol or glycerin tannin is necessary,
§ 311, GraBdval and Lajou^^s Helliod, * — -The alkaloids are precipitated from a
solution slightly ficiditlcil by hydrsjcldoric or sulphtiric acid by a salation of liydrarg-
potasfiium iodide, Tba precipitate is collected on a Jilter, waab^ and tben Ira us
ferred to a flaak ; drop by drop> a aolution of sod turn sulphide h addeij ; after eaeh
addition the suspended pi^eipitatB is sbakon and allowed t*i stand for a few minutes,
and a dri>p of the liquid taken out and teat«d mth load acetate ; directly a alight
brown colour appeai*s, sufficient sodic sulphide has bi^n added. The liquid is now left
for half au hour* with oocasioual shaking. Then snlpburic acid is added nntU it is
juiit acid, and the liquid is tilt^red and the mercury sulphide well washed. In the
filtmte will he the sulphate of any alkaloid lu solution ; this liq^uid is now made
alkalitte with soda carbonate and shaken up, as in Dragondorirs process, with
appropriate sol vents ; such, for c3:ampIo, as ether, or chlorofonu, or acetone, or arayltc
alcohol^ according to the ^tartioular alkaloid the analyst is soarching for, and the
solvent Anally separated and allowed to evaporate, when the alkaloid ia found in the
iMidiie.
I S12. Identiflcation of the AJkalold^. — Hanng obtained, in one way or othor,
a crystalline or aiDorphoUK (iubstanco, suppo^Gd to be an alkaloid, or, at all eventip an
iciive vogptable priiiciplt^ the next step is to Identify it.
In medico-legal ri»car<:heti there ia seldom any considerahle quantity of th«
male rial to ^ ork upon. Hence the greatest care niust be taken from the commence-'
ment not to wa«te the substance in uselees teeti^ but to study well at the outset what
— by the methcid of extraction used, the microscopic appeara&co^ the rmction to
litmus-paper, and the solubility iu different meufltrna — it is likely to be. However
minute the quantity niay be, it ia saaentiaL to divide it into different parts, in order
to apply a variety of teats ; but aa any attempt to do tlu9 on the solid substance will
probably entail loss, the best way is to diaaolva it in a watch-glass in half a c.c. of
■loohol, ether, or other suitable solvent. Droplets of thb ttolution are then placed
on watch-glasses or slips of microscopic gla^^ and to these drops, by the aid of a
glaAB rod, different reagents can be appliedj and the changes watched under the
miefOflCOpe as the drops slowly evapomte.
§ 313, Behrona' Method of Identiflcation uf the Alkaloid*. —The micro-chBmi-
cal methods of Behrens, aided by a few s^njcial teste, are useful for the identification of
certain of the alkaloids. The t^e^ult^ ar^ trustworthy, provided similar te^ia are
applied to pure samples of the particular alkaloid believe*! to be pmseut*
Boh r ens + divides the alkaloids as follows t —
1, Alkaloids which are capable of being distilled from au aqueous solution.
2, Alkaloids soluble in water, but which cannot be distilled.
3, DiSkultly soluble bases precipitable by sodium carbonate soluble in soda, but
* ** Dosage des alcaloides h Vaide de Viodure double de mercure et de potassium/'
par MM. A. Grandvalet Henri Lajoux, Jotim, de PAarmodtf, Sser. I. xxviii. 1S2-156.
t ZeiL /. anaL Ckemitf 1^04, 333,
17
258 POISONS: THEIR EFFECTS AND DETECTION. [§314.
precipitable from the alkaline solution by sodium bicarbonate or ammonium carbonate,
such as morphine, apomorphine, and cupreine.
4. The rarer opium bases precipitable by sodic carbonate insoluble in caustic
soda solution, such as narcein, narcotine, papaverine, and thebaine.
5. Bases precipitable by sodium carbonate, but not precipitable by sodium
bicarbonate ; strychnine, brucine, veratrine.
6. Quinine bases precipitable by sodium carbonate, also by sodium bicarbonate
if not in too dilute solution.
7. The rare quinine bases.
The individual members of the group are then identified by their behaviour to
potassic ferrocyanide, cobalt thiocyanide, platin chloride, and other reagents described
in this work under the particular alkaloid.
§ 314. Sublimation of the Alkaloids. — A very beautiful and elegant
aid to the identification of alkaloids, and vegetable principles generally,
is their behaviour towards heat.
Alkaloids, glucosides, the organic acids, etc., when carefully heated,
either — (1) sublime wholly without decomposition (like theine, cytisin,
and others); or (2) partially sublime with decomposition; or (3) are
changed into new bodies (as, for example, gallic acid) ; or (4) melt and
then char ; or (5) simply char and burn away.
Many of these phenomena are striking and characteristic, taking place
at different temperatures, subliming in characteristic forms, or leaving
characteristic residues.
One of the first to employ sublimation systematically, as a means of
recognition of the alkaloids, etc., was Helwig.^ His method was to place
a small quantity (from ^ to tx^Vtt ^^ ^ mgrm.) in a depression on
platinum foil, cover it with a slip of glass, and then carefully heat by a
small flame. After Helwig, Dr. Guy t greatly improved the process by
using porcelain discs, and more especially by the adoption of a convenient
apparatus, which may be termed "the subliming cell." It is essentially
composed of a ring of glass from ^ to f of an inch in thickness, such as
may be obtained by sections of tubing, the cut surfaces being ground
perfectly smooth. This circle was converted into a closed cell by resting
on it one of the ordinary thin discs of glass used as a covering for micro-
scopic purposes^ and supporting a similar disc. The cell was placed on
a brass plate, provided with a nipple, which carried a thermometer, and
was heated by a small flame applied midway between the thermometer
and the cell ; the heat was raised very gradually, and the temperature at
which any change took place was noted. In this way Dr. Guy made
determinations of the subliming points of a large number of substances,
and the microscopic appearances of the sublimates were described with
the greatest fidelity and accuracy. On repeating with care Dr. Guy's
* Das Mikroscop in der Toxicologie.
t Phamu Joum, Traits. (2), viij. 719 ; ix. 10, 68. Forensie Medicine, London,
1875.
§3*4-]
SUBLIMATION OF THE ALKALOlDSp
259
determinatiotiB, however, the senior author could iti no single instaoee
agree with liis ^tihlimiug pointB, nor with the appat^tus he figures
and describee couhi two coneeciitive ohservatioufi e,^actly coincide.
Further^ on ejtamiuing the variotis subliming temporaturea of substances,
aa stated by different authors^ the widest discrepancies were found —
differences of 2 or even 3 degrees might be referred to errors of
observation, a want of exact cujneidence in the thermometers employedi
and the like ; but to what, for example, can we aficribe the irrecon-
eilable statements which have been made with regard to theinet
According to 8 1 ranch, this substance auVilimes at 177°; according to
Mulder, at 184-7". But that both of these observations deviate more
than 70" from the truth may be proved by any one wlio cares to place a
few ragnns. of theiue, enclosed between two watch-glasaea, over the
water- bath ; in a few minutes a distinct sublimate will condense on
the upper glass, and, in point of fact, theine will be found to sublime
seTeral degrees below 100^
Binee this great divergency of opinion is not found either in the
speciHc gravity, or the boiling-points, or any of the like determinations
of the physical properties of a substance, it is self-evident that the
processes hitherto used For the determination of anblimlng points are
faulty. The sources of error are chiefly —
(1) Defects in the apparatus employed^th© temperature read being
rather that of the metallic surface in the immediate vicinity of the
thermometer than of the tjiibstance Itself.
(2) The want of agreement among observers as to what should be
called a sublimate — one considering a sublimate only that which is
evident to the naked oye^ another taking cognisance of the earliest
microscopic film.
(5) Ko two persons employing the same process.
With regard to the apparatus employed, the senior author adopts
Dr. Quy^B subliming cell ; but the cell, instead of resting on a metallic
solid, floats on a metallic Ho id. For any temperature a little above
100* this fluid is mercury, but for higher temperatures fusible metal is
preferable.
The exact procedure is as follows:— A porcelain crucible (a in fig.),
about 3 inches in diameter, is nearly filled with mercury or fusible
metal, as the case may be ; a minute speck (or two or three crystals of
the substance to be eiamined) is placed on a thin disc of microscopic
covering glass, floated on the liquid, and the cell is completed by the
glass ring and upper disc. The porcelain crucible is supported on a
bmss plate (/>}, fixed to a retort-stand in the usual way, and protected
from the unetiual cooling ejifect^ of currents of air by being covered by a
tiaak (c), from which the bottom baa been removed. The neck of the
26o
POISONS: TliEIR EFFECTS AND DETECTION.
[§ 314-
iiask convenieiitlj supports a thermometer, which pasties through h cork,
and the bulb of the thertiiotiaeter is immersed in the bath of liquid metal.
In the fii'st exiiminatiou of a substance the temperature h raised some-
what rapidlj, takiu^^ off the upper disc with a forceps at everj 10* aud
exchangmg it for a fresh diacj until the subtitanee m destroyed. The
second e]tamiiiation is conducted much more slowly, and the discs
exchanged at every V or 5°, whiUt the final determination is effected by
raising the temperature with great caution, and exchanging the discs at
about the points of change (already partially determined) at every half
degree, AU the discs are examined microscopically. The most con-
venient definition of a sublimate is this — the most minute tilms, dots, or
crystals, which can be observed by J- inch
power, aud which are obtained by keeping
the subliming cell at a definite temperature
for 60 seconds. The commencement of many
stiblimates assumes the shape of dots of
extraordinary minuteness, quite invisible to
the unaided eye; and, on the other hand,
since the practical value of sublimation is
nminly as an aid to other methods for the
recognition of substances, if we go beyond
short intervals of time, the operation, other-
wise simple aud speedy, becomes cumber-
some, and loses its general applieability.
There is also considerable diacreptmcy of
statement with regard to the melting-point
of alkaloidal bodies ; in many instances a
viscous Btate intervenes before the hnal com-
jtlete resolution into fluid j and one observer
will consider the viscous state, the other complete flnidityj as the
melting-point,
In the melting-points given below, the same apparatus was used, but
the substance was simply placed on a thin disc of glass floating on the
metallic bath before described (the cell not being completed), and
examined from time to time microscopically, for by this means alone
can the first drops formed by the most minute and closely-adherent
crystals to the glass be discovered.
Cocaine melts at 93*, and gives a faint sublimate at 98' ; if put
between two watch-glasses on the water-bath, in fifteen minutes there
is a good cloud on the upper glass.
Aconitine turns brown, and melts at 1 79' C. ; it gives no character-
istic sublimate up to 190",
Morphine, at 150*, clouds the upper disc with nebulse; the oebulaj
Sabliinijj;; <
§3^4]
SUBLIMATION OF THE ALKALOIDS.
261
arie reaoJired by high aiagnifying pt^jwens inlo minute dote ; thebe dots
giradimUj become coarser, luid are generally converted into crystals at
188' ; the alkaloid browns at or al>out 200**
Thebaine subliraes in theiue4iko cryatala at 135" ; at higher tempera-
tures (160"' to 200"), needles^ cubes, and prisma are observed. The
residue on the lower disc, if examined before carbonieation, in fawn-
coloured with non-chanicteristiu spots*
Karootine gives no sublimate ; it melts at 155* into a yellow liquid,
which, on raiding the temperature^ ever becomes browner to final black-
ness. On examining the residue before carbotiiaation, it is a rich brown
atnorphoua substance ] but if narcotine be heated two or three degrees
above its melting pointy and then cooled slowly, the residue is ery stall ine
—long, fine needles radiating from centres being common.
Karceine gives no sublimate^ it melts at ISi"" into a colourless
liquid, which undergoes at higher temperatures tbe usnat transition of
brown colours. The aubstance, heated a few degrees above its melting-
painty and then allowed to cool slowly, shows a straw-coloured residue,
divided into lobes or drops containing feathery crystals*
Papaverine gi ves no s u bl i mate ; i t m el ts at 1 3 0 ", The r esid u e, h oated
a little alH>ve its melting-pointy and then slowly cooled, is amorphous,
of a light brown colour, and in no way characteristic,
Hyoscyamine gives no crystalline sublimate ; it melts at 89*, and
appears to volatilise in great part without decompositioti. It melts into
an almost colourless fluid, which, when solid, may exhibit a network
not mil ike vegetable pareuchyma ; on moistening the network with
water, interlacing crystals immediately appear* If, however, hyoscya-
mine be kept at 94* to 95° for a few minutes, and then slowly cooled,
the edges of the spots arc arborescent, and the spots themselves
crystalline.
Atropine (daturine) melts at 97* ; at 123' a faint mist appears on
the upper disc. Crystals cannot be obtained ; the residue is not
characteristic,
Solanine, — ^The npper disc is dimmed with nebulae at 190°, which
are ooarst^r and more distinct at higher temperatures ; at 200' it begins
to brown, and then melts; the residue consists of amber-browti non-
cbamcteristic drops.
Strychnine gives a minute sublimate of fine needles, often disposed
in lines, at 160*; about 221* it melts ; the residue (at that temperature)
is resinous.
Brudne melts at 151* into a pale yellow Uqnid, at higher tempera^
tores becoming deep brown. If the lower disCj after melting, be
ea^mined, no crystals are observed, the residue being quite transparent,
with branching lines like the twigs of a leaHess tree ; light mists, pro-
262 POISONS: THKIR EFFECTS AND DETECTION. [§315-
duced rather by decomposition than by true sublimation, condense on
the upper disc at Ids'" and above.
Saponin neither melts nor sublimes ; it begins to brown about 145*",
is almost black at ISd**, and quite so at 190**.
Delphinine begins to brown about 102" ; it becomes amber at 119",
and melts, and bubbles appear. There is no crystalline sublimate;
residue not characteristic.
Pilocarpine gives a distinct crystalline sublimate at 153" ; but thin
mists, consisting of fine dots, may be observed as low as 140°. Pilo-
carpine melts at 159" ; the sublimates at 160" to 170" are in light
yellow drops. If these drops are treated with water, and the water
evaporated, feathery crystals are obtained ; the residue is resinous.
Theine wholly sublimes ; the first sublimate is minute dots, at 79" ;
at half a degree above that very small crystals may be obtained ; and
at such a temperature as 120", the crystals are often long and silky.
Theobromine likewise wholly sublimes ; nebulae at 134", crystals
at 170" and above.
Salicin melts at 170" ; it gives no crystalline sublimate. The melted
mass remains up to 180" almost perfectly colourless ; above that tem-
perature browning is evident. The residue is not characteristic.
Picrotozin gives no crystalline sublimate. The lowest temperature
at which it sublimes is 128" ; the usual nebulse then make their appear-
ance ; between 165" and 170" there is slight browning ; at 170" it melts.
The residue, slowly cooled, is not characteristic.
Cantharidin sublimes very scantily between 82" and 83" ; at 85" the
sublimate is copious.
The active principles of plants may, in regard to their behaviour to
heat, be classed for practical purposes into —
1. Those which give a decided crystalline sublimate :
(a) Below 100", e,g, cocaine, theine, thebaine, cantharidin.
{h) Between 100° and 150", e,g, quinetum.
(c) Between 150" and 200", e,g, strychnine, morphine,
pilocarpine.
2. Those which melt, but give no crystalline sublimate :
(a) Below 100", e,g, hyoscyamine, atropine.
{b) Between 100" and 150", e,g, papaverine,
(c) Between 150" and 200", e.g, salicin.
{d) Above 200", e,g, solanine.
3. Those which neither melt nor give a crystalline sublimate, e,g,
saponin.
§ 315. Melting-point. — The method of sublimation just given also
determines the melting-point; such a determination will, however.
§ 3i6.]
MKLT1NG-P0U!JT— IDENTl FICATION,
^3
seldom compare with the melting*poinU of the variaus alkaloids m
giTeo in tdxt-booka, because tbe latter meltiug-points are not determined
in the same way. The usual method of determining melting-points ia
to place a very small quantity in a thin glaa^ tube closed at ono end ; the
tube should be almost capillary* The tube m faatened to a thermometer
by means of platinum wire, and tbeu the bulb of the thermometer,
with Its attached tube, is immersed in strong sulphunc actd or parai!in^
contained in a tiask. Tbe thermometer should be suspended midway
in the liquid and beat carefully applied, so iia to raise tbe temperature
gradually and equably. It will be found that rapidly raising the heat
gives a diflerent melting-point to that whicb is obtained by slowly
raising the heat. During tbe process careful watching is necessary :
most substances change in bue before they actually melt. A constant
melting-point, however often a substance Is purified by recry stall isation,
is a sign of purity.
§ 3 1 6. Identification by Organic Analysis. — ^In a few cases (and in
a few only) tbe analyst may have sufficient material at band to make
an organic analysisj either a^ a means of identihcatiou or to confirm
other tests. By the vacuum process described in " Foods," in whioh
carbon and nitrogen are determined by measuring the gases evolved
by burning the organic subatauce in as complete a racuura as can be
obtained, very minute quantities of a substance can be dealt with, and
the carbon and nitrogen determined with fair accuracy. It is found
in practice that the carbon determi nations appear more reliable than
those uf the nitrogen, and there are obvious reasons why this should
be so.
Theoretically, with the improved gas-measuring appliances, it is
possible to measure a o,c. of gas; but few chemists would care to create
a formula on less than 10 c.c. of C0^», Now, since 10 c.c» of CO^ is equal
to 5^33 mgrms. of car bun, and alkaloids average at least half their
weight of carbon, it follows that 12 mgrms, of alkaloid represent about
the smallest quantity witb which a reliable single combustion can
be made.
Tbe following determinations may also be of service occasionally in
identifying the alkaloids.
OMygmi. — The majority of the alkaloids contain oxygen, but there
is no oxygen in coniine, mcthylconiine, y-coniceinej nicotine, nicotinine,
niooteine, nicotelline, sparteine, lupinidine, curarine, couessine, aribine,
adenine, and hymeuodictine.
Methoj^yl groups may be determined by Zeisel^s method, which
consists in boiling from 0'2 to 0*3 gramme uf tbe substance with
10 c.c. of hydriodic acid of sp, gr* 1 *6tJ| and passing the methyl iodide
formed into a solution of silver nitrate. From the weight of silver
264 POISONS: THEIR EFFECTS AND DETECTION. [§317-
iodide formed, the number of methoxyl groups may be calculated,
one molecule of silver iodide = one methoxyl group. There is one
methoxyl group in quinine and codeine, two in hydrastine and
brucine, three in narcotine, four in papaverine and aconitine, and six
in pseudaconitine.
Nitrogen, — By a modification of ZeiseFs method the methyl groups
attached to nitrogen may be determined, methyl being the only
alcoholic radical which occurs attached to the nitrogen of alkaloids.
Herzig and Meyer have shown that when the hydriodic acid salt
of the base is subjected to dry distillation, the methyl groups are
eliminated as methyl iodide, and may be determined by means of
silver nitrate. Thus it has been found that chrysanthemine and
caffeine contain one methyl group; cusohygrine, narceine, and theo-
bromine contain two; trigonelline, arecoline, methyl coniine, nicotine,
hygrine, pseudopelleturine, atropine, cocaine, morphine, codeine, nar-
cotine, and eserine contain one; and lupinine, lupauine, cinchonine,
and harmaline none.
§ 317. Quantitative Estimation of the Alkaloids.— For medico-
legal purposes the alkaloid obtained is usually weighed directly, but
for technical purposes other processes are used. One of the most
convenient of these is titration with d.n. acid, using a suitable
indicator.
Kippenberger * has shown, in a special research, that the choice of
an indicator is not indifferent, some indicators giving to titration values
for the alkaloids entirely erroneous; he gives the following list of
suitable indicators; those in brackets may be used, but are not as
suitable as the others.
Atropine. — lodeosin (methyl-orange), azolithmin, haematozylin, lacmoid, cochi-
neal, uranine.
MoBPHiNB.— (lodeosin), cochineal, lacmoid.
Aconitine. — lodeosin, azolithmin, heematozylin, cochineal.
Veratrine.— lodeosin, haematoxylin, cochineal, lacmoid.
TuEBAiNE. — lodeosin, uranine (haematoxylin), cochineal, lacmoid.
Codeine. — lodeosin (azolithmin), uranine, h«ematoxylin, cochineal, lacmoid.
Cocaine. — Lacmoid, uranine, cochineal, haematoxylin.
Strtchninb. — lodeosin, azolithmin (uranine), hematoxylin, cochineal, lacmoid.
Brucink. — lodeosin, azolithmin (uranine), haematoxylin, cochineal (lacmoid).
Nicotine. — (lodeosin, uranine, cochineal), lacmoid.
Coniins. — lodeosin (methyl-orange, azolithmin), haematoxylin, alkannin, cochi-
neal, lacmoid, Congo-red.
Sparteine. — Azolithmin (uranine), haematoxylin, phenolphthaleiii, alkannin.
Papaverine. —Lacmoid.
A reagent of general application is found in the so-called Mayer's
reagent, which consists of 13*546 grms. of mercuric chloride, and 49*8
• JZeU,/, anal, Chemie, 1900, 801.
% 3^7'] ESTIMATION OF THE ALKALOIDS. 265
grms. of iodide of potassium in a litre of water. Each c.c. of such
solution precipitates —
Of Strychnine 0167 gnn.
,, Brucine, -0283 „
„ Quinine, '0108 ,,
,, Cinchouine, '0102 ,,
,, Quinidine, *0128 ,,
,, Atropine, '0146 ,,
„ Aconitine, '0268 „
,, Veratrine, '0269 „
„ Morphine, '0200 ,,
„ Narcotine '0206 ,,
„ Nicotine, '00406 „
„ Coniine -00416 ,,
The final reaction is found by filtering, from time to time, a drop on
to a glass plate, resting on a blackened surface, and adding the test
until no precipitate appears. The results are only accurate when the
strength of the solution of the alkaloid is about 1 : 200, and when the
solutions are pure ; so that it is absolutely necessary first to ascertain
approximatively the amount present, and then to dilute or concentrate,
as the case may be, until the proportion mentioned is obtained.
Similarly, the iodine solution described on p. 253 may be used volu-
metrically by precipitating the alkaloid by the solution, filtering, and
then ascertaining by means of thiosulphate solution the amount of free
iodine in the filtrate; if the iodine solution is standardised by approxi-
mately equal weights of the particular alkaloid under investigation, the
process is capable of giving fair results, although more adapted for
technical use than for forensic cases, as the precipitates, both with
iodine and Meyer's reagent, have not always a definite composition,
being influenced by solubility, concentration, and the presence of other
bodies.
It is useful for quantitative purposes to combine an alkaloid with
gold or platinum, by treating the solution with the chlorides of either
of those metals — the rule as to selection being to give that metal the
preference which yields the most insoluble and the most crystallisable
compound.
The following table gives the percentage of gold or platinum left on
ignition of the double salt : —
Atropine,
Aconitine,
Amanitino,
Berberine,
Brucine,
Cinchonine,
Cinchonidine,
Ot.ld.
Platinum
31-57
20-0
44-23
...
2916
1811
16-62
27-36
27-87
266
POISONS: THKIK EFFECTS AND DETECTION. [§ 3 1 8, 3 1 9.
Gold.
Platinum.
Codeine,
19-11
Coniine,
29-38
Chirarine,
32-65
Delphinine,
Delphinoidine,
Emetine,
26-7
29-0
15-8
29-7
Hyoscyamine,
Morphine, .
Muscarine,
34-6
43-01
19-52
Narcotine, .
15-7
15-9
Naroeine,
...
14-52
Nicotine,
...
34-25
Papaverine, .
Pilocarpine, .
Piperine,
Quinine,
35-6
40-0
17-82
23-6 to 25-2
12-7
26-26
Strychnine, ,
Thebaine, .
29-16
18-16
18-71
Theine,
37-02
24-58
Theobromine,
.
25-55
Veratrine,
21-01
...
II.— Liquid VolatUe Alkaloids.
THE ALKALOIDS OF HEMLOCK — NICOTINE — PITURIE— 8PAETK1NE.
1. THE ALKALOIDS OF HEMLOCK (CONIUM).
§ 318. The Conium macidatumy or spotted hemlock, is a rather
common umbelliferous plant, growing in waste places, and flowering
from about the beginning of June to August. The stem is from three
to five feet high, smooth, branched, and spotted with purple; the
leaflets of the partial involucres are unilateral, ovate, lanceolate, with
an attenuate point shorter than the umbels ; the seeds are destitute of
vitta, and have five prominent orenate wavy ridges. The whole plant
is foetid and poisonous. Conium owes its active properties to the
liquid-alkaloids Coniine and y-Conicei'ne, with a crystalline alkaloid,
Conhydrine. Small quantities of Pseudoconhydrine and Methylconiine
also occur in the plant. The alkaloids are in the plant combined with
malic and caffeic acid.
§ 319. Coniine (conia, conicine), (CgHiyN)— specific gravity 0-862
at 0', 0-845 at 20*; melting-point, - 25"; boUing-point, 166-6\ Pure
coniine has been prepared synthetically by Ladenburg, and found to
be a-propyl-piperidine, CgHj^NC^H;, but the synthetically-prepared
piperidine has no action on polarised light. By uniting it with dextro-
tartaric acid, and evaporating, it is possible to separate the substance
§3*9.]
tfEBnX)CK,
267
itito dejctro-a-propyl-pipcridiiie and lavo-a-pi*opyl-pi|jendme. The foruier
is in every respect identical with coiiiine from hemlock ; it is a clear,
oily riuid, poBsesaiag a peculiarly unpleasant^ mousy odour, One part
is soUible in 150 p^rts of watery '^ lu 6 parts of ether, and in almost all
proportions of amyl aleohol, chloroform, and bensiene. It readily
volatilise!, and^ provided air is excluded, may be distilled unc banged.
It ignites easily, and burns with a smoky Rame. It acts as a strong
base, precipitating the oxides of nietala aud alkaline earths from their
aolutiona, and it coagutateg albumen* Couiine forms salts with hydro-
chloric acid {CgHjj^N.HCi), phosphoric acid, iodic acsd, and oxalic acid,
which are iu well-marked crye^tals. The sulphate, nitrate, acetate,
and tartrate are, on the other hand, uou-crystalline.
If couiine is oxidised with nitric acid, or bichromate of potash, and
diluted Bulphurtc acid, butyric acid is formed ; and sinco the latter has
an unmistakable odour, and other characteristic properties, it has been
proposed as a test for coniinc. This may be conveniently jjerformed
thus : — A crystal of potasslc bichromate is put at the bottom of a test
tube, and some diluted sulphuric acid with a drop of the supposed
confine added. On heatings the butyric acid reveals itself by its odour,
and can be distilled into baryta water, the butyrate of baryta being
subsequently separated in the usual way, and decomposed by sulphuric
acidj etc.
Another test for couiine is the following : — If dropped into a solution
of alloxan, the Utter is coloured after a few minutes an intense purple-
redj and white needle-shaped crystals are separated, which dissolve in
cold potssh^lye into a beautiful purple-blue, and emit an odour of the
base.t T}Ty hydrochloric acid gives a purple -red, then an indigo-hlue
colour, with conliue ; but if the acid is not dry, there is formed a bluish-
green crystalline mass. Thia test, however, is of little value to the
toxicologiat, the piire substance alone responding with any definite result.
The ordinary precipitating agents, according to Dragcudorir, act as
follows;—
Pota&s. biamuth iodide.
I ; 2000, a strong orange precipitate,
1 : 3000. The drop of the reagent ts surrounded with a nuiddy border,
1 : 4000. The drop of the reagent is surrounded with a muddy border,
1 : 5000, fitill perceptible.
1 : 6000* The last limit of the reaction.
Pbosphomolybdic acid gives a strong yellow precipitate ; limit,
1 : 5000.
* The saturated wAt^ry elation of couiine at 15* becomes oluudy if geutly
irmnned, and clears &gmn on nooling.
t SchwitrawilMfcdli, yiettcljtikraschr./. prakL Phntm^t vi^. 170.
268 POISONS : THEIR BFFBCTS AND DETECTION. [§ 32O.
Potass, mercuric iodide gives a cheesy precipitate ; limit, 1 : 1000 in
neutral, 1 : 800 in acid, solutions.
Potass, cadmic iodide gives an amorphous precipitate, 1 : 300. The
precipitate is soluble in excess of the precipitant. (Nicotine, under
similar circiunstances, gives a crystalline precipitate.)
FlUckiger recommends the following reaction : * — " Add to 10 drops
of ether in a shallow glass crystallising dish 2 drops of coniine, and cover
with filter -paper. Set upon the paper a common-sized watch-glass
containing bromine water, and invert a beaker over the whole arrange-
ment. Needle shaped crystals of coniine hydro-bromine soon form in
the dish as well as in the watch-glass." Hydrochloric acid, used in the
same way, instead of bromine water, forms with coniine microscopic
needles of coniine hydrochlorate ; both the hydro-bromide and the
hydrochlorate doubly refract light. Nicotine does not respond to
this reaction.
Coniine forms with carbon disulphide a thiosulphate and a sulphite.
If carbon disulphide, therefore, be shaken with an aqueous solution of
coniine, the watery solution gives a brown precipitate with copper sul-
phate, colours ferric chloride solution dark brown-red, and gives a milky
opalescence with dilute acids. If coniine itself is added to carbon
disulphide, there is evolution of heat, separation of sulphur, and forma-
tion of thiosulphate. Nicotine docs not respond to this reaction.
§ 320. The Constitution of the Coniine Bases.— Coniine is the
dextromodification of a'propylpiperuline,
CH2
H2C
,/\
CHo
\/
N
H
Coniine.
If the hydrochloride is distilled with zinc dust eonyrine or a-propyUpijH-
dine is formed,
N
Conyrine.
The conireines are a-propylpiperidines. Five isomers have been
prepared, of which a-couiceXne and y-coniceine are more poisonous
than coniine.
* Iieacti(m$, by F. A. Fluckiger, Detroit, 1893.
§ 321.]
HEMLOCK.
269
a-coniceine is a liquid which boils at 158*. y-oonicelne occurs in
Conium maculatum and also in commercial coniine; it is a liquid
boiling at 17r-172*, optically inactive, and reduced by tin and HCl or
sodium and alcohol to inactive coniine,
HaC
CHa
/\CH
H2C V • C-CsH7
N
H
7-comceine.
Conhydrine is found in Conium maculaium. Crystallises from ether
in colourless leaflets. Melts at 118'. Distils at 225"-226'. Soluble in
alcohol and in ether. Polarises to the right. It is an hydroxylated
coniine, and may be provisionally represented thus —
H vH, OH
H2C '^^ CHo
HjC
Y
H
CH-C3H7
PseudoconhydHne is isomeric with conhydrine and has similar
properties. It is a crystalline deliquescent powder, soluble in water,
alcohol, and ether. Melts at 10^-102^ boils at 229'*-23r. Polarises
to the right. Is probably a stereoisomer of conhydrine.
Methylconiine is a colourless liquid. Sp. gr. 0*8318 at 24*". Boils
at 173'-174'. Polarises to the left.
CHa
HaC /\ CHa
HaC V y Cn — C3H7
N
CH3
Methylcoji Hne,
§ 321. Pharmaceutical Preparations. — The percentage of coniine in
the plant itself, and in pharmaceutical preparations, can be approxi-
mately determined by distilling the coniine over, in a partial vacuum,*
* This is easily effected by uniting a flask containing the alkaloidal fluid, air-
tight, with a Liebig*s condenser and a receiver, the latter being connected with
Bunsen's water-pump, or one of the numerous exhausting apparatus now in use in
every laboratory.
270 POISONS : THEIR EFFBCT8 AND DETECTION. [§ 322, 323.
and titrating the distillate with Meyer's reagent, each c.c. = '00416 grm.
of coniine. It appears to be necessary to add powdered potassic chloride
and a small quantity of diluted sulphuric acid before titrating, or the
precipitate does not separate. In any case, the end of the reaction is
difficult to observe.*
The fresh plant is said to contain from about '04 to 09 per cent.,
and the fruit about 0*7 per cent, of coniine.
The officinal preparations are — the leaves, the fruit, a tincture of
the fruit, an extract of the leaves, the juice of the leaves (Sticcus canii)^
a compound hemlock pill (composed of extract of hemlock, ipecacuanha,
and treacle), an inhalation of coniine (Vapor conti), and a poultice
(Cataplasma conii) made with the leaves.
§ 322. Statistics of Coniine Poisoning. — F. A. Falck t has been
able to collect 17 cases of death recorded in medical literature, up to
the year 1880, from either coniine or hemlock. Two of these cases
were criminal (murders), 1 suicidal, 2 cases in which coniine had been
used medicinally (in one instance the extract had been applied to a
cancerous breast ; in the other, death was produced from the injection
of an infusion of hemlock leaves). The remaining 12 were cases in
which the root, leaves, or other portions of the plant had been
ignorantly or accidentally eaten.
§ 323. Effects on Animals. — It destroys all forms of animal life. The
senior author made some years ago an investigation as to its action on
the common blow-fly. Droplets of coniine were applied to various parts
of blow-flies, which were then placed under glass shades. The symptoms
began within a minute by signs of external irritation : there were rapid
motions of the wings, and quick and aimless movements of the legs.
Torpor set in speedily, the buzz soon ceased, and the insects lay on
their sides, motionless, but for occasional twitching of the legs. The
wings, as a rule, became completely paralysed before the legs, and
death occurred at a rather variable time, from ten minutes to two
hours. If placed in a current of air in the sun, a fly completely
under the influence of coniine may recover. Coniine causes in frogs,
similar to curarine, peripheral paralysis of the motor nerves, combined
with a transitory stimulation, and afterwards a paralysis of the motor
centres ; in frogs the paralysis is not preceded by convulsions. DragendorfF
experimented on the action of coniine when given to Ave cats,
the quantities used being *05 to *5 grm. The symptoms came on
almost immediately, but with the smaller dose given to a large
cat, no effect was witnessed until twenty-five minutes afterwards ;
* Dragendorff, Die chemisehe fV$rthb&stimmung einiger starkvnrkender Droguen^
St Petereb., 1874.
t Prakt, Toxieologie, p. 273.
1 324^326.]
ITEMLOCK,
271
this was tha longest interval. One of the earliest phenoineim
was dilatation of the pupil, followed bj weakness of the limbs pairing
into jfarElyaiSj the hinder legs being affected prior to the fore. The
rcsipiratiou became troubled, and the frequency of the breatiiiiig tlini-
imiBhed; the heart in each case acted irregularly, and the sensation
generally was blunted ; death was preceded bj convulwiona. In the
cases in which the larger dose of '4 to '5 grm, was administered, death
took place within the hotir, one animal dying in eight minutes, a aeeond
in eighteen minutes^ a third in twenty minutes, and a fourth in fifty-
eight minutes. With the smaller dose of -051 grm, given to a large catp
death did not take place until eight hours and forty-seven minutes after
administration.
ij 32't, Effects on Man, — In a case recorded by Bennet,* and quoted
in most works on forensic medicine, the symptoms were those of general
muscular weakness deepening into paralyai^« The patient had eaten
hemlock in mistake for parsley ■ in about tM'enty minutes he experienced
weakness in the lower extremities^ and staggered in walking like a
drunken man ; within two hours there was perfect paralysis of both
upper and lower extremities, and he died in three and a quarter hours.
In another case, related by Taylor, the symptoms were also mainly those
of paralysis, and in other instances stupor, coma, and slight convulsions
have been noted.
^ 325. Physiological Action. — It is generally agreed that coniine
paralyses, first the ends of the motor nerves^ afterwards their trunks,
and lastly, the motor centre itself. At a later period the sensory nerves
participate. In the earlier stage the respiration is quickened, the pupils
contracted, and tfie blood -pressure increased ; but on the development of
paralysis the breathing becomes slowed, the capillaries relaxed, and the
blocMl-pressure sinks. Death takes place from cessation of the respir-
ation, and not primarily from the heart, the heart beating after the
breathing has stopped, Coniine is eliminated by the urine, and is also
in part separated by the lungs, while a portion is, perhaps, deoomposed
in the body.
g 326, Post-mortem Appearances, — There Is nothing characteristic
in the appearances after death.
Fatal Dose. — The fatal dose of coniine is not accurately known ;
it is about 150 mgrnjs. (2 3 grains). In the case of Louise lierger, 10
to 15 drops appear to have caused death in a few minutes. The auto-
experiments of Dwor/j^k, Heinrich, and Dillaberger would indicate that
one drop may cause unpleasant symptonis* Albers, in the treatment of
a woman suffering from cancer of the breast, witnessed convulsions and
loss of consciousness from the third dose of 4 mgrms* ("06 grain) ; and
* Mm. Mtd, and Surg. Jvurn^t July 1845, pu 169.
272 POISONS : THEIR EFFECTS AND DETECTION. [§ 327, 328.
Eulenberg, its full narcotic effects on a child after subcutaneous in-
jection of 1 mgrm. (-015 grain).
§ 327. Separation of Goniine from Organic Matters or Tissues. —
The substances are digested with water, acidulated with HoSO^, at a
temperature not exceeding 40*", and then filtered. If the filtrate should
be excessive, it must be concentrated ; alcohol is then added, the liquid
refiltered, and from the filtrate the alcohol separated by distillation.
On cooling, the acid fluid is agitated with benzene, and the latter
separated in the usual way. The fluid is now alkalised with ammonia,
and shaken up once or twice with its own volume of petroleum ether ;
the latter is separated and washed with distilled water, and the alkaloid
is obtained almost pure. If the petroleum ether leaves no residue, it is
certain that the alkaloid was not present in the contents of the stomach
or intestine.
The affinity of coniine with ether or chloroform is such^ that its solu-
tion in either of these fluids, passed through a di^ filter, scarcely
retains a drop of water. In this way it may be conveniently purified,
the impurities dissolved by water remaining behind.
In searching for coniine, the stomach, intestines, blood, urine, liver,
and lungs are the parts which should be examined. According to
Dragendorff, it has been discovered in the body of a cat six weeks after
death.
Great care must be exercised in identifying any volatile alkaloid as
coniine, for the sources of error seem to be numerous. In one case ♦ a
volatile coniine-like ptomaine was separated from a corpse, and thought
to be coniine ; but Otto found that in its behaviour to platinic chloride,
it differed from coniine ; it was very poisonous — '07 was fatal to a frog,
*44 to a pigeon, in a few minutes. In the seeds of Lupirms lutetis there
is a series of coniine-like substances,! but they do not give the character-
istic crystals with hydrochloric acid.
2. TOBACCO— NICOTINE.
§ 328. The different forms of tobacco are furnished by three species
of the tobacco plant, viz., Nicotianum iahctcum, N. rustica^ and N.
persica.
Havana, French, Dutch, and the American tobaccos are in the main
derived from N, tabacum ; Turkish^ Syrian, and the Latakia tobaccos
are the produce of N. rusiiea. There seems at present to be little of
N. persica in commerce. The following alkaloids have been isolated
from the aqueous extract from tobacco : — Nicotine, CjoHj^Nj ; Nicotin-
ine, CiqHi4N2; Nicotelne, CioHijNg; and Nicotelline, CioHgNg.
* Otto, AnleUung z, AusmiUlung d. Oifie, 1875.
t Sievert, Zeiiachrift fUr NaturvHsaenschaften, 1869.
§ 329^] yicxmxK 273
Tbe goieiml compositioD of the whole jdant maj be gathered from
the following table : —
TABLE SHOWING THE COMPOSITION OF FRESH LEAVB3 OF TOBACCX)
(POSSELT AND REINMANNX
Nieodne And other alkaloids, OHMO
Concrete volatile ml, 0*010
Bitter extractiTe, 2*870
Gum with malate of lime, 1*740
Chlorophyll, 0*267
Albmnen and glaten, 1*308
Malic acid, 0*510
lagnine and a trace of starch, 4*969
Salts (sulphite, nitrate, and malate of potash, chloride of \
potaadom, phosphate and malate of lime, and malate V 0734
of ammonia), J
Silica, 0*088
Water, 88*280
100-836
§ 329. Quantitative Estimation of Nicotine in Tobacco. — Keller's
process (J.CS., Abs., 1899, ii. 193) gives fair results, and is as follows:
— 6 grm& of tobacco dried over quick-lime are powdered and treated
with 60 grms. of ether, 60 of petroleum ether, after the addition of 10
c.c. of 20 per cent. KOH solution ; after digesting 3-4 hours, 100 grms.
of the ethereal liquid are placed in a 200 c.c. flask, and a strong current
of air passed over to expel ammonia; 10 c.c. of water, 10 c.c. of alcohol,
and a drop of a 10 per cent, solution of iodeosin are added and the
whole shaken; this causes the nicotine and iodeosin to pass into the
aqueous liquid. D.n. HCl. acid is now added until the liquid is colour-
less ; the slight excess of acid is titrated back with d.n. ammonia. One
C.C. of the acid equals 16*2 mgrms. of nicotine.
M. Popoirci * has proposed a method based on Kissling's process of
extraction, but the estimation is a polari metric one ; in this way the
difficulty of separating nicotine from ammonia is obviated. From 20
to 40 grms. of dry tobacco are treated with 10 c.c. of alcoholic soda
solution (6 per cent. NaOH in 100 c.c. of 57 per cent, alcohol) and
extracted with ether in a Soxhlet apparatus. The ether extract is
treated with 10 c.c. of a tolerably concentrated solution of phospho-
molybdic acid in nitric acid and shaken ; the phosphomolybdate of
nicotine (with ammonia) is precipitated, the ether is separated, and the
precipitate treated with water to bring up the volume to 50 c.c. ; lastly,
8 grms. of BaOH are added; the yellow solution after standing for
some hours is filtered and polarised.
• Ztschr,f, physiol. CTiem,, 1889, 446.
i8
274 POISONS : THEIR EFFECTS AND DETECTION. [§ 329.
The following table
is used : —
Grins, of Nicotine in
Rotation in 2 dm. tube
One minute of a degree
50 c.c. solution.
(minutes).
corresponds to grm. Nicotine.
2-00
337
0-00594
175
298
0-00588
1-50
268
0-00582
1-25
217
0-00676
1-00
175
0-00572
0-76
133
0-00564
0-60
89
0-00562
0-25
45
0-00556
Mr. Cox^ has determined the amount of nicotine in a number of
tobaccos as follows : —
Twenty-five grammes (or more or less, according to the amount of the
sample at disposal) of the dried and powdered tobacco were intimately
mixed with slaked lime, and distilled in a current of steam until the con-
densed steam was no longer alkaline ; the distillate was slightly acidu-
lated with dilute H2SO4, and evaporated to a conveniently small bulk.
This was made alkaline with soda, and agitated repeatedly with successive
portions of ether. The separated batches of ethereal solution of nicotine
were then mixed and exposed to the air in a cool place. This exposure
to the air carries away ammonia, if any be present, as well as ether.
Water was added to the ethereal residue, and the amount of nicotine
present determined by decinormal HgSO^, using methyl-orange as an
indicator. One c.c. of decinormal H2SO4 represents 001 62 gramme of
nicotine (CiqE^^Nj).
TABLE OF RESULTS, ARRANGED ACCORDING TO PER CENT.
OF NICOTINE.
Variety examined. Nicotine per cent.
1. Syrian leaves (a), -612
2. American chewing, -985
3. Syrian leaves (6), 1*093
4. Chinese leaves, 1 -902
5. Turkish (coarse cut), 2-500
6. Golden Virginia (whole strips), .... 2-501
7. Gold Flake (Virginia), 2-501
8. "Navy-cut "(light coloured), .... 2-530
9. Light returns (Kentucky), 2-733
10. " Navy-cut " (dark * ' all tobacco "), ... 3 -640
11. Best*' Bird's-eye," 3-981
12. Cut Cavendish (a), 4-212
18. "BestSliag"(a) 4-907
14. *' Cut Cavendish "(6), 4-970
15. ** Best Shag" (6), 5-000
16. French tobacco, 8-711
17. Algerian tobacco (a), 8*813
18. Algerian tobacco (6), 8*900
t Phann, Jmm., Jan. 20, 1894.
i 3300
NICOTINE,
275
It is therefore obvious that the strt^ugtli of tobacco in uicotme
varies between wide limita,
§330. Hicotiue i^ mothjl-pyridtyl-pyri-olidiiici
Q
Yc
and has been recently aynthetised by Pictet and Rotschy;* the sue-
oeasive step.^ of the syuthesia iire as follows: /i-iimmo-pyridlne-rnucate
Is distilled and N./i» pyr idyl -pyrrole obtained ; the vapour of thiB is
passed through a red-hot tube, when it iaomemes to a |3'p3?riclyl-
pyrrole; on acting ou this Isist product with methyl-iodide, methiodiile
of nieotyriue is Foniied, the same as on carefully oxidising natural
nicotine ; nicotyrine can be obtained from the iiioth iodide by distillation
with lime. By acting on nicotyrine with iotline and NaOH, an iodine
substitution compound is obtained, which is reduced by xinc and
hydrochloric acid to dihydro-nicotyrine ; this substance is tranafomied
into the perbroniide, and on reduction of this, inactive nicotine is
obtainal. By fractional crystallisation of the tartrates the inactive
nicotine is divided into la>vo- and dextro- rotatory nieotineSj the former
being identical with the natural product.
B-p. RtBanp, 1)1074" D^OVr M^
24*M-24B'2 730^5 I'Ol^ 1*0097 - UO'SS'
34e -240*5 734 5 1*0177 rOo&2 - ltJO'93
M^*b-2ii5 129 1-0171 1*0004 +1«3"I7
Katiiml itioQtine, 1.
rotatory, .
I. Nicotine from the
flynthdtiaed bn^,
d. Hicotinie from tliP
ayiith(9ti9«tt ^MUte,
The deitro-artifieial nicotine ha^ ap|mreutly a siiyhter and some-
what diireretit physiological action to ordinary nicotine* The odour of
nicotine, especially on warming, is strong and unpleasantly like tol*acco,
and it has a sharp, caustic taste. It aljsorbs water when ux posed to the
air, and dissolves in water in all proportions, partly separating froiu
such solution on the addition of a caustic alkali, The aqueous solution
acts in many respects like ammonia, saturating acids fully, and may
therefore be in certain cases estimated with accuracy by titration, 49
parts of HgSO| corresponding to 162 of nicotine.
Alcohol and ether dissolve nicotine in every proportion ; if such
solutions are distilled, nicotine goes over first* The salts which it forms
with hydrochloric, nitric^ and phosphoric acids crystalline with difficulty;
tartaric and oxalic acid form white crystalline sulti*, and the latter,
oxalate of uicotiue, ig soluble in alcohol, a property which distiuguiihes it
* ^ifT., 1&04, 1225.
h
276 POISONS; THEIR EFFECTS AND DETECTION. [§ 33O.
from the oxalate of ammonia. The best salts are the oxalate and the acid
tartrate of nicotine, from which to regenerate nicotine in a pure state.
Hydrochloride of nicotine is more easily volatilised than the pure
base. Nicotine is precipitated by alkalies, also by many oxyhydrates,
lead, copper, etc. It is also precipitated by tannin and gallic acids ; an
alcoholic solution of tannin completely precipitates an alcoholic solution
of nicotine. By the action of light, it is soon coloured yellow and brown
and becomes thick, in which state it leaves, on evaporation, a brown
resinous substance, only partly soluble in petroleum ether.
A very excellent test for nicotine^ as confirmatory of others, is the
beautiful, long, needle-like crystals obtained by adding to an ethereal
solution of nicotine a solution of iodine in ether. The crystals require a
few hours to form. The various iodides, partly intramolecular and partly
additive, and the conditions under which they form, have been studied
by Kippenberger.*
Chlorine gas colours nicotine blood-red or brown ; the product is
soluble in alcohol^ and separates on evaporation in crystals.
Cyanogen also colours nicotine brown ; the product out of alcohol is
not crystalline. Platin chloride throws down a reddish crystalline pre-
cipitate, soluble on warming. A drop of nicotine poured on dry chromic
acid blazes up, and gives out an odour of tobacco camphor; if the ignition
does not occur in the cold, it is produced by a gentle heat. A solution
of nicotine in chloroform on the addition of iodine forms fine red crystals
(Roussiu's crystals), CjQHj^NgHIjIg + a; CHClg : the best proportions
seem to be the reaction of 2 atoms iodine on I molecule of nicotine.
It is scarcely possible to confound nicotine with ammonia, by reason
of its odour; and, moreover, ammonia may always be excluded by
converting the base into the oxalate, and dissolving in absolute alcohol.
On the other hand, a confusion between coniine and nicotine is apt
to occur when small quantities only are dealt with. It may, however^
be guarded against by the following tests : —
(1) If coniine be converted into oxalate, the oxalate dissolved in
alcohol, and coniine regenerated by distillation (best in vacuo) with
caustic lye, and then hydrochloric acid added, a crystalline hydrochlorate
of coniine is formed, which doubly refracts light, and is in needle-shaped
or columnar crystals, or dendritic, moss-like forms. The columns after-
wards become torn, and little rows of cubical, octahedral, and tetrahedral
crystals (often cross or dagger-shaped) grow out of yellow amorphous
masses. Crystalline forms of this kind are rare, save in the case of
dilute solutions of chloride of ammonium (the presence of the latter is,
of course, rendered by the treatment impossible); and nicotine does
not give anything similar to this reaction.
*' ZeU, anal. Chemie, 1908, 232.
^n^-]
NICOTINE,
^77
(2) Coulitie Qoagulates albutnea ; iiicotino doob not,
(3) Nicotine yielda a ohamcteristic oryBtalline preciipitfttii with an
aqueous sokitian of merannc chloride ; the similar precipitate of couiiue
is amorj^hous,
(i) An alcoholic solutioii of eoniine miKed with carbon diBulpbtdc
18 coloured yellow — nicotine ia not ; on adding to the solution a few drops
of a dilute sohition of copper sulpliate (1 : 200) or ferric chloride, tMiniine
precipitates yellow or brown — nicotine does not precipitate. On diii£o]v-
ing nicotine^ even in tracers, in epi-ehlor-hydiin aud beating to boiling, a
deep red colour is protlnced ; eoniine gives no colour.^
% 33 L Effects on Aidmals.^Nicotme is rapidly fatal to a] J animal
life— from the lowciit to the highest forms. Very minnte quantities in
water kit I infusoria. Fish of 30 gnns. weight die in a few minutes
from a milligramme of nicotine ; the syniptoma observed are rapid mo%'e-
mentfii then shivering and speedy paralysis, with decreased motion of
the gills, and death. With frogs, if dose^t not too large are employed^
there Is first great restlessnessi then strong tetanic convulsions, and a
very peculiar position of the limbs ; the rcspimtion after fatal defies
soon ceases, but the heart beat^ even after death. Birds also show
tetanic convulsions followed by paralysis and speedy death- The
symptoms witnessed in mammals poisoned by nicotine are notesi^entially
dissimilar, With large doses the effect ia similar to that of prussic
aoid^ — visL^ a ery^ one of two shudderiDg cronvulsions, and death. If the
dose is not too large, there is trembling of the limbs, excretion of ficcea
and urtue, a peculiar condition of stupor, a staggering gait, and tfien
the animal falls on ita side* The respirmttoa, at first quickened, is
afterwards slowed, and becomes deeper than natuml ■ the pulse, also,
with moderate doses, is tirst slowed, then rises in frcqueucyj and tiually,
again fails. Tetanic convulsions soon develop j during the tetanus tlie
pupils have been noticed to l>e contracted, but afterwards dilated ; the
tongue and mouth are livid, aud the vessels of the ear diluted. Very
ehanieteristic of nicotine poisoning as witnessed in the cftt, the rabbity
and the dog, is its peculiarly violeat action^ for after the administration
of from one to two drops» the whole course from the commencement of
symptoms to the death may take place in five minutes. F, Vas has
drawn the smoke of tobacco from an immense pipe, and condensed the
products; he fiuds the well- washed tarry products without physiological
action, but the soluble liquid affected the health of rabbits,*— they lost
weight, the number of the blood corpuscles was decr©as©il, and the
hiemoglobin of the blood diminished, t
The larger animals, such as the horse, are affected similarly to the
' H. MelkPT, ^iL una!, CA*m., 180S, S45-35S.
h ArckU\ f\ Ejtptt\FaihoL U. Ffiarm,, lid* xauiiL
27 S
POISONS: THEIR EFFECTS AND DETKCTION.
[§ 332^
iinallar domestic animals. A votonuary siirgeuu, Mr. Johti Howard, of
Woolwich,* hae recoiled a case in which a home 8u fierce] from the moat
violent symptoms of nicotine-poisonings after an appHcation to his sktn
of a strong dauoction of tobaccOp The symptoms were trembling,
particularly at the posterior part of the shoulders, as well as at the
flanks, and both fore and hind extremities ] the superficial muscles were
generally relaxed and felt flabby, and the pupils were widely dilated,
TJiero was also violent dyspnma, the respirations being quick and ahortj
puke 32 per minute, and extremely feeble, fluttering, and indistinct.
M' hen made to walk, the animal appeared to have partly lost the use of
liis hind limbs, the posterior quarter rolling from side to side in an
unsteady manner, the legs crossing e^ch other, knuckling over^ and
appearing to be aeriotmly threatened with paralysis* The anus was very
promioeut, the bowels extremely irritable, and tcnesmxis was present
He passed much flatus, and at intervals of three or four minutes, small
quantities of foeces in balls^ partly in the liquid state, and coated with
sHmy muciiB. There was a staring, giddy, intoxicated appearance
about the head and eyes, the visible mucous membrane being of a
dark red colour. A great tendency to collajjse was evident, but by
treatment with cold douches and exposure to the open air, the horse
recovered »
In a case occurring in 1863, in which si^ horses ate oats which had
been kept in a granary with tobacco^ the symptoms were mainly those
of narcosis, and the animals died.t
§ 332, Effects on Man.^ — Poisoning by the pure alkaloid nicotine is
so rare that, up to the present| a few cases only are on record. One of
these, viz,, the poisoning of M, Fougnies by Count Bocarme and his
wife, LB ever memorable in the history of toxicology, being the first
instance in which a pure alkaloid had been criminally imed. The
detection of the poison exercised the attention of the celebrated chemist
StaSp For the unabridged narrative of this interesting case the reader
may consult Tardieu^a ^imh Mklko-Uyfth mr V Empoi&tmimmmit
Bocarme actually studied chemistry in order to prepare the alkaloid
himself^ aiid^ after having succeeded in enticing his victim to the chateau
of Bitremontj administered the poison forcibly. It acted immediately,
and death took place in five minutes. Bocarme now attempted to hide
all traces of the nicotine by pouring strong acetic acid into the mouth
and over the body of the deceased. The wickedness and cruelty of the
crime were only equalled by the clumsy and unskilful manner of its
perpetration. The quantity of nicotine actuaUy used in this case must
have been enormous, for Stas separated no less than ^4 grm, from the
ttomach of the victim*
* V^^itti, Joumalt vol* iii, t AnrtaU* F^iirifmirtd, BniiaUm, 186S,
§ 3330
NrCOTIHR
279
Allot ber known c£^e of aicotine-po [soiling was that of it man who
took it for tUe parpoiio of sukide. The case h related by Taylor, It
occurred in June 18G3, The gentleman dnink an unknown quantity
from a bottle^ he stared wildly, fell to the Hour, heaving a deep sigh,
and died quietly without coavulBion. A third caee happened at
Cherbourg,* where an ofticer committed suicide by taking nicotinei
but how much had been tiwallowed, and what were the symptoms, are
equally unknown, for no one saw him during life after he had taken
the poison.
Poisoning by nicotine, pure and simple, then is rare* Tobacco-
poisoning is very common, and ba^ probably been experienced in a
mild degree by every smoker in first acquiring the habit. Nearly all
the faUil oases are to )je aaeribed to accident ; but criminal cases are
not unknown. Cbristiaon relates an instance in which tobacco in
the form of snulf was put into whisky for the purpose of robbery.
In 1S54 a man wa^ aeoused of attempting to poison his wife by
putting snutt* into her ale, but acquitted. In another case, the father
of a ohild, 10 weeks old, killed the infant by putting tobacco into ita
month. He defended himself by saying that it was applied to make
the child ^leep.
In October 1855,t a drunken sailor swallowed (perhaps for the
purpose of suicide) his quid of tobacco, containing from about half an
ounce to an ounce. He liad it some time in his mouthy and in half an
hour suffered from frightful tetanic convulsions. There waa also
diarrheea ; the pupils were dilated widely ; the heart's action becamo
irregular ; and towaids the end the pupils again contracted. He died
in a sort of syncope, seven hours after swallowing the tobacco.
§333. In 1829 a curious instance of ]K>iaoning occurred in the
case of two girls, 18 years of age, vvbo suffered from severe symptoms
of tobacco-poisoning after drinking some coffee* They recovered ; and
it was found that tobacco bad been mixed with the coffee-berrieSj and
both ground up together. J
Accidents have occurred from children playing with old pipes. In
1877^ a child, aged 3, used for an hour an old tobaeco-pipe, and blew
soap bubbles with It. Symptoms of poisoning soon showi^ themselves,
and the child died in three days.
Tobacco J nice J as expressed or distilled by the heat developed in the
usual method of smokiug, is very poisonous. Sonnenschetn relates the
case of a drunken student, who was given a dram to drink, into which
his fellows bad poured the juice from their pipes. The result was fatal.
• Ann. iVHtfijienc, 1, p. 404, 180L t Edm, MU, Jimwn,, 1S&6.
X BftrkhaUBoa, Pr. Fer. 2%,, ivii p. 8a, 1838,
§ S'ha^rm. Jmm., 1877, p. 377,
2So
POISONS: THEIR EFFECTS AKD DETECTION.
333'
Deatb from smoking is not unknown,* H el wig saw de^th follow in the
case of two brothers, who smoked seventeen and eigiiteen German
[>ipefuls of tobaoco. Marshall Hallt records the case of a youug
man, IB years of age, who, after learoing to enioke for two days,
attempted two conaecntive pipes. He suffered from very serious
symptoms, and did not completely recover for several dayg, Gordon hm
also recorded severe poisoning from the consecutive amokiug of nine
cigars. The external application of the leaf may, as already shown in
the case of the horse, produce all the efifecta of the internal ad minis-
tratioQ of nicotine. The old instance, related by Hildebrand, of the
ill]iei& of & whole squadron of busbars who attempted to smuggle
* The questioD m to wlietlu^r there is raacb uicotine in tfiliiwico'itmokc* aiunut be
considered settled ; but it h j^robablo th&t moE!t of the poLHOUuiiu tiyni|ituiiiE pruduced
are referable to the pyridpiis hoses of tlio geuoral fomiuU (C|,H^_j|N), und aoiue
At leiuit of its genuicidal yaluv m due to the presence of foniiia aldehyde. Vohl und
Euknb«rg (j^rcA, Phanna^**, 2j cilvi, p, 130) uiadc stjuie very en ireful t«xj»t?nments
on the smoke of fstrong tcjhafjco, i)Ur»t both in pipes and aim in cigara. The nicthtxi
adopted w&^ to draw tlie sinoku iiiiit ihtxtugh jKiUsh^ and thiTL thiougli dilute
sulphuric acid, Tlio jxjtaab absorbed prUHsic acid, hydi-ic 8ulifliidt% formic, acetic,
propionic, butyric, valeric, and cartiolic acids ; while in the acid the lnusea wens
fixed ^ afid thc^se were found to cotiBist of the whole series of pyridene basue^ from
pyridene (C5H4N), boiL -point 117', picolinc (C^HyN), b«ul point 133% lutiditie
{CrHflK), boU^-potut 164'j upwards. When smoked in piix^s, the cliief yitld was
pyridene ; when in cigars, celHdino (CgHjiN) ; and iu general « pijie-tsmokuig was
found to produce a greater number of volatile bu^^es* The action of theeje base;^ h^a
been investigntad by seveml obscrvera. Thtiy all have a special action on the urgati-
bm, and all iltow ati Increase in physiological actidty an the iserlea b (Vftcended. The
lowest ]iroduce merely exoLt^ment from irritation of tlie encephalic nervous centra,
Atid the highest^ i>aralysi9 of those centres. Death pryceeda from gradual failure of
the reapiratoiy movements^ loading to ni^pliyxia — (K«ndrick and Lhiwar, Proc, Rf^f},
Sac*, xxiL 442 ; xxiii, 290). A, Qautier tbund tliat Uibac^o smoked In a pipe pro-
duced basic comiKiunds, a large quantity of nicotine, uud a higher homologuc of
nicotine, Cj^HnNgj which piO'exii^tH in tobacco leavei^, and a ham CrtHJtf 0, wliich
saenis to be a hydrate of picoline— (Gt^m^^. Mend*, L cxv, pp, 992, i)93). The
derivatiires of the pyrxdeii© series are alao active, The niethiodidea strongly excite
the braiu and jiamiyBc the extretniliee. A fiimilar but inoi'e vnergt^ttc action iu
exerted by the ethyl and allyl dcriTatives ; the iod*al1yl derivatives arc stnmg
poasotts. Mathylic [lyrideuc carbuxylate m almost inatitive, but the coi-rcspondiiig
aramonitim salt gives rise to symptoms reaembling epilepsy— (Ramsay, PML Mtrg,,
[5] iv, p. 241, 1S77). One member of the pyridene aeries 3 Intidine has Witi folly
investigated by C, Greville Williams and W, H. Wat^m—{Pjvc. Me^. Soc, vol,
xxxii* p, 162, 1S81)> They miuclnde thai it alfeets the heait profoundly, causing
an lucroaHe iu ita tonicity, hut the action is almost confined to thtt ventricles. The
auridee are but little atfected^ and coiitiuue to lieat after the ventriclea have
stopped, The rate of the hoiirt's beat in slowed, and the iuhibiU^ry power of the
vagua arrested. By its action on the nervoiui cf^lltt of the spinal cord, it in the
first place leugtheus the time of ]^f!ex action^ and then arrssts that function.
Finally, they i*oiut out that it is aotagouiatlc to atrychume, and may bo BUocesafulIy
employed to arrcat the action of ^trj'chniue on the i^pioal curd.
t Min. UtdL afu£ Bur{f, Jmn^ xa, 18ie.
§ 334']
NICOTINK.
281
tobac(iii hy coucealing the leaf ii^xt to their skiu, is well known, and is
supported by several similar cases. The common practice of the
peasantry, in many parts of England, of applying tobacco to atop
the bleeding of woundsj and also aa a sort of poultice to local stwellings,
has certainly its dangers. The symptoms — whether nicotine has been
taken by absorption through the broken or unbroken skin, by the
bowel, by absorption through amokmg, or by the eipressed juicej or
the consumption of the leaf itself— ehow no werj great difference, save
in the question of time. Pure nicotine acts with aa great a rapidity
as prnsaic acid; while if, eo to Bpeak^ it is entangled in tobaecoj it takes
mot% time to be iaparated and absorbed ; besides which, nicotine, taken
in the concentrated condition, is a strong enough base to have slight
cauitic effects, and thns leaves some local evidences of its presence, in
order to investigate the effects of pure nicotine, Dworzak and Heinrich
made auto-ejtperiments, beginning with I mgnn* This small d<^e pro-
duced unplet^sant sensatioujs iu the mouth and throat, salivation, and a
peculiar feeling spreiiding from the region of the stomach to the fingers
and toes. With 2 mgrms, there was headache, giddiness, numbness^
disturbances of vision, torpor, dulness of hearing, and quickened respira-
tions. With 3 to 4 mgrms., in about forty niiuutes there was a great
feeling of faintness, itUcnse depression^ weakness, with pallid face and
cold ejttremities, sickness, and purging. One experimenter had shivering
of the extremities and cramps of the muscles of the back^ with difficult
breathing. The second suflered from muscular weakness, fainting, fits of
shivering, and creeping sensations about the arms. In two or three
hours the seTerer eftects passed away, but recovery was not complete
for two or three days. It is therefore evident, from these experiments
and from other cases, that ex^cessive muscular prostration, difficult
breathing, tetanic cramps, diarrhoea, and vomiting, with irregular pulse,
represent both tobacco and nicotine poisoning. The rapidly-fatal result
of pure nicotine has been already tiientioned ; hut with tobacco-
poisoning the case may terminate lethally in eighteen minutes. This
rapid termination is unusual; with children it h commonly about an
hour and a half although in the case previously mentioned, death did
not t«ike place for two days.
^334. Physiological Action.— Nicotine is absorbed into the blood
and eicr«ted unchanged, in part by the kidneys and in part by the
saliva (Dragendorfl)* According to the researches of Itfisenthal and
Krocker,* nicotine acts energetically on the brain, at first exciting it,
and then lessening its activity ; the spinal marrow is similarly aifected.
The oonvukions appear to have a cerebral origin ; paralysis of the peri*
pberal nerves follows later than that of the nerve centres, whilst
282 POISONS: THEIR EFFECTS AND DETECTION. [§335-337-
muscular irritability is uuaffected. The convulsions are not influenced
by artificial respiration, and are therefore to be considered as due to
the direct influence of the alkaloid on the nervous system. Nicotine
has a striking influence on the respiration, first quickening, then slowing,
and lastly arresting the respiratory movements : section of the vagus is
without influence on this action. The cause of death is evidently due
to the rapid benumbing and paralysis of the respiratory centre. Death
never follows from heart-paralysis, although nicotine powerfully influ-
ences the heart's action, small doses exciting the terminations of the
vagus in the heart, and causing a slowing of the beats. Large doses
paralyse both the controlling and exciting nerve-centres of the heart ;
the heart then beats fast, irregularly, and weakly. The blood-vessels
are first narrowed, then dilated, and, as a consequence, the blood-
pressure first rises, then falls. Nicotine has a special action on the
intestines. As 0. Nasse * has shown, there is a strong contraction of
the whole tract, especially of the small intestine, the lumen of which
may be, through a continuous tetanus, rendered very small. This is
ascribed to the peripheral excitation of the intestinal nerves and the
ganglia. The uterus is also excited to strong contraction by nicotine ;
the secretions of the bile and saliva are increased.
§ 335. Fatal Dose. — The fatal dose for dogs is from ^ to 2 drops ;
for rabbits, a quarter of a drop ; for an adult not accustomed to tobacco
the lethal dose is probably 6 mgrms.
§ 336. Post-mortem Appearances.— There seem to be no appearances
so distinctive as to be justly ascribed to nicotine or tobacco poisoning
and no other.
A more or less fluid condition of the blood, and, generally, the signs
of death by the lungs, are those most frequently found. In tobacco-
poisoning, when the leaves themselves have been swallowed, there may
be some inflammatory redness of the stomach and intestine.
§ 337. Separation of Nicotine from Organic Matters, etc.— The
process for the isolation of nicotine is precisely that used for coniine
(see p. 272). It appears that it is unaltered by putrefaction, and may
be separated and recognised by appropriate means a long time after
death. Orfila detected it in an animal two or three months after death ;
Melscns discovered the alkaloid unmistakably in the tongues of two
dogs, which had been buried in a vessel filled with earth for seven
years ; and it has been found, by several experiments, in animals buried
for shorter periods. Nicotine should always be looked for in the
tongue and mucous membrane of the mouth, as well as in the usual
viscera. The case may be much complicated if the person supposed
to be poisoned should have been a smoker; for the defence would
• Be'itrdge zur Physiologie der Darmbeweguruft Lelpsic, 1 866.
§337A, 53^]
FITURIBL
283
natu rally be t\r,it there had h&eu mther exce&aive siooking or chewing,
or eveu 8waJluwmg accidea tally a quid of tobacco,* A plouiainc has
baeu discorered similar to iiicobine, Wolckeiih&ar separated als^o nn
alkaloid not imlikc nicotine from the corj^ae of a woman addicted to
intemperate habits ; but this base waa not poiaonouB, nor did it give
any crystala when an ethereal solution was addt?d to an ether solution
of iodine- It will be well always to au]>port the chemical evidence by
teats on animal life, since the intensely poisonous action of nicotine
seems not to be sbLired by tlie nicotino-like ptomaines.
g 337a, Antidote to Nicotine. — C» Zalaekas^t in experiments on
animals with escrine and strychnine^ tiuds that neither of these alkaloids
are antagonistic to any extent to nicotine ; he, however, obtained good
resulta from the expressed juice of Nasturtium officirhale^ two iojections
of which completely counteracted the effect of a fatal dose of nicotine
(26 mgrms.) in a rabbit*
3. PITUBIKt
g 33s. Pi tune (C,|Hf,N) L^ u liquid, iiicotiue-like alkaloid^ obtainfid from the
Didioma iufpHHtodii^ u amall shrtib ar trou bc^longiiig to the tmt^ml order Solatiaca^^
iudigeiioiiB Iti Auairi^liti, Tlio natives mix piturie leaves with aahea from ^omo other
plant, and cbew tliflm. Piturie ia obtained by eitractiag th« plant with boiling
irater acidified with auli>huric acid, concentrating the liquid bj eva|K>ratlon, and
then ftlkalifiing and distiUing with caustic sodA^ mud receiving ihe distill 11 tc in
liydioohlcuie acid. The solution of the liydrochlorate is aft«rwanis alkalised and
diAlCeii up with ether, wliicb readily dissolves out the piturie* Tht! ether Eujlutlon of
piturie is evaporated to diyn^ss in a current of bydro^^en, and the crude piturie
purified by di^tillatieu in hydr<i|(6ei, or by chaugiug it into its salts, and again
woovering, etc. It i?* clear and oolourloss when pure and freab, but beeoniea yellow
@r brown when expo^d to air und light. It boils and dietik at 243° to 24i^« It la
soluble in all pniixirCions in alcohol , water, and ether , its taste h aerid and
imngent ; it is volatile at ordinary ti:;ni]H^rijtureH, causing wbite fumes with bydro-
ehlorijd acid ; it is very irritating to the mucous membra tiva^ having ^ smell like
iiiootin« at Brat, and then, when it becomes bruwner, like pyridine* It forms salts
with acid^ but tbe acetate, sulpha te^ and by drochl orate are varnish -like (ilm^ having
no trace of crystalllsatian ; the oxalate is u crystallLno salt* Hturie gives preeipi*
tates with mercuric chloride, cupric iulphate, gold chloride, mercur-iiotssdc iodide,
tannin, and an akoholic solution of iodine. If an ethereal eolution of iodine is added
to ao ethereal solution of pituriOj a pnicipitate of ye]|owish*red needles, readily
aolublf' in alcobol, rs di^posited, Ths icMiine compound mt4ts at 110'", while the iodibtt
ctimponnd of nicotine melta at 100", Piturie is distinguisbed fnmi coniine by lis
arineous solution not becoming turbid either on be4ting or un the addition of chlorint»
water ; it differs from jiicoline hi »j>ecilic gmvity, picoline being '9$ 13 «ii>ecilic gravity
at 0"^ and piturie sinking in water ; it dilfera from aniline by not 1:K:Jng coloured liy
chlorinated lime. From njeotine it liaa several distinguishing maik>!, otie of the best
• III an ojfjHjriment of DrageudorfTa, nicotine in said to have lieen detected in
3S gniia» of the saliva of a ;>erson who imd half an hour previomly amoked a oigari
t See "The Alkaloid from Piturie," by Prof. Leversidg^, Chem, N§u^, U&rth IB
*iid 2$, ISdl,
^rii
284 POISONS: THEIR EFFKCTS AND DETECTION. [§339-341.
being that it does not change colour on warming with hydrochloric acid and the
addition to the mixture afterwards of a little nitric acid. The physiological action
seems to be but little dliferent from that of nicotine. It is, of course, poisonous, but
as yet has no forensic importance.
4. SPARTEINE.
§ 339. In 1851 Stenhouse * separated a poisonous volatile alkaloid from Spartiuvi
scopariuTtit the common broom, to which he gave the name of si>arteine. At the
same time a crystalline non -poisonous substance, scoparin, was discovered.
Sparteine is separated from the plant by extraction with sulphuric acid holding
water, and then alkalising the acid solution and distilling : it has the formula
(G15H9QN3), and belongs to the class of tertiary diamines. It is a clear, thick, oily
substance, scarcely soluble in water, to which it imparts a strong, alkaline reaction ;
it is soluble in alcohol, in ether, and chloroform ; insoluble in benzene and in petro-
leum ; it boils at 288^ Sparteine neutralises acids fully, but the oxalate is the only
one which can be readily obtained in crystals. It forms crystalline salts with platinic
chloride, with gold chloride, with mercuric chloride, and with zinc chloride. The
picrate is an especially beautiful salt, crystallising in long needles, which, when dried
and heated, explode. On sealing sparteine up in a tube with ethyl iodide and
alcohol, and heating to 100** for an hour, ethyl sparteine iodide separates in long,
neodle-like crystals, which are somewhat insoluble in cold alcohol.
Effect on AnimalB. — A single drop kills a rabbit ; the symptoms are similar te
those produced by nicotine, but the pupils are dilated. f
;6. ANILINE.
§ 340. PropertieB.— Aniline or amido- benzol (CSH5NH.J) is made by the reduction
of nitro-benzol. It is an oily fluid, colourless when quite jmre, but gradually
assuming a yellow tinge on ex})osure to the air. It has a peculiar and distinctive
smell. It boils at 182 '5°, and can be congealed by a cold of 8*^. It is slightly soluble
in water, 100 i)arts of water at 16** retaining about 3 of aniline, and easily soluble in
alcohol, ether, and chloroform. It does not blue red litmus-i)a])er, but nevertheless
acts as a weak alkali, for it precipitates iron from its salts. It forms a large number
of crystalline salts. The hydrochloride crystallises in white plates, and has a melting-
jioint of 192**. The platinum compound has the formula of (C8H5NH2HCl).2PtCl4, and
crystallises in yellow needles.
§ 341. Symptoms and Effects. — Aniline, like picric acid, coagulates albumin.
Aniline is a blood poison ; it produces, even during life, in some obscure way,
methsemoglobin, and it disintegrates the red blood corpuscles ; both these eflects
lessen the i)ower of the blood corpuscles to convey oxygen to the tissues, hence the
cyanosis observed so frequently in aniline poisoning is explained. Engelhardt t has
found that aniline black is pniduced ; in every drop of blood there are fine black
granules, the total effect of which produces a pale blue or grey-blue colour of the skin.
Aniline has also an action on tlie central nervous system, at first stimulating, and
then paralysing. Schmiedeberg finds that para-amido-pheuol-ether-sulphuric acid is
produced, and ap]>ears in the urine as an alkali salt ; a small quantity of fuchsine is
also produced, and has been found in the urine. Some aniline may be excreted
unchanged.
• FhU. Trans,, 1861.
t To the nicotine group, gelsemine (Ca4Ha8Na04) and oxalathylin (CgHioN-j) also
belong, in a physiological sense, but gelsemine, like sparteine, dilates the pupil,
t BrUrage zur Tox» dc3 AnUins, Jiiaufj^-Diss,, Dorpat, 1888.
§ 342-344-]
OPIUM.
28s
Tlie symfitoms are giddin«8H, we&knee9| cyanosiaj blueneas of tlie mkin^ sinking of
the tempcnitoT^, And ilHatAiion of the pupiL The pulse is sm&ll ftuil fr^queut^ the
tkiii moUt and cold. The jiAtlent smells of Aniline, Tow&rdfi Ihc end com a and con-
Tulmons set itip Tbe nnnc nmy be blown to brown-blicki tmd m&y contoin hyaline
eylindera, Tlie blood shows the spectrum of luetliwmoglobin, and has the iH^cullanties
alre^y nientioQod, Slii>uld the patient rt'coverj jaundiei^ often follows. The out-
ward application of aniliitw produces eczema*
Chrrinic puiaoniu^ by aniline is oe<!^asioually seen &mt»ng workers in the manufac-
ture of aniline- He&dachfl| low of musoular power, diminished sensibility of tht«
akin, vomiting, Iubs of apt«tite, jiallor, eruptions on the sldn, and gencrral malaise
are the chief symptoms. The [Ksrapi ration has l>een noti^^l ta Imve a reddisb colotjr,
Ca»e» of aniline poisoning are not oomnion ; Dr. Fred, J. Smith has teeorded one
in the Lttnctf of Jarmarv 13, 1894.* The patient, a woman, 4*2 yearn of age» of
alcoholic tendencies, swallowed, 13th December lS&3j at L40 r.M., about 3 onncea of
marking-ink, the great e>it p:irt of whieh oonsiftttMl of aniline ; in a very little wbile
she becanif? unt'onscioUH, and i^mained so until dealb* At 3 p*M- hi'r lijie were of a
d&rk puriile^ the general surface of the sktci was deadly wliite, with a slight bluiflh
tinge I the pujiils were small and sfnggish^ tho biieatbing stertorous^ and the pnlae
fuU and slow — GO per miimte. The stomach was washed out, ether injected^ and
oxygen iwiniiniHtered, but the f*atient died comatose almost exactly twelve hours after
the poison had been taken.
The post-mortem eiaminaticm showed slight congestion of the Inng^ ; the heart
was relasrex] in all its chauibers, and empty of hlood— it had a |»eculiar gn^en-hlue
an^caraneo. All the organs were healthy. The blood w^is not spectroHcopit^iilly
eitamined.
g 812, Fatal Dose. — This is not known, bnt an adult would jtrobably be killed
l>y a aingk dose of nnything over (J grms, Kwovery under treatment ha.H been known
after 10 grnis. ; tht^ faUl dofi« for rabbite is 1-1 Tj grm,, for dogs 3-5 grms.
§ 343, Detection of Aniline. — Aniline is e^ytily separated and detected. Organic
fluids are alkalii^ed by a solution of j>otash, and distilled. Tlie orfjana^ finely divided,
are extracted with water acidulated with sn1}ihnric acid^ the fluid filtei^d, and then
ftlkftlisetl and distilled. The distillate is shaken up with ether, the ether separated
and allowed t^ evaporate i<pontaneously. Any aniline wnll be in the residue left after
evaporation of the ether^ and may be identified by the following tests :— An aqueoua
solution of aniline or its salts is colonred blue by a little ehloiide of lime or hypo^
chlorite of soda \ later on the mixtare becomes red. Tlie blue colour has au absorp-
tion band, when cKamined speotroficopieally, extending from W.L. 656 to fi$0, and
therefore in the ri*d and ycJlow from Fraonhof(^J''» 11 n*' 0, and oreilappinj^ IK
Another to^t for aniline is the addition of kairine, hydrut^dorie aeiil, and s^fMlinni
nitrite J which strikes a blue colour.
Ilh— The Opium Group of Alkaloids.
§ 344. General GompoBition. — Opium containa a larger nuuiber of
basic substances than any plant juice known. The list reacihes at present
to some 21 nitrogenised bases, and almost each year there have been
additions. Opium is a gummy mass, coneiatiiig of the juice of the
incised utiripe fruit of the Papaver mmniferum hardened in the air,
* See also a ca^ re^iorted by K, Debio^ in which a j^r^on drank 10 gnnH, and
r»eo«red. Btr. A'lmy. ff*WA#»., 1888, Nr. 1,
286
POISONS: THKIR EFFECTS AND DBTKCTION.
[§344.
The following is a nearly complete list of the constituents which have
been found in opium : —
Alkaloids. — I. The Morphine Grouj). Veiy poisonous (except Pseudomorphiue).
Morphine, CjyHijNOs. I Pseudomorphine (CiwHi8N08)2.
Codeine, CisHmNOa. | Thebaine, OuHaNOa.
II. The Papaverine Group.
Cryptopine, CajHasNOg.
Papaveramine, C2,Hj,N0b.
Narcotine, C.J2H23NO7.
Gnoscopine, C22H2:iN07.
Oxynarcotine, C22H23NO8.
Narceme, C23H27NO8.
Hydrocotaniine, C,2Hi5N03.
Xanthaline, O^Hy^jd^-
Other CoiiBtitnents.
Opiauine.
Fat.
I Resin.
, Caoutchouc.
I Gummy matters— Vegetable mucus.
I Ash, containing the usual constituents.
Papaverine, CaoH2iN04.
Codamine, CaoH2BN04.
Laudanine, C20H26NO4.
Laudanidine, C.^H25N04.
Laudanosine, C21H27NO4.
Tritopine (C2iH^7Nb3)20.
Meconidine, C21H23NO4.
Lanthopine, C23H25NO4.
Protopine, CaoHigNOa.
Lactic Acid.
Acetic Acid.
Meconidine, C21H23NO4.
Meconine, C10H10O4.
Meconic acid, C7H4O7.
Thebolactic acid.
The various opiums differ, the one from the other, in the percentages
of alkaloids, so that only a very general statement of the mean composi-
tion of opium can be made. The following statement may, however, be
accepted as fairly representative of these differences : —
Per cent.
Morphine, 6 to 23
Narcotine, . 4 to 8
Other alkaloids, 6 to 2
Meconin, under 1
Meconic acid, ... 3 to 8
Peculiar resin and caoutchouc, 5 to 10
Fat, lto4
Gum and soluble humoid acid matters, . 40 to 50
Insoluble matters and mucus, 18 to 20
Ash, 4to8
Water, 8 to 30
The general results of the analysis of 12 samples of Turkey opium,
purchased by Mr. Bott,* from leading druggists in London, Dublin, and
Edinburgh, are as follows : —
Water. — Highest, 31*2; lowest^ 18-4; mean, 22*4 percent.
Insoluble Residue.— Highest, 47-9 ; lowest, 26-45 ; mean, 3248 per
cent.
Aqueous Extract. — Highest, 56-15; lowest, 2090; mean, 45 90 per
cent.
• Year Book of Pliarmacy, 1876.
§ 345» 346^
OPIUM.
287
Crude Morplime (contaiiMiig about /^ of pure morphine). — Highest,
12"30 ; lowest, 6*76 ; mean, 9*92 per cent, which e(iuals 1 2 "3 per cent,
of the dried dnig.
Ferman Opium^ exauiined iu the s^ime way, varied in crude morphine
from 2 1 to 8*5 per cent. ; Malwa, from 5*88 to 7*30. In 18 samples of
diflferent kinds of opium, the mean percentage of crude morphine was
8'S8 per cent. (11 per cent, of the dried opium). According to Gtiibourt,
Smyrna opium, dried at 100", yields 1 1*7 to 21*46 per centj the mean
being 12 to 14 per cent. ; Egyptian, from 5*8 to 12 per cent. ; Persian,
11*37 per cent In East Indian Patna opium, for medical use, be found
T'72 ; in a sample uaed for smoking, 5*27 per cent ; in Algerian opium,
12*1 per cent ; In French opium, 14*8 to 2 2 9 per cent
§ 345. Action of Solvents on Opium. ^Tbe action of various solvents
on opium has been more especially studied by several scientists who are
engaged in the extraction of the alkaloids.
Water disa^jlves nearly everytbing except resin, caoutchouc, and
woody fibre. Free morjihine would be left insoluble; hut it seems
always to be combined w^itb meconic and acetic acids. The solubility
of free narcotine in ivater ia extremely smalL
Alcohol dissolves resin and caoutchouc, and all the alkaloids atui
their coi 11 bi nations, with meconic acid, etc.
AmyHc Alcohol dieaolves all the alkaloids, if they are in a free state,
and it also takes up a little of the re sin.
Ether, Benzene, and Carbon Sulphide do not dissolve the resin, and
, only slightly morphine^ if free ; but tbey dissolve the otber free alkaloids
as well as caautcbouc.
AcidB dissolve all the alkaloids and the resin.
Fixed AlkalieiS, in excess, dissolve in part resin ; they also dissoWe
morphine freely ; narcotine remains iiisolul>le*
Lime Water dissolves morphine^ but h a solvent for narcotine only
in presence of morphine*
Ammonia dissolves only traces of morphine; but narceine and
codeine readily. It does not dissolve the other alkaloids, nor does it
dissolve the resin.
§ 346. Assay of Opium. — Tlie following proce^^es may be described : —
Process of Teschemacher and Smith.— This process, with a few
modi heat ions, is as follows: — 10 grms. of opium are as completely as
possible exhausted with proof spirit at a boiling temperature. The result*
iug alcoholic extract is treated with a few drojjs of ammonium oicalate
solution, and the solution is almost neutralised with ammonia, The
solution is ooncentrated to one- third, cooled, and filtered. The filtrate
is further concentrated to 5 c.c, and transferi'ed to a small Ha.'ik, or to
the extraction tube figured on p. 163; it is wnshod into this by 4 c.o.
288 POISONS : THEIR BFFECTS AND DETECTION. [§ 346.
of water and 3 c.c. of 90 per cent, alcohol ; next 2 c.c. solution of
ammonia (sp. gr. 0*960) and 25 c.c. of dry ether are added. The flask
is corked, shaken, and then allowed to rest over-night.
The ether is decanted, or drawn off, as completely as possible. Two
filter-papers are taken and counterpoised — that is to say, they are made
precisely the same weight. The filters are placed one inside the other,
and the precipitate collected on the inner one ; the precipitate is washed
with morphinated water — that is to say, water in which morphine has been
digested for some days. The filter-papers with their contents are washed
with benzene and dried, the outer paper put on the pan of the balance
carrying the weights, and the inner filter with the precipitate weighed.
The precipitate is now digested with a known volume of decinormal acid,
and then the excess of acid ascertained by titration with decinormal
alkali, using either lacmoid or cochineal ; each c.c. of decinormal acid
is equal to 30*3 mgrms. of morphine.*
Dott's Process. — Dott has proposed a new process, which he
states has given good results. The process is as follows: — 10 grammes
of powdered opium are digested with 25 c.c. water; TS grammes
barium chloride dissolved in about 12 c.c. water are then added, the solu-
tion made up to 50 c.c, well mixed, and after a short time filtered ;
22 C.C. (representing 5 grammes opium) are mixed with dilute sulphuric
acid in quantity just sufficient to precipitate the barium. About 1 c.c.
is required, and the solution should be warmed to cause the precipitate
to subside, and the solution to filter clear. To this filtered solution a
little dilute ammonia, about 0*5 c.c, is added to neutralise the free acid,
and the solution concentrated to 6 or 7 c.c, and allowed to cool. 1 c.c.
spirit and 1 c.c. ether are then added, and next ammonia in slight excess.
The ammonia should be added gradually until there is no further pre-
cipitation^ and a perceptible odour of ammonia remains after well stirring
and breaking down any lumps with the stirring rod. After three hours
the precipitate is collected on counterpoised filters and washed. Before
filtering, it should be noted that the solution has a faint odour of
ammonia: if not, one or two drops of ammonia solution should be added.
The dried precipitate is washed with benzene or chloroform, dried, and
weighed. It is then titrated with n/lO acid, until the morphine is
neutralised, as indicated by the solution reddening litmus-paper, t
* Pharm, Journal , xix. 46, 82 ; xxiL 746. Wright and Farr, Chemist and
Dniggist, 1893, i 78.
t Other methods of opium assay have been published : see A. B. Prescott's
method {Proceedings of Amer. Pharm, Assoc. , 1878); Alien {Commercial Org,
Analysis^ vol. ii. p. 473) ; E. R. Squibb*s modification of Fliickiger's method
{Pharm. Joum. (3), xii. p. 724) ; a rapid mode of opium assay, MM. Fortes and
Lanjlois {Joum. de Pharm. et de Chrm., Nov. 1881) ; Year Book of Pharmacy, 1882.
To the above may be added— (1) ScJiacht*8 MetJiod.^5 to 10 grms. of dry, finely-
§346.]
opmw.
289
Bouzard Metliod.— Heat B grms- of the sample with 100 o.c. of
water in a clojjied tlask for one hour, cool, add 3 grnia. of slaked lime,
shake during one hour, 6 Iter. Take 0 1 '6 c.c. of the filtrate and place
in a corked flask with 5 c,c. of 90 per cent, alcohol and 30 c,c. of ether
and *i grms, ammonium chloride* Shake during thirty minnteSi and
allow to stand for twelve boiira ; filter ; remove the ether from the filter
mth a pipette ; wash the flask and filter with morphinated water until
free from chlorides, then wash once witli 10 c.c. of distilled water and
pour on to the filter 15 c*c, of ether which, after a few minutea, remove
with a pipette* Expose the filter to the air for thirty minutes, then place
in a beaker and gently heat with 20 c.e» of njlO H^SO^ ; cool and
titrate with 7;/ 10 NaOH, using methyl-orange as an indicator, 1 c.c,
f»/10 H^>SO^ = 0'02S3 grm. morphine; add '05 grm. to the weight
found.
If tincture of opium is to be estimated take 100 e.c. and evaporate
to 30 o.c, add 3 grms, of slaked lime and make np to 100 cc.j add
2 CO, of water, shake during one hour, filter and treat 60 o.c of this
filtrate as above.
powdered opium are digestecj with suffictetit distil led water to make & thin palp.
After twenty -four hotire the whole h thrown on 11 weighed filter, and wiiiili<?d until
the w&Hhtngs are almoat colourless and lAsLele^. The [lortioii ini^aluble in water h
dried at lOD'' and weighed ; in g^^od opium this should oot exceed 10 ^r oerat. The
filtrate is evnjicirated until it Is about one-fifth of the weight of the opitim Uken
originallj ; it in then coolud, fil teredo aud treated with pure animal charcoal, no til the
dark bruwii colour i^ changed into a browniah -yellow. The li^tiid h then reBItered,
precipitated with a <ilight exct;ss of amnionta^ allowed to stand tu an open Tsssel
until all odour of ammonia dbappeara, and at the same time frequently stirred, in
ord(|^ that the prectpttate tnay not bc'come cry3tal!ine< — a fonu whloh in always mora
difficult to purify. The precipitate i^ now collected on a tared filter, waahed, dried,
and weighed. With an opium containing 10 \^r cent, of morphine, ita weight is
usually 14 pr cent. A portion of the pretupitate b tlien detached from the filter,
weighed, and exhausted, first with ether, und afterwards with boiling alcohol
(0 'SI specific gravity). Being thus purified from nareotine^ and ooutaining a little
colouring matter only, it may now he dned And weighed, and the amoiint of mor*
phine calculated, on the whole, from the data tjbtained,
(^) Flcitry has projK>sed a titration by oxalic acid as follows : — 2 gtina. of the
iH>wdeit!d opium aru macerated a few hour^ with 8 c,o» of aqneotij} oxalate of
ammonia, hr<*uglit on a filter, and washed witli 5 c,c, of wat«r. To the filtrate an
equal rolunie of 80 i>er c^nt. alcohol and ammonia to alkaline reaction i^ added ;
andj after atanding twi^ntj^-four hours in a closed Hask, it is filtered, and the Raak
rinsed out with some c.c, of 40 per cent^ aleohoL The filler, with ita contents,
afler diylllg, is placed in the same flask [which sliould not !)e cleansed), a few
dfops of alooholie logwood solution am added, with an exeesu of oxalic M^td iolu<
tion of known strength, the whole being made up to 100 c,c This is divided
into two pftrta, and the excess of acid titrated bock with diluted aodadye. If
the oxalic acid aoluttoti is of the strength of 4'42 gmis. to the litre, every g>c. of
the o%a]io acid solution which ha» l>ecoine Ixiund up with morphine, corresponds to
0*02 gniii of inor[ihine.
19
290 POISONS : THEIR EFFECTS AND DETECTION. [§ 347.
§^347. Medicinal and other Preparations of Opium.— The chief
mixtures, pills, and other forms, officinal and non-officinal, in which
opium may be met with, are as follows : —
(1) Officinal.
Compound Tincture of Camphor, P. B. (Paregoric).— Opium, cam-
phor, benzoic acid, oil of anise, and proof spirit : the opium is in the
proportion of about 0*4 per cent., or 1 grain of opium in 240 minims.
Ammoniated Tincture of Opium (Scotch paregoric). — Strong solution
of ammonia, rectified spirit, opium, oil of anise, saffron, and benzoic
acid. Nearly 1 per cent, or 1 grain of opium in every 96 minims.
The Compound Powder of Eino, P. B.
Opium, 5 per cent.
Cinnamon, 20 „
Kino, 75 „
The Compound Powder of Opium, P. B.
Opium, ....... 10*00 per cent.
Black Pepper, 13-33 „
Ginger, 3333
Caraway Fruit, 4000
Tragacanth, . . . . . . 333 „
Pill of Lead and Opium, P. B.
Acetate of Lead, 75*0 per cent.
Opium, 12*5 „
Confection of Roses, 12*5 „
Tincture of Opium (Laudanum). — Opium and proof spirit. One
grain of opium in 14*8 minims — that is, about 6*7 parts by weight in
100 by measure.
The amount of opium actually contained in laudanum has been
investigated by Mr. Woodland,* from fourteen samples purchased from
London and provincial chemists. The highest percentage of extract was
5*01, the lowest 3*21, the mean being 4*24; the highest percentage of
morphine was '70 per cent., the lowest '32, the mean being '51 per cent.
It is, therefore, clear that laudanum is a liquid of very uncertain
strength.
Aromatic Powder of Chalk and Opium. — Opium 2*5 per cent., the
rest of the constituents being cinnamon, nutmeg, saffron, cloves, carda-
moms, and sugar.
• Year Book of Pharmiry^ 1882.
§ 347-]
opnm.
291
Oompound Powder of Ipecacuanha (Dover's Powder).
10 per ceuL
. 80 ..
Opium,
Ipecacuanha,
Hulphate of I'otaali^
Gonfectioti of Opitnn (Oonfectio opii) is composed of ayrup and
compound powder of opiutu ; tujcording to its formul% it coiibaius 2'4 per
amii, of opium by weight.
Extract of Opium con tains the solid cotislitueata capable of extrac-
tion by wiiter ; it sliould eotitain 20 per cent, of morphinej and 13 therefore
about double the atrength of dry powdered opium.
Liquid Extract of Opium has been nho examined by Mr* Wood*
land : * ten samples yielded as a mean 3'05 per cent, of dry extract,
the highest numbor lieing 4'90 per cent., the lowest 3 02* The mean
percentage of morphine was '28 per cent^, the highest amount being '37,
and the lowet^t 19 per cent.
Liniment of Opium is composed of equal parts of Itiudanum and
soap liiiinicut; it should contain alx^ut 0*0375 per cent, morphine.
The Ooiupoutid 3aap-pill is made of soap and opium^ one part of
opium in every 5 '5 of tiie tiiiiss— <«* about 18 per cent.
Ipecacuanha and Morphine Lozenges, as tlie hi^t, with the addition
^ of ipecacuanliii ; each loKcnge eontiiins ^'^ grain (1 H mgrms,} morphine
hydrochlorate* j=.% grain (5 4 ragrma*) ipeeacuanlia.
Morphia Suppositories are njade witli hydrochlorute of morphna*,
ben^oated lard, white wax, and oil of tbeubronia ; each ^iippotiitory
contains | grain {32 '4 mgrnis.) of morphine salt.
Opium Lozenges are composted of opuim ex tracts tincture of toln
*ugar, gum, extract of Hip 10 rice, and waten I'Jich lo;fieuge contains |\j
grain (6 '4 mgrms,) of extract of opium, or about ^^ grain (1*3 nigrm.)
morphine.
The Ointment of GaUs and Opium contaiofi one part of optum in
14-75 parts of the ointment — ue. opium 6 '7 per cent*
Opium Wine, P. B. — Sherry^, opium extract, cinnamon, and cloves.
A Wit 5 parta of opium extract by weight in 100 parts by measure
(22 grains to the ounce).
Solutions of Morphine, both of the acetate and hydroclilomte, P, B.,
are made with a little free acid, and with rectified Hpirit. The strength of
each is half a grain in each flnitl drachm ('0324 grm. in 3*549), or *dl
part by weight in 100 parts by measure.
Solution of Bimeconate of Morphine,— One fluid oa. contains 5|
grains of bimeconate of morphine.
Morphia Lozengee are made witli the same aeeetiuories ajs opium
• %* Hi.
292 POISONS : THEIR EFFECTS AXD DETECTIOX. [§ 347.
lozengefl, substituting inoq)hine for opium ; each lozenge contains ^
grain of hjdrochlorate of Tnoq)hia(r8 mgrm.).
Syrup of Poppies. — The ordinary syrup of poppies is sweeteneil
laudanum. It should, however, be what it is described — viz., a syrup
of poppy-heads. As such, it is said to contain one grain of extract of
opium to the ounce.
^2; Patent and other XoK-OrFiciNAL Preparations of Opium.
Oodfrej*! Cordial is made on rather a large scale, and is variable in strength and
crrnipofiition. It usually contains about 1} grains of opium in each fluid ounce,* and,
aM other constituents: sassafras, molasses or treacle, rectified spirit, and various
flavouring ingredients, esjiecially ginger, cloves, and coriander ; aniseed and caraways
may also }te detected.
Grinrod*! Bemedj for Spaims consists of hydrochlorate of morphine, spirit of
sal-volatile, ether, and camphor julep ; strength, 1 grain of the hydrochlorate in
every 6 ounces.
Lemanrier*! Odontalgic EHenee is acetate of morphine dissolved in cherry-
laurel water ; strength, 1 grain to the ounce.
Nepenthe is a [^reparation very similar to Lig. Opii sedaiir,^ and is of about the
same strength as laudanum, t
Black Drop (known also by various names, such as Armstrong's Black Dnip)
is essentially an acetic acid solution of the constituents of opium. It is usually
considered to be of four times the strength of laudanum. The wholesale receipt
for it is: Laudanum, 1 oz., and distilled vinegar 1 quart, digested for a
fortnight. The original formula pro|M)0ed by the Quaker doctor of Durham,
Edward Tunstall, is— Opium, sliced, ^ lb. ; good yeijuioe,^ 8 pints ; and nutmeg,
1) oz. ; boiled down to a syrup thickness ; | lb. of sugar and 2 teaspoonfuls of
yeast are then added. The whole is set in a warm place for six or eight weeks,
after which it is evai)orated in the open air until it becomes of the consistence of
a syrup. It is lastly decanted and filtered, a little sugar is added, and the liquid
made up to 2 pints.
** Knnet* Drope ** seem to be com[K>sed of oil of caraway and laudanum.
Powell*! Balsam of Aniseed, according to evidence in the case of Pharmaceutical
Society v. Amnion {Pharm, Joum,, 1894), contains in every oz. ^ grain of morphine.
Dalby*B Oarminatiye—
Carbonate of magnesia, 40 grains.
Tincture of castor, and compound tincture of
cardamoms, of each 15 drops.
Laudanum, ^ n
Oil of aniseed, 8 „
Oil of nutmeg, 2 drops.
Oil of peppermint, In
Peppermint water, 2 fl. ounces.
Dose, from a half to one teaspoonful. Another reci{>e has no laudanum, but instead
syrup of poppies.
* If made according to Dr. Paris* formula, IJ grains in an ounce.
t It may be regarded as a purified alcoholic solution of meconate of morphia, with
a little excess of acid, and of about the same strength as laudanum. — Taylor,
t Verjuice is the juice of the wild orab.
§ 348.] OPIUM. 293
Chlorodyne— Browu*8 Chlorodyne is composed of —
Chloroform, 6 drachms.
Chloric ether, 1 ,,
Tincture of caj»icuni, ^ ,,
Hydrochlorate of morphine, .... 8 grains.
Scheele's prussic acid, 12 drops.
Tincture of Indian hemp 1 drachm.
Treacle, 1 „
Atkinson's Infant Preserver-
Carbonate of magnesia, 6 drachms.
White sugar, 2 ounces.
Oil of aniseed, 20 drops.
Spirit of sal-volatile, 2^ drachms.
Laudanum, . . . . . 1 ,,
Syrup of saffron, 1 ounce.
Caraway water, to make up, . . . ! 1 pint
Boerhaave's Odontalgic Essence-
Opium, i drachm.
Oil of cloves, ^ >i
Powdered camphor, 5 ,,
Rectified spirit IJ fl. ounces.
§ 348. Statistics.— During the ten years 1894-1903, 1505 deaths
in England and Wales were attributed to some form or other of opinm
or its active constituents ; 882 were due to accident or negligence ; 621
were suicidal and 2 were homicidal deaths. To these may be added
the deaths of 66 males and 36 females (102 total) from the accidental
taking of chlorodyne, the suicidal deaths of 36 males and 3 females
from the same drug, and 9 children dying from soothing syrup, making
a grand total of 1655 deaths from some form or other of opium or its
active constituents in ten years. The sex distribution of the deaths
ascribed to accident and those ascribed to suicide are detailed in the
following tabular statement : —
DEATHS IN ENGLAND AND WALES DURING THE TEN YEARS 1894-1903
FROM OPIUM, LAUDANUM, MORPHINE, Etc.
Accident. i Suicide.
Males, 536 J Males, 432
Females, 346 1 Females, 189
Total, . 882 I Total, . 621
Of European countries, England has the greatest proportional number
of opium poisonings. In France, opium or morphine poisoning accounts
for about 1 per cent, of the whole ; and Denmark, Sweden, Switzerland,
Germany, all give very small proportional numbers ; arsenic, phosphorus,
and the acids taking the place of opiates. The more considerable mor-
294 POISONS: THEIR EFFECTS AND DETECTION. [§ 349, 35O.
tality arises, in great measure, from the pernicious practice — both of the
hard-working English mother and of the baby-farmer — of giving infants
various forms of opium sold under the name of ^^ soothing syrupsj**
** iri/ants' friends " ^* infants' preservatives^^* ^^ nurses' drops,'' and the like,
to allay restlessness, and to keep them during the greater part of their
existence asleep. Another fertile cause of accidental poisoning is mistakes
in dispensing ; but these mistakes seem to happen more frequently on
the Continent than in P]n gland. This is in some degree due to the
decimal system, which has its dangers as well as its advantages, e,g, : — A
physician ordered 5 decigrm. of morphine acetate in a mixture for a child,
but omitted the decimal point, and the apothecary, therefore, gave ten
times the dose desired, with fatal effect. Again, morphine hydrochloratc,
acetate, and similar soluble salts are liable to be mistaken for other white
powders, and in this way unfortunate accidents have occurred — accidents
that, with proper dispensing arrangements, should be impossible.
§ 349. Poisoning of Children by Opium. — The drugging of children
by opium — sometimes with a view to destroy life, sometimes merely for
the sake of the continual narcotism of the infant — is especially rife in
India.* A little solid opium is applied to the roof of the mouth, or
smeared on the tongue, and some Indian mothers have been known to
plaster the nipples with opium, so that the child imbibes it with the
milk. Europeans, again and again, have discovered the native nurses
administering opiates to the infants under their care, and it is feared
that in many cases detection is avoided.
The ignorant use of poppy-tea has frequently caused the death of
young children ; thus in' 1875 an inquest was held at Chelsea on the
body of a little boy two years and a half old. He had been suffering
from whooping-cough and enlargement of the bowels, and poppy-tea
was by the advice of a neighbour given to him. Two poppy -heads were
used in making a quart of tea, and the boy, after drinking a great
portion of it, fell into a deep sleep, and died with all the symptoms of
narcotic poisoning.
§ 350. Doses of Opium and Morphia. — Opium in the solid state is
prescribed for adults in quantities not exceeding 3 grains, the usual dose
being from 16*2 mgrms. to 64*8 mgrms. (J to 1 grain). The extract of
opium is given in exactly the same proportions (special circumstances,
such as the habitual use of opium, excepted) ; the dose of all the com-
pounds of opium is mainly regulated by the proportion of opium contained
in them.
The dose for children (who bear opium ill) is usually very small ;
single droi)s of laudanum are given to infants at the breast, and the dose
cautiously increased according to age. Most practitioners would consider
* Soe Dr. Chever's Jurisprudence, 8rd ed., 232 et aeq.
I3SI-J
OPIUM.
half a grain a very hill dose, and, m eases requiring it, would seldom
preecribe at first more tliaii ^V ^ 1 grain,
Tbe dose of solid opium for a horse is from 1*77 grmt. to 7*08 grwEt
{^ drachm to 2 drachms); in extreme ciiaea, however, 4 drachms {14'16
grms.) have been given.
The dose for large cattle is from 648 gnu. to 3'88 griDi. (10 to 60
grains) ; for calvesj ^648 grm, { 1 0 grains) ; for dogs it is greatly regulated
by the size of the animal, 16*2 to 1 29 "6 mgrms, (| grain to 2 grains).
Fatal Dose. — CmBB are recorded of infanta dying from extremely
imall doaea of opium, e.f?. "7, 4"3, and 8*1 mgrms. (^, y'^, and | of a
gmin); but in mieh instances one cannot help suspecting some mistake^
It may, however, be freely conceded that a very small quantity might
be fatal to infants, and that 3 ragrma. given to a child under I year
would probably develop serious symptoEns.
The smallest dose of solid opium known to have proved fatal to
adults was equal to 259 mgrms. (4 grains) of crude opium {Taf/lor%
and the smallest doee of the tincture (laudanum), 7*0 c,c. (2 drachms)
{Tatjlor) ; the latter is, however, as already shown, uncertain in its
composition.
A dangerous dose (save under special circumstances) is:— For a
horse, 1 4 '17 grma. (4 dmchms); for cattle, 7-04 grms. {2 drachma); for
a dog of the size and strength of a foxhound, i204 mgrms. (3 grains).
Enormous and otherwise fatal doses may be taken under certain con-
ditions by persons who are not opium-eaters* The aentor author haa
seen 13 egrms, {2 grains) of morphine acetate hijccted bypodermically
in a strong man suftering from rabies with but little effect, Tetiinus^
strychnine, convulaions, and excessive pain all decrease the scuaibOity
of the nervous system to opium,
% 351. (General Method for the Detection of Opium. — It is usually
laid down in forensic works that, where poisoniug by opium is suspected,
it is sufhcient to detect the presence of meconic aoid in order to establish
that of opium. In a case of adult pQisontng there is generally substance
enough available to obtain one or more alkaloids, and the presence of
opium may, without a reasonable doubt, be proved, if meconic acid (as
well as either morphine, narcotine, thebaine, or other opium alkaloid)
has been detected. Pills containing either solid opium or the tincture
usually betray the presence of the drug by the odour, and in such a case
there can be no possible difficulty in isolating morphine and meconic
acid, with probably one or two other alkaloids. Tho method of extrac-
tion from organic Huids is the same as before deacribed, but it may, of
course, be modified for any special purpose. If opium, or a preparation
of opium, be submitted to Dragendorff's process (see p. 256 )i the follow*
ing is a sketch of tlie chief points to be noticed.
296
POISONS: rUElR EFFECTS AND MTECTIOK,
[S 35^'
If the s^jlutioD IB arid—
(1) fieuzetie mainly extracts vieismdn, which disaolvas in sulpiiuric
acid very gradually (in twenty-four to forty-eight hours}, with a green
colour passing into red, Meconin has no alkaloidal reaction.
(2) Ainyl alcohol dissolveB email quantities of nmi-miic acid^ identified
by striking a hlood-red colour with ferric chloride.
If now the amyl alcohol is removed with the aid of petroleum ether,
and the fluid made alkaline by ammonia, —
(1) Benzene extracts narcotine^ mdeme^ and ih-ebniiie. On evapora-
tion of the benzene the alkaloid al residue may be dissolved in watetj
acidified with sulphuric acid, and after fUtration^ on adding ammonia m
«a506«if, thehaiihe ami narrotin^ are precipitated, Cfideitie remaining in
aolution. The dried precipitate, if it eon tain thebaine, become® blood-
red when treated with cold concentrated Bulphuric acid, while narcotine
ia shown by a violet colour developing gradually when the substiince
is dissolved in dilute sulphuric acid 1 : 5, and gently warmed. The
codeine in the ammoniacal solution can be recovered by shaking up
with benzene, and recognised by the red colour which the solid substance
gives wheu treated with a little sugar and sulphuric acid.
(2) Cblorofonn especially dissolves the narmnBt which, on evapora-
tion of the chloroform, may be identified by its getieral characters, and
by its soiutioii in Friihde^s reagent becoming a beautiful blue colour.
Small quantities of morphine may be extracted with codeine.
(5) Amyl alcohol extracts from the alkaline solution morphine,
identified by its physical characters, by its forming a crystalline precipi-
tate with iodine and hydriodic acid^ and the reaction with iodic acid to
be described.
§ 352, Morphine (Ci,Hi^N0{0H)3-!-H^0). — Morphine occurs in
commerce as a white powder, sp. giv 1*205, nsually in the form of more
or less perfect six-sided prisms, but sometimes in that of white silky
needles. When heated in the subliming cell (described at p, 260 )|
faint nebulse, resolved by high microscopic powers into minute dots,
appear on the upper disc at 150', As the temperature is raised the
spots become coarser, and at 188*" distinct crystals may be obtained, the
best being formed at nearly ^OC, at which temperature morphine begins
distinctly to brown, melt, and carbonise. At temperatures below 188',
instead of minute dots, the sublimate may consist of white circular spots
or foliated patterns. One part of morphine, according to P. Cbastaing,
is soluble at a temperature of 3^ in 33,333 parts of water; at 22°, in
4545 parts ; at 42*, 4280; and at 100', 4562, It is scarcely soluble in
ether or benaene. Absolute alcohol, according to Pettenkofer, dissolves
in the cold one-fortieth of its weight; boiling, one-thirtieth. Amyl
alcohol, in the cold, dissolves one*fonTth per cont.t and still more if the
§ 353^]
MORPHINE.
397
iilkalold be thrown out of au ai^ueoua acid solutiou by ammonia in the
presence of aniyl alcohol ; for under aucb circumstances the inorphinc
has no time to become crystalline* According to Schlimpert, I part
of morphine requires 60 of chloroform for solution ; according to
Pettenkofer, 175. lOU party of tetraobloride of carbon dissolve "032
morphine {J. Schindelmeiaer, Chemilfer-Zeitungf xxv. 129)*
Morphine is easily soluble iti dilute iicidBj as well m in uoluttons of
the caustic alkalies and alkalmc earths ; carbonated alkalies and chloride
of ammonium also dissolve small quantitieB, The acid watery, uud the
alcoholic solutions, turn the plane of polansatioii to the left ; for
sulphuric, nitric, and hydrochloric acids [a]r- 89"8* ; in alkaline solution
the polarisation is lesSj [«]/* = 45*22*. It is alkaline in reaction, ueutml-
ising acids fully ; and, in fact, a convenient method of titrating morphine
is by the use of a centinormal sulphuric acid^each c.c* equals 2 '85
ragrmH. of anhydrous morphine,
^ 353. The mXis of morphine are for the most part crystalline, and
are all bitter, neutral, and poisonous. They are insoluble in amylic
alcohol, ether, chloroform, benzene, or {jetroleum ether.
Morphllie meconate is one of the most so bible of the morphine
salts -y it Is freely soluble in water. Of all salts this is most suitable
for subcutaneous injection ; it is the form in which the alkaloid exists
in opium.
Morphine hydrochlorate (C^^Hj^jNOaliCl) crystallises in silky fibres ;
it is reatiily soluble in alcohol^ and is soluble in cold, more freely in
boiling, wiiter. The purest morphine hydrochlorate is colourless, but
that which is me^t frequently met with in commerce is fawn or buff-
colon retl.
Morphine acetate is a crystallisable salt, soluble in water or alcohol i
it^ ts in part decomposed bj boiling the aqueous solution, some of the
acetic acid escaping.
Morphine Tartrates, —TLese are readily soluble salts, and it is im-
[Kirtant to note that the morphine might eseai^e detection, if the expert
trusted alone to the usual test of an alkaloidal salt giving a precipitate
wlien the solution is alkaltsed by the fixed or volatile alkalies ; for tlie
tartrates of morphine do not give this reaction^ nor do they give any
precipitate with calcic chloride. By adding a solution of potassium
acetate in spirit, and also alcohol and a little acetic acid to the con-
centrated solution, the tartrate is decomf>osed, and acid tartrate of
potassium is precipitated in the iuaoluble form ; the morphine in
the form of lioetate remains in solution, and then gives the usual
reactions.
The solubility of morphine salts in water and alcohol huE been in-
vestigated by Mr. J, U, Lloyd* His results are as follows: —
298 POISONS : THEIR EFFECTS AND DETECTION. [§ 354.
Morphine Acetate.
11-70 parts of water by weight at Id'O' dissolve 1 part of morphine
acetate.
61*5 parts of water by weight at 100* dissolve 1 part of morphine
acetate.
68-30 parts of alcohol by weight (-820 specific gravity) at Id'O" dissolve
1 part of morphine acetate.
13-30 parts of alcohol by weight (-820 specific gravity) at 100" dissolve
1 part of morphine acetate.
Morphine Hydrochlorate.
23*40 parts of water dissolve at 15* 1 morphine hydrochlorate.
•51 part of water dissolves at 100' 1 morphine hydrochlorate.
62*70 parts of alcohol ('820 specific gravity) dissolve at 15° 1 morphine
hydrochlorate.
30*80 parts of alcohol (-820 specific gravity) dissolve at 100" 1 morphine
hydrochlorate.
Morphine Sulphate.
21*60 parts of water at 15' dissolve 1 morphine sulphate.
•75 part of water at 100* dissolves 1 morphine sulphate.
701*5 parts of alcohol (*820) at 15' dissolve 1 morphine sulphate.
144*00 parts of alcohol (820) at 100' dissolve 1 morphine sulphate.
§ 354. Constitution of Morphine and Codeine.— Morphine is a
tertiary base. It forms diacetyl and dibenzoyl derivatives, hence it
contains two hydroxyl derivatives, one a phenol, the other an alcohol.
Morphine when mildly oxidised forms pseudomorphine identical with
natural pseudomorphine.
Pseudomorphine.
Sulphuric, hydrochloric, phosphoric and oxalic acids, the alkalies,
and zinc chloride have a twofold action on morphine, giving conden-
sation products and a dehydration product, apomorphine CiyHj^NOa,
which has a powerful emetic action. Apomorphine is an amorphous base
soluble in alcohol, ether, and chloroform. Codeine is the monomethyl
ester of morphine,
C,^Hi.NO(OH)(OH) C,7H,.NO(OH)(OCH3)
Moqihinc. Codeine.
Codeine by loss of water yields apocodeine CigHj^NOg. By treating
codeine with concentrated hydrochloric acid at 100*, chlorcodidc,
CigHgoClNOg, is obtained; on heating this with hydrochloric acid at
150', methyl chloride and apomorphine result. Morphine has been
354.]
MORPHINE.
299
converted into codeine by heating with methyl iodide and caustic
potash when the phenol hydroxyl of the morphine is alkylated,
Ci7Hi7NO(OH)3 + CH3l + KOH -> Ci^HiyNOCOHKOCHg) + KI + Hp
Morphine. Codeine.
When codeine methyl hydroxide is distilled it yields methyl-
inorphiniethine (OH)(CH30)Ci7HigO = N - CHg + HgO ; this heated with
OHv
HCl gives methyldioxyphenanthrene >Ci4H8 and dimethyloxethyl-
CH3O
amine OH - C2H4 - N(CH3)2. The first of these has been shown to be
the monomethyl ether of dioxyphenanthrene or methyl nwrpfiol; the free
base from this is known as mat-pholy and has been proved to be 3, 4 dioxy-
phenanthrene, and methyl morphol is 3-methoxy-4-oxyphenanthrene,
OH OH OH ^OCHs
\ /
<z>— <_>
\ /
Morphol. Methylmorphol.
The nitrogenous base formed on heating methylmorphimethiue
CH2OH
with HCl may be represented thus, | dimethyl ethyl
CH2N(CH3)2
oxethylamine, and from the formation of this compound morphine is
considered to contain an oxazine ring of the form
O
HaC
/\
CHa
HjC s^y CH2
NH
this is called morphol ine.
Morphine and codeine thus appear to be ring systems containing the
phenanthrene complex in connection with a morpholine ring, and the
following formula has been proposed for morphine,
CH
HO-C '^"^ CH
CH--a
^H» H>V^'^''*^
Morphine.
300 POISONS: THEIR EFFECTS AND DETECTION. [§355-
§ 355. Tests for Morphine. — (1) Ono hundredth of a milligrm. of
pure morphine gives a blue colour to a paste of ammonium molybdate
in sulphuric acid; 20 mgrms. of ammonium molybdate are rubbed with
a glass rod in a porcelain dish, and well mixed with 5 drops of pure
strong sulphuric acid and the morphine in a solid form applied ; titanic
acid and tungstates give similar reactions.
(2) Morphine possesses strong reducing properties; a little solid
morphine dissolved in a solution of ferric chloride gives a Prussian
blue precipitate when ferridcyanide solution is added. A number of
ptomaines and other substances also respond to this test, so that in itself
it is not conclusive.
(3) Robert's Test. — 2-3 drops of formalin are mixed with 3 c.c. of
strong H2SO4; this reagent is mixed in a watch-glass with the dry
substance. Morphine becomes purple-red, then violet, then clear blue.
The solution examined spectroscopically shows a band in the yellow and
orange ; dionin, codeine, and heroine give similar reactions ; methylphen-
morpholin gives an intense red colour.
(4) Iodic Acid Test. — The substance supposed to be morphine is
converted into a soluble salt by adding to acid reaction a few drops of
hydrochloric acid, and then evaporating to dryness. The salt thus
obtained is dissolved in as little water as possible— this, as in toxi-
cological researches only small quantities are recovered, will probably
be but a few drops. A little of the solution is now mixed with a very
small quantity of starch paste, and evaporated to dryness at a gentle
heat in a porcelain dish. After cooling, a drop of a solution of 1 part
of iodic acid in 15 of water is added to the dry residue ; and if even the
Tfj.hru o^ * grain of morphine be present, a blue colour will be developed.
Another way of working the iodic acid test is to add the iodic acid
solution to the liquid in which morphine is supposed to be dissolved
and then shake the liquid up with a few drops of carbon disulphide. If
morphine be present, the carbon disulphide floats to the top distinctly
coloured pink. Other substances, however, also set free iodine from
iodic acid, and it has, therefore, been proposed to distinguish morphine
from these by the after-addition of ammonia. If ammonia is added to
the solution, which has been shaken up with carbon disulphide, the pink
or red colour of the carbon disulphide is deepened, if morphine was
present; on the contrary, if morphine was not present, it is either
discharged or much weakened.
(5) Lloyd's Test. — A mixture of hydrastin and morphine mixed
with a few drops of sulphuric acid develops after about five minutes a
blue- violet colour. This reaction has been investigated by J. L. Mayer *
and shown to be almost distinctive.
* ZeU. /. analyt. Ohemie, 1902, 576
3SS]
MORPHINE.
301
(6) Vanadic Acid Test, — VauarUteof atiimotiiaisdisaolved in strong
Bulphuric acid ; the aeki must l>e ad fled until the yellow colour dis-
appears and a colourless H<ii<itioii ia obtained; morphine wanned with
a few drops of thia aohition producer a fine green colour, or, If the
sohitiou ia diluted, a bluish-gietm colour*
(7) Ttingstic Acid Te»t. — A solution of auy thing like I per oent* of
sodium tniigatato is imipplieable ; but if a dilute solution of the salt is
taken (aay 1 oigrm. per c.c.) and acidiiied with sulphimc acid, the
solution gives a violet colour with morphine or morphine salts.
(8) Titanic Acid Test, — ^Titanic acid is dissolved in stroug stilphurie
acid Ity the aid of heat ; the aolutiou should bo syrupy and clear. A
drop of this solution added to solid morphine strikes immediately a
black colour.*
Other Beactioas.— There are aoxne very interesting reactions besides
those just mentioned. If a saturated Bolution of chloride of zinc be
added to a little solid morphine, and heated over the water- bath for
from fifteen muiutes to half an liour, the liquid develops a beautifui and
peraistent green colour* This would be an excellent test for morphine
W€re it not fur tlie fact that the colour is produoetl with only pure
n^orphine. For example, the ruction is not obtained from morphine
in very well-formed crystals precipitated from ordinary laudanum
by auimonia, the least trace of resinous or colouring matter seriously
interfering. By the action of nit fie acid on morphine^ the liquid
Ijecomes orange-red, and an acid product of the fonnula Ci^,Il,iNO,, is
produced, which^ when heated in a closed tube with water at lOO"*,
yields trmitrophenol or picric acid. On adding a drop of sulphuric
acid to solid morphine in the cold, the morphine solution liecomea
of a faint pink ■ on gently warming and continuing the heat until
the acid begins to volatilise, the colour changes through a series
of bruwntsh and indeHnite hues up to black* On cooling and
treating the black sp<it with water^ a green solution m obtained,
agreeing in hue with the same green produced by chloride of lehic.
Vidali t has proposed the following test : — Morphine is dissolved in
strong Bulphurie acid, and a little arsenate of sodium is added ; on
gently warming, a passing blue colour develops ; on raising the tempera-
ture higher, the liquid changes into green, then into blue, and finally
again into green, Codoine acts very similarly, C. Reichard {Chetn,
Zeii.^ 1904) uses As^G^ dissolved in strong NaOH solution; to ace*
of this is added morphine and then strong H^BO^; an intense and
permani-^nt purple colour develops. The following test originated with
• C. Eoicharti^ J'fii./* an&lyt, Chtmit^ 1903, 95.
f D* Vitiali, liulL FaitmuTiiL. Miknu, 1881^ ji, 1S7 t D, li Dutt, Ttar Emtk qf
Phannacy^ 1882.
302
POISONS; THEIR EFFECTS AND DETKGTION,
[S 3SS.
Siebold (American Journal of Pharmcunj^ 1873| p. 544) : — The siippjsed
raorphiiie ia heated gently with h few drops of concentrated aulphuric
aoid and a little pure potass to perch I orate. If morphine be present
the liquid tmniediiittfly takes a pronounced brown colour — a reaction
aaid to be pectdifir U> morphine, and to succeed with j*^ of a mgrm. In
order to obtain absohitelj pure [Mjrchlorate^ potaasic perchlorate is
heated with hydrochloric acid so long as it disengages chlorine; it is
then washed with distilled water, dried, and preaerved lor use. There
is also a test known «a ** Pellagrins " ; it depends on the production of
apomorphiue. The auspected alkaloid is dissolved in a little strong
hydroehloric acid, and then a drop of concentrated Hnlphtiric acid is
added, and the mixture heated for a little time from 100"* to 120",
until it assuinea a pnrple-black colour. It is now* cooled, some hydro
chloric aoid again added^ and the miicture neutralised with sodic
carbonate. If nioq>hine be present, on the addition of iodine in
hydriodic acid, a cheny-red colour is produced, passing into green.
Morphine and codeine are believed alone to give this reaction.
The acetate of morphine^ and morphine itself, when added to ferric
chloride solutionj develop a blue colour. When 1 molecule of morphine
is dissolved in alcohol, contaming 1 molecule of Hodium hydroxide, and
2 vols, of methyl iodide are added, and the mixture gently heated, a
violent reaction sets in and the main product its codeine meth iodide
(Ci^Hi^jNOgOCHiMel), If only half the quantity of methyl iodide is
added, then free codeine is in small quantity produced ; if ethyl iodide be
substituted for methyl^ a new base is formed homologous with codeine.
If morphine is heated with iodide of methyl and absolnte alcohol m a
closed tube for lialf an honr at IQO'', methyl iodide of morphine is
obtained in colourless, glittering, quadratic crystalSj easily soluble in
water {C^^H^,,NOgMeI + H^O) : similarly the ethyl iodide compound can
be produced.
If morphine is heated for from two to three hours in a closed tube
with dilute hydrochloric aeid, water Is eliminated —
and the hydrochlorate of apomorphine is prmluced. This succeeds when
even J mgrm. is heated with ^j^ c,c* of strong HCl, and the tests for
aponiorphine applied.
If concentrated sulphuric acid be digested on morphine for twelve to
fifteen hours {or heated for half an hour at 100*), on adding to the
cooled violet-coloured solution either a crystal of nitrate of potash or of
chlorate of potash, or a drop of dilute nitric acid, a beautiful violet^blue
colour is produced, which passes gnidually into a dark blood -red.
j^ of a mgnn, will respond distinctly to this test. FHihde's regent
§356.]
MORPHINE.
303
strikes with morpKine a beiiutiful violet colour, pagaitig from blue into
dirty green, ami finally almost vanishing. ^^^ of a mgroi* will reiipoiid
to the teat, but it is tiot itself coneluBive, since papaverine and certain
glucosides give an identical reaction.
^ 356. Symptoms of Opium and Mort^hine Poisonrng. — The
symptoms of opium and morphine poisoning are so much alike, that
clinically it is inipoi^sible to diatinguiah them ; therefore they may be
considered togetUur.
Action on Animals — Frogs. — The action of morphiiie or opium on
frogs is peculiar ; the animal at first springs restk^ssly about, and then
falls into a condition extremely anBloguus to that seen in strychnine
poisoning, every motion or external irritation producing a tetanic con-
vulsion* This condition is, however, aometimea not olmerved- The
tetanic stage is followed by paralysis of reflex movements and cessation
of breath ingt the heart continuing to beaL
Dogs. — 0'3 to 0*5 grm. of morphine meconate, or acetate, injected
directly into the circulation of a dog, shows its elfecta ahnost immediately*
The dog becomes uneasy, and moves its jaws and tongue as if some
peculiar taste were experienced ; it may bark or utter a whiue^ and then
in a minute or two falls into a profound sleep, which is often to deep
that while it lasts — usually several hours — an operation may be per-
formed. In whatever attitude the limbs are placed, they remain. The
respiration is rapid and stertorous, and most reflex actions are extin*
guished. Towards the end of the sleep, any sudden noise may startle
the animal, nud when he wakes his faculties are evidently confused.
A partial paralysis of the hind leg has often been noticed, and then the
dogf with his tail and pelvis low, has something the attitude of the
hyena. Hence this condition (first noticed by Bernard) has been
called the " hyenoid '* state. If the dose is larger than 2 to 3 gnus.
(51 to 46 grains), the symptoms are not dif similar, save that they
terminate in de.ith, which is generally preceded by convulsions,*
"* MM. Gras«ct &nd Amblard hftVfs studied the Action of morphtDe in causing con-
rtilHioiit; in the tnainmalia^ They fomid that if small doBca of hydrcK^1)l!>mtij or
morphine (fifim I to If* ceiitigrammes) art adminiiterod to dog^et^ the britjf sleep
wLicli y produeetJ may be a^xomjiarded bj ]iartijtl musoulur contractions (in one
|«iw, for inBtancp), which are renewed at v^arijiblu interval a. Then o<x£ur true con-
vulsive Hhocloi in the whole body or in the hind hml:p9. After an inlorv^ah the
phe!noTn«'na recur in more intense d(?gr*.e, and *iru followed l>y true convukionH*
Hcgalarly, ten m &ixt&ea times a mitiute, at each inspiration, the hind luiihs pre^nt
a series of ctiiivnhive movements, whicli may becomL* gener»I. Sometimes they arp
exeited by ejcternal atlmulationr but thcj ara usually spontaneous. The id^ep may
eonthitie pr*>fouiid dnring thia oonmbive i^riod, or jt may hewnn© dbtinctly lighter.
These convulBtve phonomeiia nuy continue, witli intervals, for au hour. DifTerenccs
aj« oheerved with difierent aniioala ; but the chief characters of the phenomena arc
fti deeeiiWL In certain animals, imti with f^mall dories* there may he a brief con*
304
poisons: THKIB effects ANn DKTECTION.
[§ 357.
G^atB. — Accord in g to Guinard, goate are proof against the narcotic
influence of morphine. Large doses kill goats, btit death is caused bj
intcrfereuce with the respiratory function. A young goat weighing 30
kilos, ahowed little effect be}^oud a alightlj increased cerebral excitabiltty
after two doaea of 8 and S'b gnus* respectively of morphine hydro-
chlomte had been adtninistered by intni venous injectiouT the second
being given an hour and a half after the tirat. To the same animal two
d&ys afterwards 1 95 grmB. were fudministered in the same way, yet the
goat recovered ^^ The letlial dose for a goat seems to be no less tiian
1000 times that which will produce narcottsm in man, and lies somewhere
between 0*25 to 0'30 per kilo, of the body weight*
Gats and the Felidse.— According to Guiuard,t morphine injected
aubcutaneonsly or lut ravenously into cats, in dosea varying from 0"4
mgrm* to 90 mgrras. per kilo.^ never produces sleep or narcotic prostra-
tion. On the contrary, it causes a remarkable degree of excitement,
increasing in intensity with the dose given. This excitement is evidently
acGompaniod by disorder in the functions of the brain, and if the dose is
large convulBiona set in, ending in death. According to Milne-Edwards,
the same symptoms are produced in lions and tigers,
Btrds^ especially pigeons, are able to eat almost incredible quantities
of opinm. A pigeon is said { to have consumed 80 1 grains of opium,
mixed with its food, in fourteen days. The explanation of this is that
the poison is not absorbed ; for Bubcut^meouH injections of salts of
morphine act rapidly on all birds hitherto experimented upon,
g 357. Phyaiological Action, — From experiments on aiiimalsj the
vulsive [>haii« at tlia commencemeot of th^ ^eap, but it is much less cchnstant than
the later period of a|>ii4nn. These couvulftions, the authorB believe, have not pi-e-
vioualy been describfid, exct+pt iia u cor! sequence of very large doaea j amonutitig to
grmmme^ The jieriod of (Cerebral excitemeutj described by Claude Bcrtiftrd h&
oocnrring at the oomnieiictinicnt of the aleeji from morpbinej h a phenomenon of
A different order. The conclaaioiia diawn from the experiuients are— (1) That
morphine is not diflmetrically oppe*»d to thebaine, as ii often stated, ain<ie it h*s, to
a certain degree, the eonvalBive properticii of the latter alkaloid. (2) That the
oxcitomo tor action ofopimii cannot be exclusively a ttribnt^d to the convulsive alka-
loidSp but h, in fact^ due tn those whieh are 80i>arific. According t^ the ordinnty
eonifwisitioij of opium, 5 eentigrannue» of utorpbine rtipreaent about a milligramme
of thebaine. lint thest' experiments show that the quantitj- of morphine has a much
more [>owerful convulsive action than a milligramme at thebaine. (3) TheiMs ia not
the supposed anta^^onLani between the t^tiou of morjjhine on tbi* frog and on the
mammalia. {4) The rt\^earehes hitherto undertaken on the antagonism tietween
morphine and other agents need to be re treated « and a »e|«rate atudy made of the
f!ul>stance^ which antagonise the convulsive and soporilic action.
* C&mpl. ^4^j(d., t civi, pp. 520-522,
+ Cfmipi, Mend, J t cxi, pp. &81-083, The k^4?ttte animals alao get excited^ and
no narootie effeet is produced by doaing them witli morphine, — Cewyif, Mend. Soc. dt
Siohifiif, t iv. , V.
t Hermann's LshrbiieJt dcr cxper. T&jcimkisi^t p' 374,
§ 3S8-]
MORPHINK.
305
essential action of morphine on the nervous \uid arterial systems has in
some meaatire been examined. There is no very considerable action on
the hearts The beats are first acodlgratedi then di mini abed in frequency ;
but very large doseti introduced directly into the circulation at once
diminish the pulsations, and no acceleration is noticed. The slowing
may go on to heart-paralysia. The slowing is central in ite origin, for
on the vagi t>eing cut, morphine always quickens. With regard to the
peripheric ends of the vagi, small doses excite, large paralyse. If all
the nerves going to the heart are divided, there is first a considerable
acceleration, and then a slowing and weakening of the pulsation. The
arterial blood-pressurei at first increased^ is afterwards diminished*
This increase of blood- pressure is noticed during the acceleration of the
pulse, and also during some portion of the time during which the pulse
is slowed. Stockman and D. B, Dott^* experimenting on rabbits and
frogs, consider that a medium dose of morphine first of all depresses the
spinal cord and then excites it^ for tetanus follows. If morphine is in
sufficient quantity tlirown into the oirculationj then tetanus at once
occurs. Tt would thus appear that depression and stimulation is
entirely a matter of dosage, Gescheidlen, in his researches on the frog,
found the motor nerves at first excited, and then depressed. When the
doses were large, there was scarcely any excitement, bat the reverse
effect, in the neighbourhood of the place of application* According to
other observers, the function of the motor nerves may be annihilated, t
According to Meihuizen, reflex action ^ at first much diminished, ia later,
after several hours^ norma], and later still again increased. The
intestinal movements are transitorily increased, Tn the dog there has
been noticed a greater (low of saliva than usual, and the flow of bile
from the gall-bladder is diminished. The pupils in animals are mostly
contracted, bnt, if convulsions occur towards death, they are dilated.
g 358. Physiological Effect of Morphine Derivatives.— By intro*
ducing methyl, or amy!, or ctliyl, into the morphine molecule, the
narcotic action is diminished, while tlte tetanic affects are increaaed.
Acetyl, diacetyl, benzoyl, and dibenzoyl morphine, morphine sulphuric
ether, and nitrosomorphine are all weaker narcotics than morphine, hut,
on the other hand, they depress the functions of the spinal cord and
bring on, in large doses, tetanus.
The introduction of two methyl groups into morphine, as in metho-
codeine* Cj-Hi^MeNO(OH) -Me, entirely alters the pliysiologiml effect
This compound has an action on voluntary muscle causing gradual
paralysis.
The cldorine derivatives, trichlormorphine and chloroodeine, have
the characteristic action of the morphine group on the central nervous
• Mrit, Med, Jmim. (*2), 18t0, 130-162. t Arch./, rf* Oejf, Fhgitioi,, v\l p, 20L
20
jd>0c;i£Uj. Lk*- 'j;^*^' iiiumtj^ .*: Hi*. iMicr "^
tW 1:. / '•V^ «ft;6{««V 'ir^b. S. V3USL UmSLL X^Sflr
tf' AtUiAftj U*' r.tsm iifUBtr liur -nru. .pTsar nansTr^ msml Tninifcr a: a.
jUK. iui^'. ^r' >«» tu;.*;'^" iiinf* una iu^ SST 5X4?*. & ic&vTZZiflft^J
i»0t9^«d»#'. MJ»<^ Il#-: r-il:,TU;i7I!TK tfR TPOf^r*^ Hrr ikC: MMK. AM
tuuMMt J: ^Jtw rrfi jl Xu^fTr ir .ST'or. zmsubiiirr cr tft: jkil.
^^fUtiUiss: uutr > uRftKrin Ti^ tAm-^ji- oi^ iibumI?7 — ^n. imsi ;
aM/ft — vjueltijas^ii. TwfT»: jr uitft ffUDK i«i» or itnw? nver i^. XM
lUKl^m: «Bi. li- t*fu^ vt Toutf*!. pn* iiaaBL. sdbcius:. or cnaraL
nn^tfRC wni L '.'jttiiiu!^ f^tici Titt jnnnit art siiL eomimfSML mt iaH*r
luijt ft xut jwr u^nm tr im diitriA bul x: j^ ssBsadr tkcrt*L TtmCL if 4.
*>ry^. » iituut v^nt '!*• piUiUr dilutee, liifr rraPTTTns;ainr' 'Stt&a. n. iXMslL
Tut: mtM^. jtm. » luu: n. vmisi. "ait nidmduaa. sm&f usu & aeot
««^ tttxii'jr mmt^fCutfVtr^ — ^lajur. ib. vmin. r^ otr jo. minuus— «aiL diei^
It «. iev Uiftm, Ii tiMjK miML mifnr "liti pmiifr im juil !« in caucDncjr
vr j^srvjut uuutr xnu^srwrnt ixmiinuni sraudiuoEu^
A tuis. #1 >«tt*> uiL v^L ji»L 'StaiLeL mutu^ diiL^ sui» ii> :,:rii£
* L. ifM^ficjUBi i»u', I/jr. in:. jr«L. Jmru :.. ISS*- ';'^*-^::fii
1.1 oc y jjiu!Uaiiuil lurt tii<iv vw-fv i,« icrnuitiiin^ 1if i'Or mnc. & t^V it-<r:v She
§359^]
MORPHIKS.
3P7
year — ^his dose being 6 grms. (92*4 grains) of solid opium — whou
out huntings of whicb sport he wua passionately foud, took cold, and,
m a remedy^ adniitiiatered to himself three times his aocuatotned doae*
Very shortly there was contraction of the left arty, disturbance of visioii,
pftin in the stonjach, fajntues«, inability to speak^ and uneouaciousuess
wbiob lasted half an hoar. Intermittent oouvulsioiiB now set in, and
pains in the limbs* There was neitlier somnolence nor deliriuni, but
great ttgitation ; repeated vomiting atid diarrhrea followed. After five
hours these symptoms ceased ; bnt he was excessively proatrate.''^ There
was complete recovery.
One may bayard a surmise that^ in auch a case, tolerance bas been
established for morphine, but not for other morphine alkaloids in the
same degree, and that the marked nervous aymptoms were in no small
degree the effect of some of fche homologous alkaloids, which, in such an
enormons dose, would be taken in sufficient quantity to have a physio-
logical action.
There are seveml instances of a relapsing or remittent form of
poisoning — a form in which the patient more or less completely recovers
consciousness, and then sinks back into a fatal slumber. One of the
best known is the case of the Hon. Mrs AuHon (January 1859), who
swallowed an onnce and a half of laudainuii by mistake. After
remain ing in a comatose condition for more than nine honrSj she
revived. The face l>ecame lUitural, the pulse steady. She was able to
recognise her daughter, and in a thick voice to give an account of the
mistake. But this lasted only tt*n minutesj wlien she again became
coumtose, and died in fourteen hours.!
In a Swedish case (|notetl by MaschkajJ i^ girl, 9 years old, in
weak he^dtb and Huflering from slight bronchitis, had been given a non-
o^einnl fkcetate of morphia lozenge, which was supposed to contain 5
nigniia. {075 grain) of morpliine acetate. She took the loscenge at
8 in the evening ; soon slept^ woke at 10, got out of bed, laughed,
t^ilked, and joked with the nurse, again got into bed, and very quickly
fell asleep. At 4 a,m, the nnrse came and found her breathing
with a ratthng sound, and the phjaieian, who arrived an hour later,
found the girl in a state of coma, with contracted pnpils, breathing
stertoroufily, and the pulse scarcely to be felt. Despite all attempts
to rouse the patient, she ditMi at 6 in the mornings twelve hours after
taking the lozenge*
• D^moutpoTCTllct, De VUtag^ Qualidmi dt POpium, P«ri*, I8?l-
t Tiiylwr, I'p. tit*
X MitJii*Kkik*a Httmlhtichj Baiid li. p. 43S ■ al^ Sveiwkd, I^ik-h'tilhk. Ftirhtfttfil,^
Apr. I, \K S»0 ; A\n\ S, i\ IflO, 1873. For other ciitMss we NikHtiiyth, JuUju Mrd.
M^d, Times mid Gm., Miut^U 20, Um*
3o8
POISONS : THEIR EFFKCTS AND DETKCTION.
[S 359-
The poat-niortem cs ami nation showed some hyperspmia of the brain
and serous efftision in the ventricles, anrl there waa al&o tubercle in the
pleura. Three lozenges similar to the one taken by the patient were
cheraically inveBtigated by Hamburg, who found that the anionnt of
acetate was very small, and that the lozenges, instead of morphine
acetate, might be considered aa prepared with almost pure morphine ;
the content in the three of morphine being respectively 35, 37^ and
42 mgrme. (that is, from half a grain to three-fifths of a grain). There
was a difference of opinion among the experts as to whether in this case
the child died from morjihine poisoning or not — n difference solely to
be ftttrihnted Uy the waking up of the child two hours after taking the
poison. KoW| considering the great prabability that a large dose for
a weakly child of that age had heen taken, and that this is not the
only case in which a relapse has occurred, it seems jimt to infer that it
was really a case of poisoning.
As unusual symptoms (or ratlier sequelae) may be noted in a few
cases, hemiplegia^ which soon passes off; a weakness of the lower
extremities may also be left, and inability to empty the bladder
thoroughly ; but usually on recovery from a large dose of opium, there
is simply heaviness of the headj a dry tongue, constipation, and loss of
apj>etite» All these symptoms in healthy people vanish in a day or tw^o.
There have also been noticed slight albuminuria, eruptions on the skin,
loss of taste, and numbness of parts of the body.
Opium, whether taken in substance, or still more by subcutaneous
injection, in sonje individuals constantly causes faintness.
Some years ago the senior author injected one-sixth of a grain of mor-
phine hj^drochl orate subcntaneously into an old gentleman, who was
euftering from acute lumbago, but was otherwise healthy, and had no
heart disease which could he detected ; the malady was instantly relieved,
and he called out, *'I ani well j it is most extraordinary/' He w^ent out
of the front door, and walked some fifty yards, and then yvBB observed to
reel about like a drunken man. He was supported back and laid in the
horizontal posture ; the face was livid, the pulse could scarcely be felt,
and there was complete loss of consciousness. This state lasted about
an hour, and without a doubt the man nearly died. Medical men in
practice, who have been in the habit of using hypodermic injections of
morphine, have bad experiences very similar to this and other cases,
and it is evident that morphine, when injected hypodermically even iu
a moderate dose, may kill by syncope, and within a few minutes.*
* See a raac of tiioriilii^ {loLsoning by hypodermic injectioci, mid recovery, by
Philip E, rfill. M.R.as., Mw*^!, Sept. 30, 1882. In this instaiioe a third of a
grain introduced BiilKiiitauoouitly cau»^ mont dungcroua aymptoais io tx gardener,
«gedlS.
1 360.]
MORPHINE.
AbttDr]jLtLHi by liypodermtu tidaihu&tnition ii^ lio raj)id th^t by fcho time,
or csven twfore tht^ neecUe of the syriuge l& withdrawn^ a coiitmijtjoii of
tho pupil may be observed.
Opium or morphiue m poisonous by whatever chanuel it gaiuB access
to the isy^tem ; the iuteatiiiat ihucqub membrane absorbs it readily^ aud
uarcotie Btlects mfiy be produced by e^tterual applications, whether a
wound is present or tjot A case of absorjition of opium by a wouud is
related iu Cliever's J uritqirudefice^^ A Bunncsc boy, about 9 or 10 years
of age, was struck on the forehead by a brickbat^ cauEiiig a gaping
wound about an inch long ; his jmrents stnttbd the wound with opium,
On the third day after the accident, and the opium still remaioing in the
wound, he became semi-eomatose, and, in short, had oil the symptoms
of opium narcosis ; with treatment he recovered. The unbroken skin
also readily absorbs the drug. Tardieu states that he had seen 30 grms,
of laudanum, applied on a poultice to the abdomen, produce death*
Christisoit has also cited a case in which a soldier suHbred from erysipelas,
and died in a narcotic state, apparently produced from the too free
application of laudanum to the inflamed part.
To these cases may bci added the one cited by Taylor, in which a
druggiat applied 30 grains of morphine to the surface of ao ulccraUd
breast, and the woman died with all the symptoms of narcotic poisoning
ten hours after the appliciitiou — an event scarcely suq>rising. It is a
curious question whether sufficient of the jjoison enters into the secre*
tious — e.ij, the milk — to render it [Kjiaonous. An inquest was held
in Manchester, Nov, 1875, on the hody of a inaie child 2 days old,
in which it seemed probable that death had occurred through the
mother's milk. She was a couflrmed opium-eater, taking a solid ounce
per week*
g 360. Biagtiosis of Opium Poisoning. — The diagnosis is at times
bet\veen poisoning by opium or other narcotic substances ; at others^
between opium and diseaBO* luseuaibility from chloral, from alcohol|
from belladonna or atropine, and from carbon monoxide gas, are all more
or less like opium poisoning. With regard to chloral, it may be that only
chemical analysis and surrounding ciroumstaucea can clear up the matter.
[n alcohol puisoniDg, the breath commonly smells very strongly of
alcohol, and there is no diflicnlty in separating it from the contents of
the stomach, et-c-, l>esides which the stomach is usually red and inflamed.
Atropine and belladonna invariably dilate the pupil, aud although just
before death opium has the same effect, yet we must hold that mostly
opium contracts, and that a widely-dilated pupil during life would, ^m* ne,
lead us to suspect that opium had not been used, altliough, as before
mentioned, too much stress rinist not be laid upon the state of the pupils.
• Third *?d.,ii, 2*^8.
310
POISONS: THKm EFFECTS AND DETECTION,
[§ 361.
lij c44rU>iJ monoxide, the peculiar rose-red condition of tlie body aflbrdw a
striking contrast tu the pallor which, for the moat part, accompanies
opium poiaoiiiug. In the rare casesj iti which con vula ions are a prominent
symptom, it uiaj he doubtful whethei' opium or strychuims has been taken ;
but the uonvulaioiis hitherto noticed in opium poiaopiug aeem to have
been rather of an epileptiform character, and very different from the
eU'ects of itrychniue. No rules can be laid down for case^ which do not
ruua noroial course * in medicine anch are being constantly met witl», and
require all the care and acumen of the trained observer* Cases of disease
render a diaguosis often extremely difflcult^ and the more ao iu those in-
stances in which a dose of laudanum or other opiate has been administered*
In a case under the observation of one of us, a woman, suffering from
emphysema and broachitit»i sent to a chemist for a sleeping dr^iught,
which she took directly it arrived* A abort time afterwards she fell into
a profound slumberi and died within six hours. The draught had been
contained in au ounce- and-a-half bottle ; the bottle was empty, and the
druggist stated in evidenoe that it only contained 20 minims of laudauumi
10 grains of potass ic bromide, and water. On, however, diluting the
single drop remaining in the bottle, and itnitating its colour with severai
sampler of laudanum diluted in the same way, the conclusion was come to
that tlie quantity of laudanum v\hich the bottle originally contained was
far iu excess of that ^^hicb had been stated^ and that it wna over
1 drachm and under 2 drachms. The body was pallid, the pupils
strongly contracted, the vessels of the brain membranes were filled with
fluid blood, tmd there wits about an ounce of serous fluid in each
ventricle. The lungs were excessively emphysematous, and there was
much secretion in the bronchi j the liver wag aliglitly cirrhotic. The
bloody the liver, and the contents of the stomach were exhaustively
analysed with the greatest ciire, but no trace of morphine, narcotino, or
mecouio acid could be separated, altliough the womsin did not livu more
than six hours after taking the draught. It was, in the woman ^s state,
improper to prescribe a sedative of that kind, and probably death had
been acceieratcd, if not directly caused, by the opium.
Deaths by apo[ilexy will only simulate opium-poisoning duritig life;
a post-mortem examination will at once reveal the true nature of the
malady. In epilepsy, however, it is different, and more than once au
epileptic tit has occurred and been follow^ed by coma^a coma which
certainly cnnnot be distinguished from that produced by a tjarcotic
poison. Death in this stage may follow, and on examining the body no
lesion may I36 found.
§361. Opium-eating. — The consumption of opium is a very ancient
practice among Eastern nations, and the picture* drawn by novelist and
traveller^ of poor, dried- up, yellow mortals addicted to this vicet, with
§ 36i.]
HORPHINK.
311
their faculties torpid, their skin lianging iii wriukies on their wasted
bodies, the conjuucfcivtc tinged with iiile, the bowels so iniictive that
there is scarcely an excretion in the course of a week^ the mental faculties
verging on idicMjy and imbecility » h onlj tnie of a percentage of those
who are addicted to the habit. In the Britiifk Mediral Jmirnai for
1694, Jan, 13 and 20, will be found a careful digest of the evidence
collated from 100 Indian medical officers, from which it appears that opium
is taken habitually by a very large number of the population through-
out Indiiv those who are aacuetoraed to the drug taking it In quantities of
from 10 to 20 grains in the twenty-four hours ; so long as this amount
is not exceeded they do not appear to suffer ill-health or any injurious
effect. The native wrestlers even use it whilst training. The habitual
consumption of opium by individuals hjis a direct medico-legal bearing.
Thus in India, among the Haji>ootSf from time immemorial, infused
opium has been the drink both of reconciliation and of ordinary greeting,
and it is no evidence of death by poison if even a considemble quantity
of opium be found in the atomiich after death, for this circumstance
taken alone would, unless the history of the case was further known, be
considered insuDicicnt proof. iSoj again^ in all climates, and among all
races, it is entirely unknown what quantity of an opiate should be con-
sidered a poisonous dose for an opium-cater Almost incredible quantities
havej indeed, been consumed by such persons j and the commonly-received
explanation, that the drug, in these caaes, passes out unabsorbed,
can scarcely be correct, for Hermann mentions the case of a lady of
Zurich who daily injected subcutaneously l to2 grms* (15-31 grains) of a
morphine salt* In a case of uterine cancer, recorded hy Dr. W. C. Ca«a,*
20 grains of moi^phine in the twelve hours were frequently used sul>
cutaneously ; during thirteen months the hypodermic syringe was used
1350 times^ the dose each time being 5 grains. It is not credible that
an alkaloid introduced into the body hypodemiically should not be
absorbed.
Opium -smoking is another form in which the drug is used, but it is
an open question as to what poisonous alkaloids are in opium smoke. It
m scarcely probable that morphine sliould be a constituent, for its sub-
liming point is high, and it will rather be de^Kisited in the cooler portion
of the pipe. Opium, specially prepared for smoking, is called ^' Chandoo ";
it is dried at a temperature not exceeding 240°. H, Moissan f has
investigated the products of smoking chandoo, but only found a small
quantity of morphine. N. Grehant and E. Martin X have also experi-
mented with opium smoke; they found it to have no appreciable ejf^ect
on a dog ; one of the writers smoked twenty pipes in succession, contain-
* LaAeat, March 25, 1382. 8£e al^ Eh*. Buiiltoii*H oAao^ Lattcet^ Muit^h 1S» 1B82,
t Obr;y3<, Ik^fd,, oiv. &88-&92. X Compi, i&iwi., cxv. 1012-1014.
312 POISONS: THEIR EFFECTS AND DETECTION. [§ 362, 363.
ing altogether 4 grms. of chandoo. After the fourth pipe there was
some headache, at the tenth pipe and onwards giddiness. Half an hour
after the last pipe the giddiness and headache rapidly went off. In any
case, opium-smoking seems to injure the health of Asiatics but little.
Mr. Vice-Consul King, of Kew-Kiang, in a tour through Upper Yangtse
and Szechuan, was thrown much into the company of junk sailors and
others, "almost every adult of whom smoked more or less." He says:
— " Their work was of the hardest and rudest, rising at 4 and working
with hardly any intermission till dark, having constantly to strip and
plunge into the stream in all seasons,. and this often in the most
dangerous parts. The quantity of food they eat was simply prodigious,
and from this and their work it seems fairly to be inferred that their
constitution was robust. The two most addicted to the habit were the
pilot and the ship's cook. On the incessant watchfulness and steady
nerve of the former the safety of the junk and all on board depended ;
while the second worked so hard from 3 a.m. to 10 p.m., and often
longer, and seemed so independent of sleep or rest, that to catch him
seated or idle was sufficient cause for good-humoured banter. This
latter had a conserve of opium and sugar which he chewed during the
day, as he was only able to smoke at night."
§ 362. Treatment of Opium or Morphine Foisomug. — The first
thing to be done is doubtless to empty the stomach by means of the
flexible stomach-tube ; the end of a sufficiently long piece of indiarubber
tubing is passed down into the pharynx and allowed to be carried into
the stomach by means of the natural involuntary movements of the
muscles of the pharynx and gullet ; suction is then applied to the free
end and the contents syphoned out; the stomach is, by means of a
funnel attached to the tube, washed out with warm water, and then
some coffee administered in the same way.
Should morphine have been taken, and permanganate of potash be
at hand, it has been shown that mider such circumstances potassic per-
manganate is a perfect antidote, decomposing at once any morphine
remaining in the stomach ; but it, of course, will have no effect upon any
morphine which has already been absorbed. In a case of opium poison-
ing, reported in the Lancet of June 2, 1894, by W. J. C. Merry, M.B.,
inhalations of oxygen, preceded by emptying the stomach and other
means, appeared to save a man, who, three hours before the treatment,
had drunk 2 ozs. of chlorodyne. It is also the received treatment
to ward off the fatal sleep by stimulation ; the patient is walked about,
flicked with a towel, made to smell strong ammonia, and so forth. This
stimulation must, however, be an addition, but must never replace the
measures first detailed.
§ 363. Post-mortem Appearances. — There are no characteristic
S 36+]
MORPHINE,
5^3
iippeurtitiL^OM afier d4;Mith ^vu iiyperaMuia of tbu bmm uiid blood'VeBaeLs
of the uiembranes, with generally aerous effuBiou into the ventricles.
The pupilti fit'(3 aotiietimea eontnictedj sotiiotime8 dilated, ttie dilatation
ouuurring, m before naentiotied, in the act of dying. The extenial
Burlace of the body is either livid or pale. The lunga are commonly
hyperiEiniu, the bladder full of urine; itill, in not a few cases,
there is nothing abnormal, and in no single case oould a pathologiistf
from th6 appearance of the organij only, declare the cause of death
with confidence.
g 364, Separation of Morphioe irom Aminal Tissues and FluidB*—
Formerly a large proportion of the opiuQi and morplane cases submitted
to chemical experts led to noreaiiltg ; but owing to the improved processcB
now adoptcii, failure, though still common, is less frequent. The con-
stituents of opium taken into the blood undergo piirtial destruotion in
the animal body, bnt u portion may be found in the secretions, more
especially in the urine and fajces. First Bouchardat* and then Lefort t
ascertiuned the excretion of morphine by the urine after medicinal
doses ; Dragendorff and Kauzmanii showed that the appearance of
morphine in the urine was con stmt, and that it could be e^ly ascer-
tained and sepirated from the urine of men and animals \ and Levinstein |
kas also sho^rn that the elimination from a Biugle dose may extend over
five or six days. The method used by Dragendorff to est met morphine
from either urine or blood is to shake the liquid (acidified with a
mineral acid) several times with amyl alcohol, which, on removalj
sepanites urea and any bile mlds. The liquid thus purihed is then
alkalised, and shaken up with amy! alcohol, and this amyl alcohol
should contain any morphine that was present, The alcoholic solution
is treated as detailed on p. 315, Considerable variety of results seems
to be obtained by different experimenters. LandsbergJI injected
hypodermically doses of *2 to '4 grm* of morphine hydrochlomte into
dogs, making four experiments in all, but failed to detect morphine in
the urine. A large dose with 2'i mgrms, of the salt gave the same
result. On the other hand, '8 grm. of morphine hydrochlorate injected
direct into the jugular vein, waij partly excreted by the kidneys, for
90 c.c* of the urine yielded a small quantity of morphine- Voitj again,
examined the urine an 1 fasces of a man who had taken morphine for
years ; he could detect none in the urine, but separated morphine from
the fajces.ll Morphine may occasionally be recognised in the blood.
* Bull G^ti, dt TJiirap., Dec. 1861.
t Jowrrt. (fc Ckifi^ , xi. OS, 1S61.
t BcH, kUrt. irtKh^nsehr., 1876, 27.
I Pfiiiget'it ArMv,, niii 413-433,
I! Arck Marm.t [a], viL pp. 28-26.
C/ifWi, Sf}c, Jmrn., May 1882, 543.
314 POISONS: THEIR EFFECTS AND DETECTION. [§ 365.
Drageudorff * found it in the blood of a cat twenty-five minutes after a
subcutaneous dose, and he also separated it from the blood of a man
who died of morphine poisoning in six hours. Haidlen t recognised
morphine in the blood of a suicide who had taken opium extract.
On the other hand, in a case where a woman died in six hours from
a moderate dose, probably of laudanum, although the quantity of blood
operated upon was over a pound in weight, and every care was taken,
the results were entirely negative. In poisoning by laudanum there
may be some remaining in the stomach, and also if large doses of
morphine have been taken by the mouth ; but when morphine has
been administered hypodermically, and in all cases in which several
hours have elapsed, one may almost say that the organ in which there
is the least probability of finding the poison is the stomach. It may,
in some cases, be necessary to operate on a very large scale; — to
examine the fsBces, mince up the whole liver, the kidney, spleen, and
lungs, and treat them with acid alcohol. The urine will also have to be
examined, and as much blood as can be obtained. In cases where all
the evidence points to a minute quantity (under a grain) of morphine,
it is decidedly best to add these various extracts together, to distil off
the alcohol at a very gentle heat, to dry the residue in a vacuum,
to dissolve again in absolute alcohol, filter, evaporate again to dryness,
dissolve in water, and then use the following process : —
§ 365. Extraction of Morphine. — To specially search for morphine in
such a fluid as the urine, it is, according to the authors' experience, best
to proceed strictly as follows : — The urine is precipitated with acetate of
lead, the powdered lead salt being added to the warm urine contained in
a beaker on the water-bath, until a further addition no longer produces
a precipitate ; the urine is then filtered, the lead precipitate washed, and
the excess of lead thrown down by SH^ ; the lead having been filtered
off, and the precipitate washed, the urine is concentrated down to a syrup
in a vacuum. The syrup is now placed in a separating tube (if not acid,
it is acidified with hydrochloric acid), and shaken up successively with
petroleum ether, chloroform, ether, and, lastly, with amylic alcohol (the
latter should be warm) ; finally, the small amount of amylic alcohol left
dissolved in the liquid is got rid of by shaking it up with petroleum
ether. To get rid of the last traces of petroleum ether, it may be neces-
sary to turn the liquid into an evaporating dish, and gently heat for a
little time over the water-bath. The acid liquid is now again transferred
to the separating tube, and shaken up with ether, after being made
* Kauzmann, Beitrdgefur den fferichUieh-chemisehen Nachweis des Morphia u.
Nareotint, Dissert , Dorpat, 1868. Drageudorff, Pharm, Zeitxhr./, Eussland, 1868,
HfL4.
t Wilrtbg, Oarrespondcnzbl,, xxziv. 16, 1896.
S 36&]
NARCOTDtE.
315
alkaline witli annaoiiia ; this will remove nuarly all nlkuloidtt saveiiior-
piiuie,— tujilur the circum8tiiU4:c*i| a very mnall qiumtity ot^ liiorphinc may
iddded be taken up by the ethor^ but not the main bulk. After separate
ing the ether, the liquid is again made slightly aeid, bo as to be abk to
precipitate uiorphine in the prcBeuce of tho solvent; the tube la warmed
on the watt^r-bath, at Icasst its own bulk of hot amy lie alcohol added and
the liquid nmde alkaline, and the whok- well shaken. The amy lie
alcohol is removed in the usual way, and shaken with a small quantity
of decinormal sulphuric acid ; thi« washes out the alkaloid from the
amyl alcohol, aud the siime amyl akohi>l can l>e used again and again.
It is heat to extract the liquid fur morphtne at letiBt thrice, and to
operate with Ixith the solution and the amyl hot* The decinormal acid
liquid is made slightly alkuline with ammotiia, and allowed to ^tand For
at least twelve hours ; any precipiUUo is eollected and wttshed with
ether, and then with water; the alkaline liquid from which the mor-
phine has l>eeii separated is concentrated to the bulk of 5 c,c, on the
water-bath, and ug^nn uHuwe^i to stand for twelve hours; a little more
morphine may often iu th»H way be obbiincth
The authors in bome test experiments, in which weighed small
quantities of morphine (60-80 mgrms,) were dissolved in a little deci-
normal sulphuric acid, and added to large quantiiies of urine, found the
process given to yitld from 80 to 85 per cent* of the alkaloid added, and
it was always recovered in fine crystals of a slight brown tintj which
responded well to tests.
Various other methods were tried, but the best was the one given ;
the method not only separates the alkaloid with but little loss, but bIm)
in a snilTciently pure state to admit of identihcation.
From the tissnes the alkaloid may be dissolved otit by the genetiil
method ^iven at p. 51, aud the ultimate aqueous solution, reduced to
a bulk of not mure tliaii 25 cc, treated by the ethereal solvents in the
way just described*
§ 306, Narcotine (C^^jHo^^iNO^) crystallises out of alcohol or ether in
colourless, traiispaveut, glittering needlesj or groups of needles, belong-
ing to the orthorhombic system.
It is only shghtly soluble in lioiling, and almost hisoluble in cold
water. One part requires 100 partii of cold, an<l '20 of boiling 84 per
c«ut alcohol; 126 parts of cold, 48 of boiling ether {specific gravity
0^735); 2*60 parts of chloroform ; 400 of olive oil; 60 of acetic ether;
300 of amyl alcohol ; and 22 parts of beujaene, for solution. The neutral
solution of narcotine turns the plane of polarisation to the left [a}r ^
ISO'S"; the acid solution to the right. Narcotine has no effect on red
litmns-paper.
Narcotine gives uo crystalline sublimate ; its behaviour In the sublim-
3i6 poisons: thbir effects and detection. [§ 366.
ing cell is described at p. 261. Its melting-poiut, takeu iu a tube, is
about 176*.
Behaviour of Narcotine with Beagents. — Narcotiue, dissolved iu
dilute hydrochloric acid, aud then treated with a little bromine, gives a
yellow precipitate, which on boiling is dissolved ; by gradually adding
solution of bromine and boiling, a fine rose colour is produced, readily
destroyed by excess of bromine. This is perhaps the best test for the
presence of narcotine. Concentrated sulphuric acid dissolves narcotine ;
the solution in the cold is at first colourless, after a few minutes yellow,
and in the course of a day or longer the tints gradually deepen. If the
solution is warmed, it first becomes orange-red, then at the margin
violet-blue ; and if heated until hydric sulphate begins to volatilise, the
colour is an intense red-violet. If the heating is not carried so far, but
the solution allowed to cool, a delicate cherry-red hue slowly develops.
If the sulphuric acid solution contains 1 : 2000 of the alkaloid, this
test is very evident ; with 1 : 40,000, the colour is only a faint carmine.
— A» Huseinann.
A solution of narcotine iu pure sulphuric acid, to which a drop of
nitric acid has been added, becomes of a red colour ; if the solution is
warmed to 150**, hypochlorite of soda develops a carmine-red; and
chloride of iron, first a violet, then. a cherry-red. The precipitants
of narcotine are — phosphomolybdic acid, picric acid, sulphocyanide of
potash, potassio cadmic iodide, mercuric chloride, platinic chloride, auric
chloride, and several other reagents.
Gonstitutioii of Narcotine. — Narcotine contains three methoxyl
groups, and also an N-CHg group, for when heated with alkalies
to 220** it yields methylamine, dimethylamine, and trimethylamine.
Heated with water or H2SO4 at 140* it yields Cn^HioO,^ opianic acid
and CjjHjgNOg hydrocotamine, Hydrocotarnine is the reduction pro-
duct of cotarnine and is a derivative of methyl tetrahydroisoquinoline,
CH,
CHA "^"^
U-
CHjO'^^i^^'N-CHs
CH.,
Hydrocotamine.
Opianic acid when oxidised forms hemipinic acvl; and, when reduced,
meconine ; and may be represented as
OHO ^^
-COOH
- OPH °^ ^° ^^ tautomeric form as
:)CH3
Opianic Acid.
§367,368.] CODEINE. 317
Narcotine is a tertiary base and contains no carboxyl or aldehyde
group, so that its formula is probably
CH2
CH30'^>^N-CH,
CH
CH O
I
-CO
I
OCH,
Narcotine,
§ 367. Effects. — Narcotine in itself has toxic action only in rather
large doses ; from 1 to 2 grms. have been given to man, and slight
hypnotic effects have followed. It is poisonous in very large doses;
an ordinary-sized cat is killed by 3 grms. The symptoms are mainly
convulsions.
§ 368. Codeine (Codomethylene), Ci7Hi70CHg(OH)NO + H20, is the
monomethyl ester of morphine ; it is an alkaloid contained in opium
in small quantity only. Mulder, indeed, quotes -66 to '77 per cent, as
present in Smyrna opium, but Merck and Schindler give '25 per cent.
Schindler found in Constantinople, '5 per cent. ; and Merck, in Bengal,
•5 per cent. also.
Codeine crystallises out of dry ether in small, colourless, anhydrous
crystals ; but crystallised slowly from an aqueous solution, the crystals
are either in well-defined octahedra, or in prisms, containing one atom of
water, and melting in boiling water to an oily fluid. The anhydrous
crystals have a melting-point of 155*, and solidify again on cooling. Its
watery solution is alkaline to litmus-paper.
It requires 80 parts of cold, 1 7 of boiling water, 76 of carbon tetra-
chloride, 10 parts of benzole, and 7 parts of amyl alcohol respectively,
for solution. Alcohol, benzene, ether, carbon disulphide, and chloi-oform
freely dissolve it, but in petroleum ether it is almost insoluble. Further,
it is also soluble in aqueous ammonia and in dilute acids, but insoluble
in excess of caustic potash or soda, and may thus be thrown out of an
aqueous solution. A solution of codeine turns the plane of polarisation
to the left, [a]r= 118-2\
Concentrated sulphuric acid dissolves codeine without colour, but after
eight days the solution becomes blue ; this reaction is quicker if the acid
contains a trace of nitric acid. If the sulphuric acid solution be warmed
to 150", and a drop of nitric acid be added after cooling, a blood-red
colour is produced. Frohde's reagent produces a dirty green colour,
31 8 POISONS: THEIR EFFECTS AND DETECTION. [§ 369.
soon becoming Prussian blue, and terminating after twenty-four hours
in a pale yellow.
Cyanogen gas, led into an alcoholic solution of codeine, gives first a
yellow and then a brown colour ; lastly, a crystalline precipitate falls.
On warming with a little sulphuric acid and ferric chloride, a blue colour
is produced. This blue colour is apparently common to all ethers of the
codeine class.
Of the group reagents, the following precipitate solutions of codeine :
— Mercuric potassium iodide, mercuric chloride, mercuric bromide, picric
acid, and tannin solutions. The following do not precipitate : — Mercuric
cyanide and potassium ferrocyanide solutions. Potassium dichromate
gives no immediate precipitate, but crystals form on long standing. It
does not give the reaction with iodic acid like morphine; it is dis-
tinguished from narceine by dropping a small particle of iodine into the
aqueous solution — the iodine particle does not become surrounded with
fine crystals.
§ 369. ElBfects. — The physiological action of codeine on animals has
been investigated by Claude Bernard, Magendie, Crum Brown and
Fraser, Falck, and a large number of others.* It has also been ad-
ministered to man, and has taken in some degree the place of morphine.
Claude Bernard showed that, when given to dogs in sufficient quantity
to produce sleep, the sleep was difibrent in some respects to that of
morphine sleep, especially in its after-effects. Thus, in his usual graphic
way, he describes the following experiment : — " Two young dogs, ac-
customed to play together, and both a little beyond the average size,
received in the cellular tissue of the axillae, by the aid of a subcutaneous
syringe, the one 5 centigrammes of morphine hydrochloride, the other
6 centigrammes of codeine hydrochloride. At the end of a quarter of
an hour both dogs showed signs of narcosis. They were placed on their
backs in the experimental trough, and slept tranquilly for three or four
hours. When the animals woke, they represented a striking contrast.
The morphine dog ran with a hyena-like gait {demarche hyenoid), the
eyes wild, recognising no one, not even his codeine comrade, who vainly
bit him playfully, and jumped sportively on his back. It was not until
the next day that the morphine dog regained his spirits and usual
humour. A couple of days after, the two dogs being in good health, I
repeated the same experiment, but in a reverse order — that is to say, I
gave the codeine to that which previously had the morphine, and vice
vend. Both dogs slept about as long as the first time ; but on waking
the attitudes were completely reversed, just as the administration of the
two substances had been. The dog which, two days before, after having
* Ami, Chein, Phys. [f*], xxvii. pp. 273-288; also, Joum. Chem. Soc., No.
ocxliv., 1888, p. 858.
§ 370.]
NARCEINE,
319
been codeini&ed, woke lively and gay, was now bewildered and half
panilyaed at th*j end of bis morphine sleep ; whilst the other w«a wide
awake /md in the beat apirits,"
Subsequent experimenters found what Bernard duey not mention —
vit,, that codeine produced epileptifarm couvidsions. Falek made some
very eareful ejtperimenta od pigeons, frogs, and rabbits. To all these
in high enough doae» it wa^ fat^iL Faluk puts the minimum lethal dose
for a rabbit at 51*2 mgrms, per kilo. Given to man, it produces a sleep
very tirailar to that described by Claude Bern an] — that la. a sleep which
k very natural, and doe^s not leave any after-effect. Therefore it ia
declared to he the beat alkaloid of a narcotic nature to give when
lengthened slumber ia desired, more espeeially since it does not con-
fiue the bowels, nor has it been found to produce auy eruption on the
skin. Before it has a full narcotic effect, vomiting has often been
excited, aiid in a few cases purging. The maximum dose for an adult
is about '1 grm^ {1'5 grain) ; three times this quantity, '3 gnus.
(4'5 grains), would probably produce unpleasant, if not dangerous,
symptoms^^
I 370. Narceine, C^jH^^^NOft+SH-jO.— Twi> of th© three aioleculeB tif water are
expelled nt 100° i the other moloculo rt^utrea a bight' r teniiwmtnie, Auliydraus
naroeinu b hygrutgcopic^ iind melts in a tube ai about 145" ; when exposed to air it
Qiiite^ with one molfruie of wat«i% and then melts at about 170*"*
The con^littition of iiaremnu, aocoiding to Freinid and Piaukforter,! mny h**
repicd^uted thus : —
CHaOa I
U
N(CH,)i
GOOH
-OCH3
OOH,
fi therefore contains Ihjtjo tnttlroxyl groups.
Nan&eiiic forms good ci^ftUls, tlio form being thit of long, four-aided rhomlnc
prisma or fine bushy imitud m^dliis.
NaroeLD0 hydj'Oi'ldoridt! cry stall bes with &|H^0 and with 311 ^0 ; thL» &iihydrQU»
Halt melts at l&uMe2^ The pktitioch bride is a deanito salt, tn.p. I&O^-IS!* ; it
decomposes at 195°-19*j''* Th« uitrite foniiB gixtd tiryatalSp which dwoitipoHe at fi7*.
* For furthi^r details as to the action of codeine, the roodor is r@ferred to L. 0,
Wiieir« monograph, Thm Cuddn (ISflS), wldcli contaijis rt'ferenee to the parlipr
liU*T»luie. S«t3 a^so HAiioyj The Old Vegekthie Nnutoiies^ Lpondi*n*
t M. Kffund and ti. B. Frunkforter, Aju^^tit, cdlxxvlt. pp, 20-58.
320 POISONS: THKIR EFFECTS AND DETECTION. [§371-
Narceine also forms crystalline salts with potassium and sodium ; these may be
obtained by heating he base at GC-TO" with a 33 per cent, of NaHO or
KHO.
The potassium compound melts at 90°, the sodium at 159"'-160^ The alkaloid is
regenerated when the alkali salts are treated with acids or with CO3. Crude narceine
may be purified by means of the sodium salt ; the latter is dissolved in alcohol and
precipitated with ether.
It is soluble in alcohol, but almost insoluble in alcohol and ether, or benzene and
ether, as well as in carbon tetrachloride ; it is slightly soluble in ether, carbon
disulphide, and chloroform. It has no reaction on moist litmus-paper.
Benzole and petroleum ether extract narceine neither from acid nor alkaline
solutions ; chloroform extracts narceine both from acid and from alkaline solutions,
the latter in small proi>ortion only. Narceine turns the plane of polarisation to the
left, a[r] — 66*7°. Narceine may be separated from narcotine by the addition of
ammonia to the acid aqueous solution ; narcotine is fully pixxiipitatcd by ammonia,
but narceine is left in solution.
In the subliming cell it melts at 134", but gives no crystalline sublimate. The
tube melting-point of the trihydrate is 170". The melted substance is at first colour-
less ; but on raising the temperature, the usual transitions of colour through different
shades of brown to black are observed. If melted, and kept a few degrees above its
melting-point, and then cooled slowly, the residue is straw-coloured, divided into
lobes, most of which contain feathery crystals.
At high temperatures narceine develops a herring-like odour ; the residue
becomes darkish blue with iron chloride. Concentrated nitric acid dissolves it with
a yellow colour ; on heating, red vapours are produced ; the fluid contains crystals of
oxalic acid, and develops with potash a volatile base. Concentrated sulphuric acid
colours pure narceine brown ; but if impure, a blood-red or blue colour may be pro-
duced. It does not reduce iron salts.
Frohde*s reagent colours it first brown-green, then red, passing into blue.
Narceine forms precipitates with bichromate of potash, chloride of gold, bichloride of
platinum, and several other reagents. The one formed by the addition of potassio
zinc iodide is in hair-like crystals, which after twenty-four hours become blue.
Weak iodine solution colours narceine crystals a black-blue ; they dissolve in
water at 100" without colour, but on cooling again separate with a violet or blue
colour. If on a saturated solution of narceine a particle of iodine is strewn, fine
needle-like grey crystals form around the iodine. A drop of **Nessler" solution,
added to solid narceine, at once strikes a brown colour ; on dilating the drop with a
little water, beautiful little bundles of crystals appear. — FlUcki/j/er.
The following group reagents precipitate narceine :— picric acid, tannin solution,
and potassium dichromate on long standing. The following give no pi-ecipitate : —
mercuric cyanide, mercuric potass, iodide, mercuric chloride, mercuric bromide, and
potass, ferrocyanide solutions.
§371. Effects.— The physiological action of narceine has been variously inter-
preted by different observers. Claude Bernard* thought it the most somniferous
of the opium alkaloids. He said that ''the narceine sleep was characterised
by a profound calm and absence of the excitability of morphine, the animals
narcotised by narceine on awaking returning to their natural state without
enfeeblement of the hind limbs or other sequelse." It has been amply confinned
that narceine (lossesses sonmiferous properties, but certainly not to the extent that
Bernard's observations led physiologists to expect In large doses there is some
irritation of the stomach and intestines, and vomiting occui-s, and even diarrhoea ;
moderate doses induce constipation. The maximum medicinal dose may be put
Campt, Rend., lix. p. 406, 1864,
§ 3;2. 373']
PAPAVEHINE,
321
iit '14 grm. (or 2 '20 gmii]8)| and a jtrobably dangerouR dose would be tliree tmie«
I 372. Papaverine (Cj^H^NO^) orystalUsea from alcohol in white needlBs or sculea.
It [lo^se^oK sc-4irce]y any alkaline reaction, but iU mlt^ have an aoid reactiot) ; it Iias
bnt little effect on a ray of polari^ light. It i£ almost insoluble in water ; it is
easily solubla in aofltonej amyl aloobol^ alcohol, and chloroform^ One part uf the
alkaloid is (iiMfAYed in M'& of hcnstene, in 7§ parta of am^l alcohol ^ and in 4dO purtii
of carbon tetrachloride. Petroleum ether diaaolTes it by the aid of iieat, but the
alkaloid separate in erystala on cooling. Chloroform extracts it t'rom either acid or
alkaline solutionfl, PapaTerine gives no cryiatalliiie aublimate. The nieltijig-point
of pure samjjles in a tube m lil", witb scarcely any colour ; it solidifies again to
crystals on eooling ; m the subliming cell it melte at 130'', an J decoii]|K)sea about
149*; the va]^kfjun{ are alkaline ; the residue ia ainorpbousj light brown j and is not
characteristic. Omeenttated aul}>huric acid colours it a deep violet-blue, and
dis£3olvett it to a violet^ slowly fading. This milution, l>y i>ermaiiganate of iHitasb, b
fii'st grfleij and then gt^y. Somo samplea of ofinimertial pajiaverine consist of
4f' [wi|iaverine, which dissolves in concentrated Hi,80j to a colourless Jiolutton.t FrtJhde's
reagent givtis a biiantiful viokt colouri which becomeji blue^ and vanishes after
twenty-four hoiui!. Diluted solutions of aalta of pa[)averine ure not precipitated by
phospho -molybdic acid. It ia preqipitated by ammonia, by the catistic and carbouatwl
alkalies, by i^ota^io'cadinic icHlide^ iodine in hydriodio acid, aud by Alkaloidal
reagentii gen erally-^ save by the iuipfjrtant exception mentioned above, A sulutfon
in amyl alcobel is also precipitated by^ bromine ; the precipitate is crystalline. Aji
alci>bo!ic solution of platinie chloride also seijarates [Miijaverine platin chloride in
ctystak. An alcfjhoUe solution of iixtine, added b) an alcoholic solution of jiapa-
veriuflj sejiarates in a little time crystals of tbe com position CaoILiNO^Ij. From the
mother-li^piort by concentration, can be obtained needlca of another i^Ddine combina-
tion, C^^H^jNOJj; the latter heated above 100' parts with free iodine. These com-
j>oupd^^ vdth iodine are deeompoeod by anirnonia and potash, papaverttio iieparatiiig«
The decumjioeitioti may l>e watched under the niierosco|je. Nitric acid precipitates
from a elation of the Bulpliate a white uttrat« soluble in excess ; the pretipttate does
not apjiear at once, but forms in the coarse of an hour - it is at fitist amorjihous, but
subsequently crystalline; this, with tta physical proiiertica, is a great as^iiitance to
iilentilication, Paiiaveriue ie a derivative of iisoqiujioline ; it coutidus four metboxyl
gron^is, Goldscbmiedt ascribes to it the following formula : —
0H*0 /^'
CHjO I
n
N
' OCH.
oc:
§ 375. Effectfl.— Claude Bernanl ranked (Mijiavormewith theeonvulsanta ; probably
the {Mtpavorine be hiid was impure. In any ca^, saljsequf tit observations Imve shown
• See J, llauchardat, La mirciim, Th^^ae, Paris, 1865 ; Harley, Tha Old
VtijcMU NcHn4ks^ Loud. ; Clu Lxjk^, ^htdes fur ia NmeHn^ tU it&n Smphk
TAera}>£iiiiqui', Th^^, Paris, 1SQ& ; alsi», Husernann^A P/lanwenstoJf'e^ in which theea
and other researches are aummarisad.
t Oswald Uvme, J, pr. Chrm., 1&03 (ii,),
21
322
POISONS 1 THEIR EFFECTS AND DETECTION, [§ 374, 375.
that it is Ui be claaaed rather witli the hypnotic jirincijilcft of ft|iiinrn* LeideMorf *
ftdminiiiterod it to tb© iii&tinc^ and tiatiid Bluwnes^ of tlie pttls^^, imisoular weflkuRss,
and drowftiness to follow. The dm&s were givpn Bubcutaiieouflly ("42 grui, of the
hydrochlnridfl), Baxt^t exi>eiiiiieQting with the frog, found that a minigramme
(»iiBad deep aleep and jsl owing of the heart's iM^tioti. Tbia tintion on the heart is
witniiaed also on tho recfltitly-removed frog*» hearty Guint«a'|iigSj otid other small
Miiiiiiilw ijoisoucd by stryclmizit; or thobulne^ and tliou given jKipaventie, did not
ponm to be so soon affbcted witli tetjtnun as when im unch remedy was admioiBtered.
In Bradbnry'a ejcpenmenta (Cronnian Lectures, Lan^t, July 189^) |>ftpoTerine proved
ta he a jwwerful depreasanL In rain 0'3 grm. l»er kilo, pri:)duce<:l uiuttciilar wcMikiic?Rs,
slowing of the respiration and piilsej diatiuet nareosis, but no tetanusL 0 2 giTfi.
per kilo, kills gninea-piga by |Kivalysis of the reapiration in ten minutes. The fatal
doaa of papaverine ftir a man is unknown* Tlie Icaat quantity likely to cause
dangerous symptomfl would he 1 grm, (16 "4 grains),
§ S74. TTiebaitie, Ci7H|aKO{OGH3)!j. — Opium seldom coutams much more than 1
per cent, of tliis alkaloid. It usually fonim Jieedles or short cryatalB- It la alkaline,
and by rubbing becomes negatively electric. It is almost inaoluhle in water, oqueotjs
ammonia, and aolutions of the alkalte». It reqnirea IQ parts of cold alcohol for
solution f and disaolvfss readily in hot^ Ether, hot or cold^ is also a gof>d s^ilvent,
100 parta of benzene are reiquired for 5'27 jiarfca of thobaine, and 100 of amyl akohol
for 1 "67 jiarfcs. Cblorofoi'm dissolves thebaine with difficulty out of both acid and
alkaline solutions ; {>etTo1eum ether eictracta it from neither. Thchaine melts in a
tube at IfiS", suhlfroea at ISS**. The aublimate h in nxinute ciystals, aimilar to
theinc; at higher temjieraturea (160° to 200") needles, cubes, and prisms are obtained.
The residue is fawn-coloured. Frobda'a reagent (as woU as concentrated sulphuric
acid) dia&olves jt^ with the production of a blood-red eolour^ pacing gradually into
yellow. The procipitat^ with picric acid is yellow and amorj)hou5i; with tannic
acid J yellow ; with gold chloride, red -yellow ; and with plat in ic chloride, citi-on-
y el low, gradually beeoming cry Rtal line. A concentrated alcoholic solution of
thebaine, just neutralised with HCl, deposits well-fonned rhombic crystals of the
com|>osition CioHaiNO^IICl + H^jO. Thebaine is hrvorotatory. It is a tertiary base
containing no hydroxyl groups. It contAins two methoryl grou|tt, and is nearly
related to mor|ihine and codeine.
If 200 mgrms. of thehaine aa* heate<i U^ btiiUng with IM c.c. of HCl and 2"8 o,c. of
water, and the solution diluted, after boiling, with 4 c.c, <if water, crystals of thebaine
hydroehloride foi-m in thf yellow fluid in the euurso of a few btmi-s. — Fiiit^iger.
I 376. Effe<!t*.— "There is no disagree raent of opiniflu as tti the action of thebaine.
By the unitefJ testimony of all who have ejtiKrrimented with it, the alkaloid belongs
to those jMJisous whieh produce tetanus^ uud the symptoms can scarcely he differ-
entiated fr^^'Ui strychnine. In Baxt'a exjjbrimont-a on frogs he showed that there was
some conaidemble difference? in details in the general course of the symptoms, acoord-
ing to the dose of the piisi^n. A small df>so (such, for example, as 75 mgn"0
injected into a frog sul^cntaneonfily piriduces ininiwliiitc excitement, the anmial
jnniping about, and this atage htatitig for alKjut a ininnte ; it then liecomea cpiieter,
and haw from three to six minuk^* ale«i> ] in a litth^ tiute this comatcjs*^ stiitt* in
followwj by reflex tetanic 8i)asm8 and then siHiutane^Jua tetanio K[«isnis, With tlvi^e
tim^ the dose, the tetanic convukions commence early^ and dejith takes place in
fitmi two to sii houw. Bait X found 6 to 7 nigrms. kill rabbits with tetanic convul-
• Ztschr. d, Wien. Aentr, pp. 48, 116, 1888,
t Arth. A^*tii, PhiiK, p. 70, 1839.
t Sil^uttg$lkr, fh IVitn, Aimtejn.f Ivi. Jip.
ph^moL, Bit h V* 112, iSaS,
2, 89, 1867 : ArcfK /. AmrL 1*.
§ 37&-378.]
APOMOBPHINE.
323
ftifjiifi in from lifteeii to twenty-fivo nvinutea. Cnmi Brown und FrrLsser him round
tliat VI mgrras. injected into viibbitii weit) fatal ; it itmy then l>e preaujuttl tliat thtj
letlml dr>Ae for a rabbit iKiibunt b mgrius. {mr kUo, A frog*B ha&tt under the action i>f
Ihebaiiiu, mid rt^nioved from tin? body, Iw^ts tji ticker oiud ccase^j earlier ihiiu one in
distilled wat^r* Ti>c)iaiiitj bas \mvti admluiateixMj L^^ tlio insane subcuUiiiCMjualy in
dosefl of from 12 to 40 mgin^fi., when a tUi'i of t<unj>emturQ irnd an luei'Otuu? in the
reapimtiiry movement* i\nd In the eirculation W(»ro noticed. •
Thf! f4t»l dose for d nmu itt not known j '5 gmi,, or iiboutS grautsi, would jiitib-
ably lie ft poisonaua i|nanlity*
§ 371 Oryptoplne (Qj,H^NOb) was* discovei^ by T. ft H, Smith ii» 1867,t It
b coil tain ed in very nijiiuto tnuse^i only in opium— something like *003 jjorcent. It
h ft crysUUiii*? HubiiUnoe, the crysttala lx"ing colon rU'AB, six-tfidt'd (irisniSi without
oiirHiri but with a bittJ^r tast«j oaiu^in^ an after* &ansatif>ri like jJepjiemiiLt. The ciyMtala
meltatiilB^, and cougml in a cjyat(*Utue form ikgain at 171'^ ; at high t4<m{ieruttireH
they are decimijuitiefl with evolution of luniuoniacttl vapour* Cryptopinu ia ijisolnblc,
or &liiicat so, in ether, water, aud oil i>f tnrftentiue ; it iii i^olablo in iicetoue, ]^ii^nc^
And ohlorofomi ; the latter is the lM?st solvent, or hot alcohol ; it i» insoluble in
iMtUoDua annnouia and in iuilutiouH of the eau.stic alkaloidn. Ct^'ptopine U E^trongly
buaie, neutralising fully xuineml acida* It is optically inactive and contains two
ntiethoxyl grouiis. Coneentrat^l sulphuric acid coIc»unt eryptopine puix^ blue^ the tijjt
gradually fading from absorption of water from the atuiisspbert?. On a crystal of
potasme nitrate Inking added, the colour change.^ int^^ a f^ieimaueut grerm. With
ferric chloride ciyptopine gives uo colour— thus distiugnishtng it from niorfdjine.
The phyaiological proji^rtiea of cryptopine have been invt-Htlgated by t>r. Harley ; J
it lias a narcotio aotion, ab^mt double as atrong aa uaraeitiu, and four timeij weaker
than morpliiue. Muuk and Sippll § found that it gave rise in anbnak to jviratynia
of the linibsj and oecasioually a^^phyxic cotivtilsions hefoj-e death.
% 377. Pfteudomorpbine (Cj-^Hi^NO-i).^— Pat'udomor|shine wos diseovored by
Pelletier and Thilxiuuiery iu 1835. It is non-jxiisououtv, and may bo hutnod by the
coudonsatioti of two moleoultJS of morpluue and the loi*a of two aiotn^ of hydrogen.
Ab precipitat4.'d hj ammonia out of the hot flolutiou^ |ttii:>udomori>biue falls a.H a white
crystalline precipitate ; but if the solution h cold, the precipitate h gelatinous* It
puaaeaaes uo tasti*^ and haa no action on vegetable colours. Ou heating, it decom*
poiea And then uielts. It dbaolves easily iu caustic alkaHe;} and in milk of limf\ but
^ insoluble in all the ordinary aleoliolic and ethereal solvents^ an well asi in diltitt^
auliihuric acid. The most soluble salt is the hydi^ochlomt^, and that rei|uiiea 70
parta of water at 20^ for aolutiou. Various salts, such as the sulphate, ofXalftU^ etet|
may be j>repared from the hydix>chl orate by double decomiKtsition, OoncQ&lritied
sulphuric acid dis^lvcs jjseudouiorijhlne gradnally, with the production of au olivo-
green colour,
I 378» Apomorphine (CiJlj-KOg). — Aj^^morphiue ia a derivative of morphine,
and is readily prpi»ared by Ritpoaifying morphine by heating it with dilute hydro-
chloric acid in su^aled tul>e^. The itmilt is ajHjnmrphine hydrochloride^ th^ morphine
losing one molecule of water^ according to the eipiatioj) C|5H,^O^T = Cj7Ui7NOa + HsO,
To ex tract ajKimorphine, the liaties am ]»reoipitate«l by »(^)dic biearlwnalCf and the
precipitate ejtractwl by *^ther or ehlorofonUj tutber of which solvent» leavea morphine
ttndhiaol VikI The afiomorphiuc is again converted into liydrocbloridej and unoe
• F, W, MHllor, Das TMmin^ tinr Mtrm^mphis, Disa., Marbuj^, 1808.
t Phtinii, Jmtm. Tram. [2], viii* pp. 4Sfi and 716.
X The Ohi l^CijtUdtlt Neundics,
§ Mnnk, Fftsiuh^ iiher dU IViricung iUs Crypiopim^ Berlin, 1873. Sippell,
M^Mi§0 wr KmtniJBt (Us Oryptaimik^ Marhui^, 1B74.
324 POISONS : TTTEIR KFFECTS AND DrTECTIOX f§ 379-382.
more precipitsted by sodk bicarbonate, and is lastly obtained as a snow-white sab-
iitance, rapidly becoming green on exposure to the air. The mass dissolres with a
beantifal green colour in water, and also in alcohol, whilst it colours ether porple-'
red, and chloroform riolet.
A test for apomorphine is the following : — The chloride is dissolved in a little
acetic acid and shaken with a crystal of potasdc iodate (KIO3) '* ^^ inmiediately
tarns red from liberated iodine on shaking it np with a little chloroform ; on stand-
ing, the chloroform sinks to the bottom, and is coloured by the alkaloid a beantifal
bine colour ; on now carefully pouring a little CS, on the surface of the liquid at the
point of junction it is coloured amethyst owing to dissolved iodine, and apocodeine
giyes a similar reaction.
Apomorphine is the purest and most active emetic known: whether injected
beneath the skin or taken by the mouth, the effect is the same — there is considerable
depression, faintness, and then vomiting. The dose for an adult is about 6 mgrms.
( '092 grain) subcutaneously administered.
§ 879. Laodanine, CjvH^NCOHXOCH,)^ crystallises from alcohol or chloroform
in colourless prisms soluble in benzol, chloroform, and alkalies, not very soluble in
alcohol and ether. Melts at 106". It is a strong tetanic poison. Laiidanidine is
probably the laevo modification of laudanine; it melts at 177"*. Laudaiumne^
Ci7Hi5N(0Cfl,)4, another tetanic poison, has been shown to be dextro-n-methyl-
tetrahydropapaverine ; its inactive form, which may be separated into active laevo-
and dextro-forms, appears to be the monomethyl ester of laudanine. It crystallises in
needles, melting at 89**, and is soluble in alcohol, ether, and chloroform, but not in
water or alkali
§ 380. Tritopine (021^^03)8'— '^'^ ^ & ^^ alkaloid that haslbeen found in
small quantities in opium. It is crystalline, separating in transparent prisms.
Melting-point 182". It is soluble in alcohol and chloroform, and slightly soluble in
ether.*
§ 881. Meconine (Opianyl) (C]oHio04) is in the form of white glittering needles,
which melt at 102*5". It may be sublimed in beautiful crystals. It is soluble in
22 parts of boiling, and 700 of cold water ; dissolves easily in alcohol, ether, acetic
acid, and ethereal oil, and is not precipitated by acetate of lead. It is optically
inactive. Meconine is the reduction product of opianic acid, and may be formed by
treating narcotine with zinc dust and hydrochloric acid. Its solution in concentrated
sulphuric acid becomes, on warming, purple, and gives, on the addition of water, a
brown precipitate. Meconine, in large doses, is a feeble narcotic ; 1 *25 grm. (20
grains) has been given to man without result.
§ 382. Meconio acid (CVH4O7), or
CO
HCil^OH
HOOC-c![ jc-COOH
crystallises in white shining scales or small rhombic prisms, with three molecules of
water (C7H4O7 + SHgO), but at 100" this is lost, and it becomes an o^iaqne white mass.
It reddens litmus, and has a sourish taste. It is soluble in 115 parts of cold, but
dissolves in 4 \y&v\» of boiling water ; it dissolves easily in alcohol, less so in ether.
It forms well-marked salts ; the barium and calcium salts crystallise with one molecule
of water, the former having the composition BaH4(C7H07)2 ; the latter, if ammonium
meconate is precipitated by calcium chloride, CaH4(C7H07)2 ; but if calcium chloride
is added to the acid itself, the salt has the composition C7H20a07 + H2O. If meconic
* £. Kander, Arch, Pharm., ccxxviii., pp. 419-431.
§ 382.]
MECCfflIC ACII>.
325
ai;id \& gi^ntly EjeattMi, It d»oompo«»OH iiilo carbon diuxiJu uiid comcinic acid {O^H fi^).
If thfi l»edt is sitionger, pyromflconic ncid (( *^H|0;i— mrUnti tliotide, water, mcath aoid.
jiud benzol 0 eir« formed. Pyromeconic liciri i» readily Bublimed in large transparent
Ub](?H. Chloridi? of Hx)tj, and soluble iron ailta ganemlly, give mtb mficoaic acid
(ovijQ m gr«5ftt dilution) a lively ltd oolour, which is not altorod by heat, uor by the
addition of HCl, nor by that of gold chloride* Sugar of lead and nitrate of s^ilver oAch
give a TSfhitt^ ureciiiitotD ; and Eoercurous and mofcqric nitrates white and ycsllow
precipitates. In any caac where tho analyst has found only meconic acid, the
question may be raised tn court as to wh*?tber it is a paiaon or not. The early
cxperimeut^ of Serturner,* Lauger, Vogelp Siininieriug^ andOra[>ot e^howod that^ in
comparatiyely speaking large dose^^ it had hut little^ if any, action on dogs or men.
Albers t haa, however^ experimented on fro^Hi| mid found that in dosi^ of '1 tu *2 grm.
there la, first, a narcotic action, and later, convulsions and deatlL According to
Selirofir,§ there is & slight narcotic action on man^
Ttie most generally ^uepted view ut the present time 19 that tha
phy Biological action of meconic acid Is simikr to tbat of lactic acid —
vi^., large dofies cause some deprcssiou and feoble mircosis*
In a special research amongst organiu fiuids for nieoouiG acid, the
subatauceH are extracted by alcohol feddy aciditlatcd with nitric acid ; ou
filtration the alcohol, after the addition of a little water, is dietillcd olf,
and to the remaining tlnid a aolutiou of acotate of lead is added, and the
whole filtered. The tiltrate will contain any alkaloids^ whilst meconic
acid, if present, ia bound up with the lead on the filter* The mectniatc
of lead may be either washed or digested hi ^strong acetic acid to purify
it, susptinded in water, and freed from lead by 8H,, ; the filtrate from
the lead sulphide may be tested by ferric chhiride, or preferably, at ouce
evaporated to drynesis, and weighed. After this operation it is identitied.
If the quantity isao small that it cannot he oouveuiently weighed, it may
be estimated colon metrically, by having a standard solution of meconic
acid, containing 1 mgrm* in every c.e. A few drops of neutral ferric
chloride are added in a Neasler cylinder to the liipiid under examination ;
and the tint thus obtained is imitated in the usual way, in another
cylinder, by means of ferric clilorido, the standurd solntioD| and water.
It is also obvious that the weight of the meconic aeid may he incrciused
by converting it into the burium i^lt — lOO parts of anhydrous baric
meconate, (BajC^R^O;), being tH|uivalent to 42 "3 of meconic acid
(C,HA)-
18ft9,
326 POISONS: THEIR EFFECTS AND DETECTION. [§ 384, 385.
IV.— The Stpychnine op Tetanus-Producing"* Group of
Alkaloids.
1. NUX VOMICA GROUP— STRYCHNINE— BRUCINE-IGASURINE.
§ 383. Nux vomica is found in commerce both in the entire state and
as a powder. It is the seed of the Strycfinos nux vomica, or Koochla
tree. The seed is about the size of a shilling, round, flattened, concavo-
convex, of a yellowish-grey or light brown colour, covered with a velvety
down of fine, radiating, silky hairs, which are coloured by a solution of
iodine beautiful gold-yellow; the texture is tough, leathery, and not
easily pulverised ; the taste is intensely bitter. The powder is not
unlike that of liquorice, and, if met with in the pure state, gives a dark
orange-red colour with nitric acid, which is destroyed by chloride of tin ;
the aqueous infusion gives a precipitate with tincture of galls, is
reddened by nitric acid, and gives an olive-green tint with persulphate
of iron. The best method, however, of recognising quickly and with
certainty that the substance under examination is nux vomica powder,
is to extract strychnine from it by the following simple process : — The
powder is completely exhausted by boiling alcohol (90 per cent.), the
alcoholic extract evaporated to dryness, and then treated with water ;
the aqueous solution is passed through a wet filter, and concentrated by
evaporation to a small bulk. To this liquid a drop or so of a concen-
trated solution of picric acid is added, and the yellow precipitate
of picrates thus obtained is separated, treated with nitric acid, the
picric acid removed by ether, and the pure alkaloid precipitated by
soda, and shaken out by chloroform.
§ 384. Chemical Composition. — Nux vomica contains two important
alkaloids : —
(1) Strychnine.
(2) Bruciue.
§ 385. Strychnine (CjjHjjgNgOg) is contained in the bean of S,
Ignatius, in the bark (false amjustura bark) and seeds of the StrycJinos
nux wmica, in the StryrJinos colubiina, L., in the Sirychnos tieute, Lesch,
and probably in various other plants of the same genus.
Commercial strychnine is met with either in colourless crystals
or as a white powder, the most usual form being that of the alkaloid
itself; but the nitrate, sulphate, and acetate are also sold to a
small extent.
The microscapical appearance of strychnine, as thrown down by the
solution of vapour of ammonia, may be referred to three leading forms —
* To this group also belong sorae of the opium alkaloids. See " Thebaine "
" Laudanine," ** Codeine," **Hydrocotamiuc."
§ 385^]
STRYCHNINE.
327
the long rectau«^iiliir priHm, the short liexngonal pri&iu, or the regular
o€tahedrou. If obtained from tlie alow evaporatiou of an alcoholic
solution^ it la usually in the form of four-sided pyramids or long pristiiB ;
but if obtained by speedy evaporation or rapid cooling, it appears as a
white granular powder If obtained from a benssenc eolation, the
deposit is usually crystalline, bnt without a constant fomi^ though at
times the crystals are extremely distinct, the short six-aided prism
prevailing ; but triangular plates^ dodeeahedral, rhombotdal, and penta-
gonal, may also be met with, Ati ethereal solution on evaporation
assumes dendritic forms, but may contain octabcdra and fonr-eided
prisms. A chloroform solution deposits rosettes, veitied leaves, stellate
dotted needles, circles with broken radii, and branched and reticulated
Forms of great delieacy and beauty. — Gut/,
Strychnine is very insoluble in water, although readily dissolved by
acidulated water. Accoi^ing to Wormley's repeated experiments, one
part of strychnine dissolves hi 8333 piirts of cold water j and, according
to Pelletier and Cahours, it dissolves in 6667 parts of cold and !35O0
parts of boiling water. It may be convenient, then, to remember that
a gallon of cold water would hardly dissolve more than 10 grains (*142
grm* per litre) ; the same amount, if boiling, about 30 grnins ('426 grm«
per litre) of istrycJuune. The solubility of one part of strychnine in
other menstrua is as follows : — Cold alcohol, 0*833 specific gravity, 120j
boiling, 10 parts (WitfBiein); cold alcohol, 0'936 speeifio gravity, 240
^vrtti (Merck) ; cold alcohol, 0 '8 15 specific gravity, 107 parts {Dragtn-
dt/rff)- ainyl alcohol, 181 parts; benzene, 164; chloroform, 6^9
{Schiimpert}^ 5 {Feittfikojer) i ether, 1250 parts; carbon disulphide,
4S5 parts; glycerin, 300 parts. Creosote and essential and fixed oils
also dissolve strychnine.
Of all the above solvents, it is evident that chloroform is the best for
purposes of separationi and next to chloroform, benzene*
If a speck of strychnine be placed in the aubliniing cell, it will be
found to sublime usually in a crystalline form at 16Q^ A common
form at this tempcmture, according t-o the writers' own observations,
is minute needles, dis^^oeed in hues ; but, as Dr. Ouy has remarked, the
Hnblimate may consist of drops, of waving patternH, and various other
forms; and, further, while the eublimates of morphia are made np of
curved lines, those of strychnine consist of lines either straight or
slightly curved, ^^ith |Mm1lel feathery hncs at right angles. On
continuing the heat, strychnine melts at about 22V , and the lower disc,
if removed and examined, is found to have a resinous residue ; hut it
still continues to yield subbmates until reduced to a spot of carbon*
The melting point taken in a tube is 268"*.
Stryuhnine is so jjowerfully bitter, that one part dissolved in 70,000
328 POISONS : THEIR EFFECTS AND DETECTION. [§ 386.
of water is distinctly perceptible ; it is a strong base, with a marked
alkaline reaction, neutralising the strongest acids fully, and precipitat-
ing many metallic oxides from their combinations, often with the
formation of double salts. Most of the salts of strychnine are crystal-
line, and all extremely bitter. Strychnine, in the presence of oxygen,
combines with SHg to form a beautiful crystalline compound : —
2G,^H^Sfi, + 6H2S + 03 = 2C,iH^N A3H,8, + 3H,0.
Ou treatment with an acid this compound yields HgSg. — Schmidt, Ber
deutsch. chem, Ges,^ viii. 1267.
In solution in alcohol of density of 0*8543 strychnine polarises light
to the left at 20* [0]^= - 11 4*7** in a concentration of 0'25 per cent. ;
when in a concentration of 0*1 per cent, the specific rotation is- 1 19*3**
[Tykociner, Rec. Trav. Chim,, i. 148]. Oudemans (Liebig's A7incU€n der
Chemie, clxvi. 76) gives for a solution in alcohol of density 0*865, and a
concentration of 0'91 per cent., a rotation of - 128*. The same author
gives the following : — 4 per cent, solution in chloroform, - 130* ; 2*25 per
cent., - 137*7* ; 1*5 per cent., - 140*7* ; and in 0*53 per cent., - 235*.
§ 386. Strychnine Salts. — The salts used in medicine are — the
mlphatey officinal only in the French pharmacopooia; the wiYra/e, officinal
in the German, Austrian, Swiss, Norse, and Dutch pharmacopoeias ; and
the (xcetate, well known in commerce, but not officinal.
The commercial Sulphate (CgiHgjNgOgjHgSO^ + 2H2O) is an acid salt
crystallising in needles which lose water at 150*, the neutral sulphate
(2C2iH22N202,H2S04 + 7H2O) crystallises in four-sided, orthorhombic
prisms, and is soluble in about 50 parts of cold water.
The Nitrate (C2iIl22N202,HN03) crystallises on evaporation from a
warm solution of the alkaloid in dilute nitric acid, in silky needles,
mostly collected in groups. The solubility of this salt is considerable,
one part dissolving in 50 of cold, in 2 of boiling water ; its solubility in
boiling and cold alcohol is almost the same, taking 60 of the former and
2 of the latter.
The Acetate crystallises in tufts of needles; as stated, it is not
officinal in any of the European pharmacopoeias.
The chief precipitates or sparingly soluble crystalline compounds of
strychnine are —
(1) The Chromate of Strychnine (C2xH22N202,CrH02), formed by
adding a neutral solution of chromate of potash to a solution of a strych-
nine salt, crystallises out of hot water in beautiful, very slightly soluble,
orange-yellow needles, mixed with plates of various size and thickness.
The salt is of great practical use to the analyst ; for by its aid strychnine
may be separated from a variety of substances, and in part from brucine
— the colour tests being either applied direct to the strychnine chromate,
S 38/" ]
STRYCHNINE.
329
or the chromate dec!om|joscd hy uuuuoiiia, and the Btrjclmiue reL*ovtjred
from the nlkaline liquid by chloroform.
(3) Sulphocyanide of Strychnine (aiH^aN^O^^CNHS) is a thick,
white precipitati% produced by the addition of a Esoliitiou of potasaic
sulphocyanide to that of a strychuiue salt ; ou warming it dissolves, but
on cooling reappears in tbo form of long sitky needles.
(3) Double Salts. — The platinum compound obtained by adding a
solution of platitiic chloride to one of strychnine chloride has the com-
position C^|H2,,N.-;O^HClPtCl2, and crystallises out of weak tjoiHng alcohol
(in which it it somewhat soluble) in gokl-Hke scales. The similar
palladium compound (C.,|HoL,Ng0.j|HClPdCl} is in dark brown needles, and
the gold compound (C^.iH,,.jN202,HClAuClg) in omn^;e-coloured neodles,
(4) Strychnine Trichloride, — Tho action of chlorine on strychnine—
by which chlorine in substituted for a portion of the hydrogen — has been
proposed as a test The alkaloid is dissolved in very dilute HCh so as
to 1)0 only just acid ; on now passing through chlorine gas, a white
precipitate is formed, which may be recrystitUised from ether; it has
probubly the composition CyiHigClgN^O^, and is extremely insoluble in
water,
(5) The Iodide of Strychnnie (C2|Hjg,N,jO^HIg) is obtained by the
action of iodhie solution on strychnine sulphate ; on solution of the
precipitate in alcohol^ and evaporation, it forms violet-coloured crystals,
very similar to those of potassic peramnganate.
J; 387, Pharmaceutical and other Preparations of Hux Vomica and
Strychjiine, with Suggestions for their Valuation.
An aqueous extract of nux vomica, officinal in the German phar-
niacoixria, appears to contain prineipajly brucine, with a small pei'centage
of strychnine ] the proportion of bi^ucinc to strychnine being about four-
fifths to one-fifth, Blossfleld found in a sample 4 '3 [yer cent, of toUil
alkaloid, and two samples examined by Grundmann consisted (No, 1) of
strychnine^ 0*6 |X^r cent. ; hruciue, *2*5S per cent,— total, 3"18 per cent. ;
(No, 2) strychnine, 0'68 per cent* j brucine^ 2*62 per cent — total, 3'3
per cent. A sample examined by Dragcndorff yielded — strychnine, OS
per cent ; brucine, 3*2 per cent, — total, 4 per cent The maximum
medicinal dose is pot at 'C grm. (9^^ grains) ♦
The spirituous extract of nui vomica, ofhcimd in the British and
all the Continental [iharmacopo^ias, diffoi's from the aiiueous in containijig
a nnich larger proportion of alkaloid^*, viz., about 15 per cent., and about
hair the total quantity being strychnine. The medicinal dose is 21 '0-
64*8 ragrms, {| grain to a grain).
Thero is also an extract of St. Ignatius bean which is used in the
United States; nearly the wliole of its alkjiloid may be referred to
strychnine.
330 POISONS : THEIR EFFECTS AND DETECTION. [§ 387.
The tincture of nux vomica, made according to the British Pharma-
copoeia, contains in 1 11. oz. 1 grain of alkaloids, or 0*21 part by weight
in 100 by volume, but the strength of commercial samples often varies.
Lieth found in one sample 01 22 per cent, of strychnine and 009 per
cent, brucine ; and two samples examined by Wissel consisted respectively
of 0*353 per cent, and 0*346 per cent, of total alkaloids. Dragendorff
found in two samples '2624 per cent, and *244 per cent, of total
alkaloids, about half of which was strychnine.
Analysis. — Either of the extracts may be treated for a few hours on
the water-bath, with water acidulated by sulphuric acid, filtered, the
residue well washed, the acid liquid shaken up with benzene to separate
impurities, and, on removal of the benzene, alkalised with ammonia,
and shaken up two or three times with chloroform ; the chloroform is
then evaporated in a tared vessel, and the total alkaloids weighed.
The alkaloids can theu be either (a) treated with 11 per cent, of nitric
acid on the water-bath until all the brucine is destroyed, and then
(the liquid being neutralised) precipitated by potassic chromate ; or (b)
the alkaloids may be converted into picrates. Picrate of strychnine is
very slightly soluble in water, 1 part requiring no less than 10,000 of
water.* The tincture is analysed on precisely similar principles, the
spirit being got rid of by distillation, and the residue treated by acidified
water, etc.
The nux vomica powder itself may be valued as follows : — 15 to 20
grms., pulverised as finely as possible, are treated three times with 150
to 300 c.c. of water, acidified with sulphuric acid, well boiled, and, after
each boiling, filtered and thoroughly pressed. The last exhaustion
must be destitute of all bitter taste. The united filtrates are then
evaporated to the consistence of a thick syrup, which is treated with
sufficient burnt magnesia to neutralise the acid. The extract is now
thoroughly exhausted with boiling alcohol of 90 per cent. ; the alcoholic
extract, in its turn, is evaporated nearly to dryness, and treated with
acidulated water ; this acid solution is freed from impurities by shaking
up with benzene, and lastly alkalised with ammonia, and the alkaloids
extracted by shaking up with successive portions of chloroform.
The chloroformic extract equals the total alkaloids, which may be
separated in the usual way.
Keller f estimated the alkaloids in nux vomica as follows : — Place
12 grms. of the powder in a flask with 80 grms. of ether and 40 grms. of
chloroform. After half an hour add 10 c.c. of a 10 per cent, solution of
ammonia. Shake at intervals for half an hour, then add 15 to 22 c.c. of
water and again shake. Now pour off* 100 c.c. of the ether mixture into
* Dolzler, ArcJi, Pharm, [3], xxiv. 105-109.
t Cheni. CerUr., i. 228, 1896.
sm
STBYCHSIINE.
331
a separating funuel and fihuke with 50 c.c. of ft 0 '3 p^r cent. HCl solu-
tion, draw oli' the acifi, add 20 e.e. more acid, sbake^ and again draw off.
Add exoe^ of amtiiouia, and cil tract the alkaloids with ether and
chloroform ; evaporate. The extracted alkaloids represent the quantity
in 10 grms. of tbc original powder.
In four samples of nax vomica eitamiiiod by Dnigendorfl^ the total
ftlkaloida ranged from 2 '33 to 2 4 2 per cent. Grate fumid in two
iamples 2 "88 per cent, and 2^86 j>er cent ruspcctively ; while Karing
from one siimple separated only 1'65 per cent. The stryehnine and
briicine are in abont equal propoitiotis, Dragendortf* finding 1"87 per
cent, strychnine and 1*145 per eeut brueine^t
The fact that sodium carbonate precipitates, and aodium bicarbonate
does not precipitiite, strychnine, hrucine and veratrine may be utilised
ae an imperfect group reagent, imperfect because long contact with an
excess of biuarbonate solution precii^itates slowly the strychnine alka-
loids; and a few other alkaloids in dilute iso lotion behave somewhat
simUarly.
In poisoning by nux vonjica there will be the mixed alkaloids to deal
with, and the proces^^ HuggBsteil hitherto for their neat (pmntitative
separation do not lead to very good reDulUi. Bchrcus believes that the
mo^t certatu process of recognise ing strychnine niixetl with much bruein©
is to preci[iitatc witK platinum chloride in presence of free hydrochloric
acid* The brueine aud fitrychniue precipitates have different forma and
grouping.
The mixeil salts may be also turned into the nitrate, potasde nitrate
addi'd, and then tbc solution almost saturated with common salt ; under
these circuuisUnees, tables of brueine nitrate first appear, and later
needles and tufts of Btrycbnine nitrate.
Fractional precipitation with pktinum chloride may also bo tried in
dilute solutions ; with nuich brueine and very little strychnine the chloro-
platiuiite of brueine comes down lirst, and it is only in the la&t fraction
that strychnine comes down.
To recognise brueine even in tmces contaminated with strychnine,
on the other band, is much easier; the solution evaporated with nitric
acid shows an oran geared edge.
St. Peterslinrg, 1874.
f Thtm* tlcUib am v^ry noc^sany, us bc&riiig on the qiic^ttieti of the futut dose of
amx vomii^it which Tmylor teU» as {Mrd, Jurisprud.^ t 40 &) was of *jme iinpartaai^a
in Mi§^ V* ffVrni in which 47 gmiim were utternjited to be givun ta milk. Tins
fftttil dr^ti nf UUK vomica must be ruled by itM alkaloidul conteiit^ which tiiay be m
low as 1 per cent., »nd as high o^ tiearly 3 per ocDt, 30 grains have jiroved faUl
{ Ttiiflor) , if the [lowrh^r in this instance was of tht^ onlinory strengthp Ihe jrorauu
died from l^& limn a gruiu ( OiiiS gnu. ) uf the untUd alkaluidti.
332
POISONS: THEIR EFFECTS AND DETECTION.
[§ 388.
A striking and very sensitive test is also the double thiocyanate of
brucine and cobalt.
This is obtained by adding to a solution of the alkaloid a
little cobalt chloride solution, and then an excess of ammonium
sulpho-cyanide ; strychnine, veratridine, and the quinine alkaloids give
under these circumstances immediate amorphous blue precipitates,
but brucine crystallises after a minute or two in blue pyramids and
tufts; after a tinie colourless rods of strychnine thiocyanate make
their appearance.
The vermin-killers in use in this country are those of Miller, Battle
Butler, Clift, Craven, Floyd, Gibson, Hunter, Stenier, and Thurston.
Ten samples from these various makers examined by Mr. Allen (Pfuirm.
Journal, vol. xii., 1889), gave the following results : —
Name
or
Mark.
1
2
3
4
5
6
7
8
9
10
Weight of
Powder
IMce.
in Grains.
5-6
Sd.
11-8
3d.
131
3d.
110
3d.
13-1
3d.
21-5
6d.
49-2
3d.
30-6
3d.
16-6
3d.
10-0
3d.
strychnine.
Nature
of
Weight in
Per-
starch.
Grains.
centage.
Wheat
0-61
10-9
0-80
6-7
Wheat
1-12
8-7
Rice
1-28
11-1
Rice
1-70
13-0
Rice
2-42
11-2
Wheat
2-86
5-8
Wheat
3-46
11-3
Wheat
3-81
19-4
Rice
4 18
41-8
Rice
Colouring Matter.
If
Ultramarine.
Ultramarine.
Ultramarine.
Ultramarine.
Prussian blue.
Soot.
Prussian blue.
Carmine.
Ultramarine.
§ 388. Statistics.— In England, during the ten years 188rl-1903,
strychnine, nux vomica, and vermin-killer account for 308 deaths. Of
these, 64 were ascribed to " vermin-killer." " Vermin-killer " may be
presumed to include not only strychnine mixtures, but also phosphorus
and arsenic pastes and powders, so that there are no means of ascertain-
ing the number of strychnine cases comprised under this heading.
Taking the deaths actually registered as due to strychnine or nux
vomica, they are about 2*0 per cent, of the deaths from all sorts of
poison. Of these deaths 171 were suicidal, 6 were homicidal, and 67
were accidental.
Schauenstein has collected from literature 130 cases of poisoning by
strychnine, and most of these occurred comparatively speaking during
recent years; 62 of the 130, or about one half, were fatal, and 15 were
homicidal It has been stated that strychnine is so very unsuitable for
the purpose of criminal poisoning as to render it unlikely to be often
used. Facts, however, do not bear out this view; for, allowing its
§ 388.] STKTCHXDiK. m
intenaelj bitter taste, yet it must be remembered that bitter liquids,
such as bitter ale, are in daily use, and a person accustomed to drink
any liquid rapidly might readily imbibe sufficient of a toxic liquid to
produce death before he was warned by its bitterness. It is, indeed,
capable of demonstration, that taste is more vivid after a substance
has been taken than just in the act of swallowing, for the function
of taste is not a rapid process, and requires a very appreciable interval
of time.
The series of murders by Thomas Neill, or, more correctly, Thomas
Neill Cream, is an example of the use of strychnine for the purposes
of murder. Thomas Xeill Cream was convicted, October 21, 1892,
for the murder of Matilda Clover on October 20, 1891 ; there was
also good evidence that the same criminal had murdered Ellen
Dunworth, October 13, 1891; Alice Marsh, April 12, 1892; Emma
Shrivell, April 12, 1892, and had attempted the life of Louie
Harvey. The agent in all these cases was strychnine. There was
no evidence as to what form of the poison was administered in
the case of Clover, but Ellen Dunworth, who was found dying
in the streets at 7.45 p.m., and died less than two hours after-
wards, stated that a gentleman gave her '' two drops " of white stuff
to drink.
In the cases of Marsh and Shrivell, Neill Cream had tea with them
on the night of April 11, and gave them both ''three long pills*' ; half
an hour after Neill Cream left them they were found to be dying, and
died within six hours. From Marsh 7 grains, from Shrivell nearly 2
grains of strjchnine were separated ; the probability is that each pill
contained at least 3 grains of strychnine. The crimiiial met Louie
Harvey on the Embankment, and gave her ** some pills " to take ; slie
pretended to do so, but threw them away. Hence it seems probable that
Neill Cream took advantage of the weakness that a large numl)er of the
population have for taking pills, and mostly poisoned his victims in this
manner. Clover's case was not diagnosed during life, but strychnine was
found six or seven months after ])urial in the body. It may bo men-
tioned incidentally that the accused himself furnished the clue which
led to his arrest, by writing letters charging certain members of the
medical profession with poisoning those poor young prostitutes with
strychnine.
One of the most famous strychnine poisoning cases was that of
William Palmer. Baron Brampton, in his reminiscences, speaks of this
case as follows : — " William Palmer was a surgeon practising at Kugoley
in Staffordshire. He was a great racing man, and owned one or two
racers. A young gentleman of considerable fortune had taken to the
turf and owned horsea Palmer and he became intimate as companions
334 POISONS: THEIR EFFECTS AND DETECTION. [§ 389.
— in short, they were at Shrewsbury races, where Palmer lost and Cook
won. The latter had considerable sums of money to receive on bets,
and Palmer, desirous of getting hold of it, poisoned the poor man with
strychnine,* took possession of his betting-book and papers, received all
money due, and then had him hastily buried. Ultimately suspicion fell
on Palmer, he was tried for the murder and hanged. There was little
doubt he had murdered several others for the sake of the money for
which he had insured their lives, notably his wife and mother, whose
name he had forged to several bills. ... I may also add that at
that time there was no known test for the discovery of strychnine
in the body, and Palmer was convicted entirely upon the symptoms
preceding death, and especially the peculiar arching of the body
after."
§ 389. Fatal Dose. — In a research, which may, from its painstaking
accuracy, be called classical, F. A. Falck has thrown much light upon
the minimum lethal dose of strychnine for various animals. It would
seem that, in relation to its size, the frog is by no means so sensitive to
strychnine as was believed, and that animals such as cats and rabbits
. take a smaller dose in proportion to their body weight. The method
used by Falck was to inject subcutaneously a solution of known strength
of strychnine nitrate, and, beginning at first with a known lethal dose, a
second experiment was then made with a smaller dose, and if that
proved fatal, with a still smaller, and so on, until such a quantity was
arrived at, that the chances as determined by direct observation were
as great of recovery as of death. Operating in this way, and making
no less than 20 experiments on the rabbit, he found that the least fatal
dose for that animal was *6 mgrm. of strychnine nitrate per kilogramme.
Gats were a little less susceptible, taking '75 mgrm. Operating on
fowls, he found that strychnine taken into the crop in the usual way
was very uncertain ; 50 mgrms. per kilo, taken w^ith the food had no
effect, but results always followed if the poison was introduced into
the circulation by the subcutaneous needle — the lethal dose for fowls
being, under those circumstances, 1 to 2 mgrms. per kilo. He made
35 experiments on frogs, and found that to kill a frog by strychnine
nitrate, at least 2 mgrms. per kilo, must be injected. Mice take a
little more, from 2*3 to 2*4 mgrms. per kilo. In two experiments on
the ring adder, in one 62*5 mgrms. per kilo, of strychnine nitrate,
injected subcutaneously, caused death in seven hours; in the second,
23*1 mgrms. per kilo, caused death in five days; hence the last
quantity is probably about the least fatal dose for this particular
snake.
* Dr. Taylor analysed the stomach and other organs, — he found antimony, but
9t saccessfVil in tracing strychnine.
§ 389.]
STRYCHNINE.
335
These observations may be conveniently thrown into the following
table, placing the animals in order according to their relative
sensitiveness.*
TABLE SHOWING THE ACTION OF STRYCHNINE ON ANIMALS.
i
Beckoned on 1 Kilo, of
1
Body Weight
1
Lowett
Highest
Animal. , Manner of Application.
Experimental
Experimental
1
Lethal Dote.
Lethal DoM.
Dose of Strychnine Nitrate In
Mgrms.
Rabbit, .
1 Subcutaneous,
0-50 1 0-60
Cat,
1
076
Dog, .
1
076
,,
' Taken by the Stomach,
20
3-90
J > •
1 ,, Rectum,
2-00
>♦
1 „ Bladder,
f^'fiO
Fox,
i Subcutaneous,
1-00
Hedgehog,
Fowl, .
,^
i-6b
2-00
ft
2 00
Frog. .
2-6b
2-10
Mouse, .
II
2-3(5
2-36
Ring Adder,
>»
' 2310
Now, the important question arises as to the place in this series
occupied by man — a question diflBcult to solve, because so few cases are
recorded in which strychnine has been administered by subcutaneous
injection with fatal result. Eulenberg has observed poisonous
symptoms, but not death, produced by 6 mgrms. (^ grain) and by 10
mgrms. (about ^ grain). Bois observed poisonous symptoms from the
similar subcutaneous administrations of 8 mgrms. to a child 6 years
old, and 4 mgrms. to another child 4 years old — the latter dose, in a
case recorded by Christison, actually killing a child of 3 years of
age. On the other hand, the smallest lethal dos€ taken by an adult
was swallowed in solution. Dr. Warner took 32 mgrms. (J grain) of
strychnine sulphate, mistaking it for morphine sulphate, and died in
twenty minutes. In other cases 48 mgrms. (y^^^ grain) have been fatal.
It will be safe to conclude that these doses by the stomach would have
acted still more surely and energetically if injected subcutaneously.
* According to Christison 's researches, 0 2 grm. (about ^ grain) is fatal to swine ;
*03 grm. (i grain) to bears, if injected into the pleura. 1 to 3 grains (*0648 to
'1944 grm.) is given to horses in cases of paralysis, although 3 grains cannot but be
considered a dangerous dose, unless smaller doses have been previously administered
without effect ; 10 grains would probably kill a horse, and 16 grains ('972 grm. ) have
certainly done so.
336
POISONS: THEIR EFFECTS Al^D DETKCTIOK.
[^ SSg,
The case of Warner is exceptional, for he waa in weak health ; and, if
calculated out according to bodj weight, presuming that Dr. Warner
weighed C8 kilos., the relative dose as atrjchnine nitrate would he '24
per kilo. — a smaller doae than for any animal hitherto experimented
upon* There is, however, far more reason for believing that the degree
of aensitiveueaa in man is about the same as that of catii or dog&, and
that the least fata! dose for man is *70 per kilo,, the facts on record
fairly bearing ont this Tie w» Ft la, therefore, probable that death would
follow if 48 mgrma, (j^^ grain) were injected subcutaneouslj into a man
of the avernge weight of 68 kiloa, (150 lbs.). Taylor estimates the fatal
doB© of strychnine for adults as from 32*4 to 129 '6 mgrma* ("5 to 2
grains); Guy puts the mlnininm at 16 "2 nigrms. ("25 grain).
Large doses of strychnine may be recovered from if correct medicjil
treatment is sufficiently prompt. Witness the remarkable inataDces on
record of duplex poisonings, in wliich the would-be suicide has unwit-
tingly defeated his object by taking sti^chnine simultaueouBly with some
narcotic, such as opium or chloral. In a case related by Schanenstein,*
a suicidal pharmacist took '48 grm. to -G grm. (7*4 to 9*25 grain a) of
strychnine nitrate dissolved in about 30 c.c. of bitter-almond water, and
then, after half an hour, since no symptoms were ex per ie need, *$ grm.
(9"25 grains) of morphine acetate, which he likewise dissolved in bitter-
almond water and swallowed. After about ten mintitea^ he still could
walk with uncertain steps, and poured some chloroform on the pillow-
case of his bed, and lay on his face in order to breathe it. In a short
time he lost coniiciousiiess, but again awoke, and lay in a half -dreamy
state, incapable of motion, until someone entered the room, and hearing
him murmur, camu to his bedside. At that moment— twxi and a quarter
hours after first taking the strychnine — the pharmacist bad a fearful
convulsion, the breathing was suspended, and he lost consciousness.
Again coming to himaelf, be had several convulsions^ and a physician
who was summoned found him in general tetanus. There were first
clonic, then tonic convulsions, and finally opisthotonus was fully
developed. The treatment consisted of emetics, and afterwards tannin
and codeine were given separately. The [mtient slept at short intervals ;
in ten hours after the taking of the poison the .seizures were fewer in
number and weaker in character, and by the third day recovery was
complete* Dr. Macredy t has also placed on record an interesting case,
in which the symptoms, from a not very large dose of strychnine, were
delayed by laudanum for eight honi-s. A young woman, 23 years
of age, pregnant, took at 10 a.m. a quantity of strychnine estimated
at 1 '5 grain, in the form of Battle's vermin-killer, and immediately after*
* Miiac1ik[i's Hfmdbuelif from Taehejikej Deutsche' Klmik, 1861*
t Lancet, Novt-mber 28, 1882.
§39o0
BTKTCHNINtt.
337
wards 2 ounces of laudanum. She wag aeeu by Dr, Macredy m four
hours, aud v/m then suHeritig from prououDced oarcotio symptoms. A
Buip^iato of EiDG emetic Wiis administered. In eight hours after taking
the strychnine, there were first observed some clonic convuleive move-
men t8 of the hands, and^ in a leas degree, the legs. These convulsion b
continued, at times severe, for several honrSj and were treated with
chloraL Recovery was speedy and complete.
In a similar ease related by Dr. Harrison,* a man, aged 54, took a
packet of Battle's vermin^killer, mixed with about a drachm and a half
of laudanum and Kome rum. At the time ho had eaten no food for
days, and had been drinking freely ; yet fifty minutes elapae^l l>efore
the usual symptom a set in, and no medical treatment was obtained until
four hours after taking the dose* He wag then given chloral and other
remedies, and made a rapid recovery.
§ 390. Action on Animals. — T h e action of atryehnine has been experi-
mentally studied on all classes of animals, from the infusoria upwards.
The effects produced on animal forms which possess a nervous system
are strikingly alike, and oven in the cephalapoda, tetanic muscular spasm
may be readily observed. Of all animals the frog shows the action of
strychnine in its purest form, especially if a dose be given of just suffi-
cient magnitude to produce toxic effects. The frog sits perfectly still
and quiet, unless acted upon by some external stimuli, such as a breath
of air, a loud noise, or the shaking of the vessel which contains it, then
an immediate tet^niic convulsion of all the musoles is witnessed, lasting
a few seconds only, when the animal again resumes its former posture,
ThiH heightened state of retlex action has its analogue in hydrophobia as
well as in idiopathic tetanuM. If the frog thus poisoned by a weak dose
IS put under a glass shade, kept moist, and sheltered from m>mid or from
other sources of irritation, no convulsions occur, and after some days it is
in its usual Viealth. If, on the other hand, by frequent stimuli, convul-
sions are excited, the animal dies. M. Richet t has contributed a valuable
memoir to the Aotdemy of Sciences on the toxic action of strychnine.
He has confirmed the statement of previous observers that, with artificial
respiration, much larger doses of strychnine may be titken without fatal
result than under normal conditions, and has also recorded some peculiar
phenomena. Operating on dogs and rabbits, after first securing a canula
in the trachea, and then iujectiug beneath the skin or into the saphena
vein 10 mgrms, of strychnine hydrochloratej the animal is immediately,
or within a few seconds, seisced with tetanic convulsions, and this attack
would be niortal, were it not for artificial rctipiration. Directly this is
* Lmttl, Mny 13, V8S2,
t *' De r Action de la Strychnine k tr&s forte dom «ur le* Mimuiu|&r9%" CompUs
Mntd,, t. xc'i, p. 131,
22
33^
POISONS: THETB EFFECTS AND DETEOTION.
[§ 391-
practiaed the attack ceases, and the heart, after a period of h\irried and
spasmodic heats, takes again ita regular rhythm* Stronger and stronger
dosea may then he injected without causing death. As the dose is thus
anf^mented, the symptoms differ. M. Richet dLatinguishes the following
periods :^(1) A jM?riod of tetanus, (2) A penod of convulsion, charac-
terised hy spasmodic and incessant contraction of all the muscles, (3)
A little later, when the quantity exceeds 10 mgrms. per ktlo.j a choreic
period, which is characterised by violent rhythmic shocks, very sudden
and short, repeated at intervals of about three to four seconds ; during
these intervals there is almost complete relaxation. (4) A period of
relaxation ; this period is attained when the dose exceeds 40 mgrms. per
kilo- Reflex action is annihilated , the spontaneous respiratory niove-
ments cease, the heart beats tumultuously and regularly in the severe
tetanic convulsions at first ^ and then contracts with frequency but with
regularity. The pupils, widely dilated at firsts become much contracted.
The arterial pressure, enonnously raised at the commencement,
diminishes gradmilly^ in one case from 0*34 mm* to 0'05 mm. The
temperature undergoes analogous olianges, and during the convnlslons
is extraordinarily elevated; it may oven attain iT or 42'', to sink in the
period of relaxation to 36*, Dogs and rabbits which have thus received
enormous quantities of strychnine (e.g. 50 mgrms. per kilo,), may, in this
way, live for several hours^ but the slightest interruption to the artificial
respiration, in the relaxed state, is followed by syncope and death,
§ 391. Effects on Man : Symptoma. — The commencement of symp-
toms maybe extremely rapid, the rapidity being mainly dependent on the
form of the poison and the manner of application. A sol nble salt of strych-
nine injected snbcutaneonsly will act within a few seconds ; * in a case of
amaurosis, related bySchuler,t 5 4 mgrms, of a soluble strychnine salt were
introduced into the punctum lachrymale ; in less than four minutes there
were violent tetanic convulsions* In a case related by Barker, the symp-
toms commenced in three minntes from a dose of *37 grm. {5 '7 1 grains)4
* In ono of M, Richet^a expenitienta, a Roluble stiyclinine salt iigected iato & dog
gubciiUucoii&ly ftcted iu fourtecD seconds^
t Quoted by Taylor from M^d. Tirn^s and Oas^H^, July 1881,
t A non* fatal dose may show its clfects rapidly, e.g, thei'e is a cariotis case of symp-
toms of poLsoQing {?Aus(^ hy tlio last dose of a aiixturo wliich m recorded lu PkarrtK
Jonni.t iefl3> 790, A medical |iTaotitioner presorilied the following niixtarei —
n. Tr. atropliAnthi, 5i,
liq. Btiychci hydrocUlorict, . » . . , . jii^s^
Sol. bismuthi et pepsin. (RichardBoii^is), , . . . 5iflf^
Bp. ammon. aromat,
8p, cldorofonni, , sa. Jias,
Aquntn nd, .,,,*.>>,« jvi
ft. mlsL
Shake the hottle.
§ 391 ]
STRTCITKINR.
339
Here the poison was not administered subcutnneoiiBlj. Such short
periods, to a witness whose mind was occupied during the time, might
seem immediate. On the other liand, when bux voniica powder has been
taken, and when strjchnine has boon given in the form of pilli no such
rapid course has been observed, or is likely to occur, the usual course
being for the symptoms to commoiico within half an hour. It is, how-
ever, also possible for them to be delayed from one to two hours, and
under certain circumstances (as in the case related by Macredy) for
eight hours. In a few caseg, there m BrBt a feeling of uneaainess and
heightened aensibility to external stimuli, a strange feeling in the
muscles of the jaw, and a catching i>f the respiration; but gen er ally
the onset of the symptoms is as sudden as epilepsy, and preidou8 to
their appearance the person may be pursuing hi a ordinary vocation #
wheuj without preliminary warning, there is a shuddering of the whole
frame, and a coavulsive seizure. The con vu la ions take the form of
violent general tet?inus ; the limbs are stretched out involuntarily^ the
hands are clenched j the soles of the feet incurved, and, in the height
of the paroxysm, the back may be arched and rigid as a board, the
Buflerer resting on head and heels, and the abdomen tense. In the
grasp of the thoracic muscles the walls of the chest are set immovable,
and from the impending suffocation the face becomes congested, the
eyes prominent and staring* The muscles of the lower jaw — in ** disease
tetanus " the first to be affected —are in ** strychnos tetanus," as a rule,
the last : a distinction, if it were more constant, of great clinical value.
The convulsions and remissions recnr until death or recovery, and, as a
rule, within tvvo hours from the commeuoeraent of the symptoms the
case in some way or other terminates. The number of the tetanic
seizures noted has varied — in a few cases the third spasm has passed
into deatii, in others there have been a great number. The duration of
the spasm is also very dilTerent^ and varies from thirty seconds to five or
Two tomstxKinfub wheu the attack threatens, and re[)4?at in nn hour if iiec«fiAary,
EiehardaoirH liquor biaruuth Rout&iiti} ^ grain of Htiychnine in etich dnochm*
The miKtitrc was alknUiie ; it contaiiiDtl 1'7 grain of strychnine and 3S*25 minim» pf
chlorofonn.
The patit^nt, a woman ^ 54 yeara of age, had iakea the previoiis do^^ wilb cou^
sidi^rable ri?lief ; hut ten minutes af|«r the last dose, irhtoh she describr^d as hr more
hitter than thuao nhe hod taken previously, she was seized with the mnnX ^ym|it^m9
of strychnine jioiMniing^ but roeoverwl afl«f fivp houra.
Tho eipkiiation lit pretty obviciuB ; the mix to re was alkaline, so that the atryeh-
nine was not in the farm of a salt, but in the free state, and was therefore dlesolviKl
by tlie chloi'oform ; the amount of strychnine taken in each dote wholly derpeuded
on whether or nut the niixture was tihuken \iolenlly and ponr^ out into tiie tea-
spoon immediately after shaking; if allowed t^) repose, the globules of chlonsform
^atumt^^d with strychnine would settle at the bottom, and there ronn a stratum rieh
iu fltrychuiue ; im that tlie laat dose would certainly «oiitum ftn ftsoeaap
340
POISONS t THKIK HFFECTS AND nETECTION. [§ 392. 393.
even eight minutes, the interval between tasting from forty- five seconds*
to one or even one and a half houm.t
§ $92. Diagnosis of Stryahnine PoiBoaing, ^However striking and
well dotined tlie picture of strychnine teUious may be, mistakes in
di^nosis are rather frc<inetit, especially wben a medical man is hastily
summoned, has tiever seen a case of similar poisoning, and has no
suRpicion of the possible nature of the seizure. If a young woman, for
instance, is the auhject, he may put it dowu to hysteria, and cei*tainly
hysteria not unfrequentiy affects somewhat similar ctmvulsions. In a
painful case in wliicli the senior author was engaged, a young woman
either took or was given (for the mystery was never cleared up fully) a
fatal dose of strychnine, and though the symptoms were well marked, the
medical attendant was so possessed with the view that the case was due
to hysteria, that, even after making the post-mortem examination, and
finding no adequate lesion, he theorised as to the possibility of some
fatal hysteric spasm of the glottis, while there was ample chemical
evidence of strychnine, and a weigh able quantity of tbe alkaloid was
actually separated from the contents of the stomach. The medical
attendant of Matilda Clover, one of Neill^s victims, certified that the
girl died from deiiiiujn tremens and syncope, although the symptoms
were typically those produced by strychnine. Such cases are par-
ticularly sad, for we now know that, with judicious treatment, a rather
large dose may be recovered from.
If tbe case be a male, a confusion with epilepsy is possible, though
hardly to be explaiiied or excused ; while in both sexes idiopathic
tetanus is so extremely similar as to give rise to the idea that all cases
of idiopathic tetanus are produced by poison, perhaps secreted by the
body itself. As for the distinction between idiopathic and strychnine
tetanus, it is usually laid down (1) that the intervals in the former ai^e
characterised by no relaxation of the muscles, biit that they continue
oontraeted and hard ; and (2) that there is a notable rise of tempemture
in disease tetanus proper, but not in strychnine tetanus. Both state-
ments are misleading, and the latter is not true, for in strycbnic poison-
ing the relaxation is not constant, and very high temperatures in
animals have been observed.
g 393. Physiologl*^ Action, — The tetanic convulsions are esBeutially
reflex, atid to he ascribed to a central origin ; the normal reflex
sensibihty is exaggerated and unnaturally exteuded. If tlie iachiatic
plexus sup[>lying the one leg of an atjimal is cut through, that leg takes
no part in the general convulsions, but if the artery of the 1^ alone is
tied, then the leg suffers from the umscular spasm, as well as the limbs
in which the circulation is unrestrained. In an experiment by Sir
* White, MfiL Med. Jmim., 1867. t Folkea, Med. Twm, X8e».
§394^]
STRYCimiNK.
34"
B, W. Ri chard son, a healthy dog was killed, andf as aoou a& pmcticable,
a, Bolutiuii of «trychiiino was injected tlirough the is^istemic vefiaels by
the tiJOTt& — the whole body becamo at once stiif and rigid a^ a board*
These facta point mimistakably to the spiiml marrow as the seat of the
toxic influence. Strychinno iu, par e^cdienm^ a spinal poison. On
phyBiological grounds the grey aubstauec of the cord i^ considered to
have an inhibitory action upon reflex sensibility, and this inhibitory
power is paralysed by atrychnioe. The spinal cord, it would appear,
ha^ the power of collecting strychnine from the circulation and storing
it up in its structure**
Much light has been thrown upon the cause of death by Kichet's
experiments.! It would seem that, in some easeSi death takes place by
a sutfocatioi] as complete as in drowning, the chest and diaphragm being
immo^ible^ and the nervouB respiratory centres exhausted* In such a
case, immediate death would be averted by a tracheal tube, by the aid
of which artificial respiration might be carried on ; but there is another
asphyxia due to the enormous interstitial combustion carried on by
muscles violently tetfmisedp ** If/' says Hichet, "after having injected
into a dog a mortal dose of strychnine, and employed artihcial respira-
tion according to the dussic method twenty or thirty times a miotite,
the animal dies (sometimes at the end of ten minuted^ and in every case
at the end of an hour or two), and during life the arterial blood is
exannne^l, it will be ascertained that it is black, absolutely like venous
blood."
This view is also supported by the considerable rise of tempemture
noticed ; the blood is excessively poor in oxygen, and loaded with carbon
dioxide. That this state of the blood is produced by tetanus, is proved
by the fact that an animal poisoned by strycbuine, and then injected
subcutaneously with curare in quantity just sul!icieut to paralyse the
muscular syatem, does not exhibit thest* phenomena. By the aid of
artificial respiration, together with the administration of curare, au
animal may live after a prodigious dose of stt7chnine*
Meyer I has investigated carefully the action of strychnine on the
blood-pressure —through a strong excitement of the vaso- motor centre,
tiio arteries are narrowed in calibre, and the blood-pressure mueh iu-
creased ; the action of the heart in frogs is slowedj but in the warm-
blooded animals quickened.
§ 394. Pofit-mortem Appearances. — There is but little characteristic
in the poet-mortera appearances from Btrychnine poisoning. The body
becomes very stiff a short time after death, and this rigidity remaina
generally a long time* In the uotoriouB Palmer case^ the body was rigid
* R. W. Lt)VHtt* Jifunu Phymol, ix, 99-111. i Op ciL
t Wi^%cr Ahxd^ SiUunffu&er^t 1871.
342
POISONS L THSIH EFFECTS AND DETECTION, [§ 395, 396.
two months after deu-th, but, on tbe other hand, the rujor nwtiia has
been known to disappear within twenty- four hours. If the convnJdotta
hEve been violent, th43ra may be minute htemorrhage^ in the brain and
other parts. The Sijuior ftuthor hm seen considerable hiEmorrhage in
the trachea from this cause. When death occurs from asphyxia, the
ordinary signs of asphyxia will be found in the lungs, tte. The heart
naostly has its right side gorged with blood, but in a few cases it is
empty and contracted.
In a case which Scbaiienstcin has recorded * he found strychnine still
undiBsolved, coating the stomach m a white powder \ but this is very
unusual, and probably unique. The bladder often contains urine,
whichj it need scarcely be said, should be preserved for chemical
investigation.
§ 395, Treatment,— 'From the cases detailed, and from the experi-
ments on animals, the direction which treatment should take is very
clear. As a matter of course, if there is the slightest prohability of any
strychnine remaining in the stomach, the poison should he removed^ It is
doubtful whether the stomach-punip can be ever applied with benefit in
strychnine poisoning, the introduction of the tube is likely to aggravate
the tetanus, but a po morphine can be injected subcutaneously. Large
and frequent doses of chloral should be administered in order to lessen
the frequency of convulsionii, or prevent their occurrence, iuid it may be
necessary in a few oases, where death threatens by suffocation, to per-
form tracheotomy, and to use artificial respiration. Where chloral or
chloroform is not at hand, and in cases of emeigency, where this may
easily happen, the medical man must administer in full doses the nearest
narcotic at hand, t
§ 396. Separation of Strychnine from Organic Matters. — The
separation of sLryehniue from organic matters, etc., is undertaken strictly
on the general principles already detailed. It may happen, however,
that in cases of poisoning there is the strongest evidence from symptoms
in the jierson or animal that strychnine alone is to be sought for. In an
instance of the kind, if a complex organic liquid (such as the contents of
the stomach) is under examination, it is best to remove the solid sub*
stances by filtration through glasis, wool, or linen, and evaporate nearly
to dryness over the water-bath, acidifying with acetic acid, and thon
exhausting the residue repeatedly with boiling alcohol of 80 per oent.
t It is e«rtu.iu that lutidine would be a valtiftble jititidote for atiyclmiue, C» G*
Willinnis fouad tlmt lutidiiiu lojccbKd iiito fro^-s already under tho influence of
strychnine, arrt^k^fl tb(j convulBiojjs, or if givtm first, and then followed l>y a fatal
dow of btrychnine, it iirt^vt^iit^d tli« ippearaLUOit of the tetanus, (See aw^, p, 280,
foouxote. )
J
§396.]
STRYCHNINK,
343
The alcobolic extract is iu iu turn evaporated tu di7n©B8, and taken up
with water; the aqueous tiolutian is passed through a wet filter^ aud
then shaken up with the usual suceessiou of fluids, viz., petroleum ether,
beusM^ne, chloroform, and amyl alcohol, which will remove a great
number of impuntiea, but will not dissolve the strychnine from the acid
solution. The amyl aleohol may lastly be removed by petroleum ether ;
and on removal of the final extractive {which should be done as
thoroughly as possible) chloroform m added, and the fluid is alkaliaed
by ammonia, which precipitates the alkaloid in the presence of the
solvent. Should the reverse process be employed — that is, ammonia
added first, and then chloroform — ^the strychnine is not so perfectly
dissolved, aince it has time to assume a cryatalliDe condition. Oh
separation and evaporation of the chloroform, the residue (if much dia*
coloured, or evidently impure) may be dtssolvcd in alcohol or l^enzene,
and recryjitallised several times. Cuahman has published an improved
method of separating strychnine, which, according to teat experiments,
appears to give good results. He describes the method as follows :^ —
''Thi! at'^mtk:!! coutantfi or viscem properly ooiumluuUtd mta w«|ghad, inid on
Aticiuot part takea for aualyiiis. The iii&^a h digested in a Ijoaker over-nigttt, al a
wiirm tempcmiurei with wiit«r ^u^ldiLlnt^fd with lUM^tlc uQid* The coutQuU of the
hettk^r uro Mlerod hy pret^ing lhn.>ugh muslin , and thmi jtftssiag through pap«r>
The altsar filtrate h (3\a[lonltl^•l *jli th« wati?r4mih to soft dryaeaifj au ezavss of
ofdiii»ry SO per o^ut alcfihul n^Id^^ &ud iMiiled ten laiuutea with sitirritig^ and
ftUowed to atand one half* hour at a wsLrm tempemtuiie. This ejctractiou b re|)eaUHJ,
the alcsohol ejcUnctJ^ uiitt^^ filt^^rnl, 6vaiKirat«d to aoft dr^'m^sf!, aud the iBsidui^
takfin up with d little wat^r acidulate with acutlc a^id, And shake u out with pure
ioetic ether iu a se^aratiiig funnel, Siiccessiive fresh porlionfi of acetic ether are
used until the solvent ahowB hy ita colour^ and by tht; e?apomtiga of a few drops^
tliat it dott mtt contain ex t motive matter. Aa many as twelve exlractlona are sotne-
timei aeoeMRry tg accuni^LiBh this. Care eliould he tukou in each cai«e to allow ttme
hi as ocimi^Iete Bejiartttion a» |to5,^tble between the two layers, Tht: purified ucid
ai|ueoi^ Uquid, which nci.d not excoerl in bulk 50 e<c., in now lutumed to the
sepaiaUir, an equi^l t|uautity of fresh aeetic ether aiided^ and enough flodlc carbonate
in sol ut bit to render the mixture slightly alkaline, and the jie[»arator la then
thoroughly ehakeu for aeveral minutes. All the alkaloid shoiild now be in Bolution
In the acetic ethflf^ but a second shaking of the alkaline liquldp with acetic ethei-^ m
always madci thtr two extracts united, and evaporatefJ in a glata dish over hot watti
to dryness. It will tiow Iw found that the reaidiie siliuwt* the alkaloid fairly imi-e^
but not pure enuugb A^r quoiUitihtive residtii^ Thy rt^idue i^ dnswilved in a few drops
of dilute aoetic msid^ warmed to complete aolution, flitered if neceiaary^ diluted to
about 30a.c.,aiid the t^ohition transferred to a amall sepinitittg funtiel ; BO o*e. of
cthef-<!h1otofi>rm (1-1) are now added; aud the aeiiarator s»haken. Afti^r sepavation
the heavier ether 'Chloroform is allowed to run oil', another lot of 30 c.o. of ether-
ehlorofortu is ^ddod, the ^^taiutor shaken, aud immediatc^ly enough ammonia- water
added Ui render the mixturb alkaliucj and the whole vtgi>rou»ly agitated for aeverml
• "The plant- mortem Detection and Estimation of Strychnine," by AUerton E.
Cuahman, Chrm, Nm% voh Ux. 'M.
344
POISONS: THEIB KPFKCTS AND ME'rECTION.
[8396-
minutoii, Aftei- Bojiamliou u coiii|>let«j tUe ntlier^cblorofonu Uyor is ran out into a
clefvu 50 cc, glA8a-sto|>pni^ 1>urette. The nlkalirK^ vrntj^r 5<i]utifin is ngitiitod with
20 C.C. moTB of the etlior-obloroforin, seijaraUd, and this oJttiact ikddwl to that in
the burette. The burette is now »up|Kirted over a small weiglied ghisa dish, which
is kts(>t wtinm on & waler^jatb, and the liquid Allowed to evaporate gcatly, drop by
dro|), !intil a sufficient (|nftntity of thu |mn) nlkaloid bus collected tn iht! centre of
the dish to render un ut^urute weighing {Kjssibltj, or elfie all of the olkuloid Uiay he
collpcted and weighed at onc^e. After all [lossibl© testa have been made upon the
weighted alkaloid, the remainder i& re-diasolvcd in a drojj or two of acetic weid, a little
water added, and tbi? dish exjMJsed uridm" & bell-glass to the funies of ammonia. After
Btatidiug Bomti time all the stryehnine h found crystallisod out in the bt»iiLtiful charao-
teriatic needle- formed cryat^ilH^ Thfj mother liquor is dmwn olT with a small ^e-
pointed tube and rubier bidb, the erystals carefully waabes<l witii 11 little water and
driixj over sulphuric acid. Tlie gla^ji dkh {Containing thvsti crystals i^ ki^jil, a» the
linal exhibit, and i» shown in evidence. Another convenient exhibit may he pre-
(tared by moistening a ^niall lilter-jiaper with a solution of the alkaloid In dilut<^
IKsetie acid, then moiateniug witb a solutioti of potassiutn dicbromate ; this* pajier,
on being dried, itiay be ke])t indelinitely. On moistening it, and touching )l at any
time with a dro]> of strong sulphuric acid, a violet film, changiug to cherry-red, is
formed at the place of contact. "
8hould aeareh be made for Euiimte portionti of strychuiue in the
tieauesj oonsideritlg the mnaXl amotint of the poiBoii which may pruduce
death, it is absolutely necessary to operate on a very large quantity of
materifth It would be advisable to take the whole of the liver, the
brain, spinal cord, spleen, duodenum, kidneys, d! the bhxjd tliat can
be obtuinedj and a considerable quantity of mui^cuhir tissue, bo as to
make in all about oue -eighth to one-teuth of the whole b^^dy ; this may
be cut up into sniall pieces, and boiled in capacious flaiaks with alcohol
acidified with acetic acid. Evaporation muat be controlled by adapting
to the cork an upright condenser.
Should the analyst not have apparatus of a eiase to undertake this at
otie operation, it may be done in septirate portions — the tiltrate from
any single operation being eoUected in a flask, atid the spirit distilled
off in order to be used for the next* In this way, a large quantity of
the organs and tissues can be exhausted by half a gallon of alcohol.
Finally, most of the alcohol is distilled off, and the remainder evaporated
at a gentle heat in a capacious dish, the final extract being treated,
evaporating to a syrup, and tisiiig Cush man's process (fi«/e, p. 343) as
just described. It is only by w^orking on this large scale that there is
any probability of detecting absorbed strytdmine in those oases where
only one or two grains have destroyed life, and even then it is possible
to miss the poison.
Stryclmine is separated by the kidneys rapidly. In a suicidal case
recorded by Schauenstein,* death took place in an hour and a half after
taking strychnine, yet from 200 cXp of the urine, Schaueusteiu was able
* MaschkA'a Bandhuch, Band 2, p. 620.
397-]
STRTOHNtHE.
u$
ta gopHrale nitrate of etrychnme in woil-formed uryeUls. Dr. Krattt*r *
haa made aorae apecial research ee on the times within which strychnine
ia excrctecl hy the kidneys. In two patients, who were being treated by
subcutaneous injection^ half an hour alter the injeetion of 7*5 mgrma. of
strychnine nitrate the alkaloid was recognised in the urine. The strych-
nine treatment wa^i continued for eight bu ten days, and then stopped ;
two days after t lie cessation, strychnine was found in the urine, but none
on the third day, and the inference dniwn is that the elimination was
complete within forty-eight hours.
Strychnine hua been detected in the blood of dogs and cats in re-
searches specially undertaken for that purpose, but sometimes a negative
rosiilt htti been obtained without apparent cause* Dragendorfl t gave
dogs the largest posiiihle dose of tttrychuine daily. On the hrst few day^^
no strychnine was found in the urine, but later it was detected, eapocially
if food was withheld. M*Adam was the fir^t who detected the aliisorbed
poisoti, recognising it in the musulos and urine of a poisoned horse, and
also in the urine of a houtid^ Dragetidorff has found it in traces in the
kidneyis, spleen, and pancretis ; Gay, in different parts of the central
nervous system, and in the saliva. So far as the evidence goes, the liver
is the best organ to examine for strychnine ; but all parts supplied with
blood, and most secretions, may contain small quantities of the alkaloid.
At one time it was believed that strychnine might be destroyed by
putrefaction, but the question of the decomposition of the poison in
putrid l>odies may he said to be settlerh So far as all evidence goes^
strychnine is an extremely stable substance, and no amount of putr^ceuce
will destroy it. M'Adam found it in a horse a mouth afti^r death, and
in a duck eight weeks after; Nnnneley in fifteen aninials forty-three
days after de^ith, when the bodies were much decomposed ; Roger in a
l>ody after iive weeks' interment ; Hichter in putrid tissues exposed for
eleven years to decomposition in open vessels j and, lastly, W, A. Noyes +
in an exhumed body after it had been buried 308 days.
It would appear from Ibsen's § ex^^eriments that strychnine gets
dissolTed in the fluids of the de-ad body — so that whether strychnine
remauis or not, greiitl}" depends as to whether the fluids are ret^iined
or are allowed to soak away ; it lu, iherefore^ most important in exhttma*
tioDS to save a^ much of the flviid as possible.
§ 397* Identification of the Alkaloid. ^*A residue containing strych-
nine, or strychnine mixed with brucine^ is identitied —
t 111 ail rtiiiimil rairtdty killed by u subcutaneous injection nf jict*t4tc of sttych-
niue, ito slrychniini was dettfcted cither in the blood or liver, — Drtujfmd&rJ',
t J&um. AvFufit. Chan. Soe., kvL 2,
I VkrtoLf^ gmM. Med., Bd« vlii.
346
POISONS: THEIK EFFECTS AND DETECTION,
[S 397^
(I) By it» alkaline retwtiou atid its bitter taste. No substance Ciiu
poBsibly be fitryobnino unleea it tastoB remarkably bitter.
{'2) By the extremely insoluble ehr ornate of strycbuiue, already
described.* A fluid containing 1 : 1000 of strychnine gives with
ehrooiate ol potash (if allowed to stand over-night) a marked precipi-
tate, dissimilar to all others, except those of lead and baryta ^ihroraates,
neither of which can iK>SQlbly occur If any of the processes described are
followed.
(3) If the chromatfi just described is treated ou a j>orcelain plate
with a drop of pure strong sulphuric acid, a deep rich blue colour,
paasing through purple iuto red^ rapidly makes its appearance. This
colour possesses an almorptiou spectrum (figured at p. 58), Dr. Guy,
neglecting iuterniediate colours, aptly compares the succession — (1) to
the rich blue of the Orleans plum ; (2) to the darker purple of the
niulberry ; and (3) to the bright clear red of the sweet ormige. These
characters — viz^j alkalinity, bitterness, and the property of precipitation
by potassic chromate in a dehuite crystalline form, the crystals giving
the colours detailed — belong to no other substance known eave strych-
nine, and for all purposes sufficiently identify the alkaloid. The same
colour is obtained by miiting a drop of sulphuric acid with stryuhniue
and a crystal, or speck, of any one of the following substances : — Ferrid-
cyanide of potash, permanganate of potash, peroxide of lead, peroxide of
manganese, and ccrous hydroxide.
Potassic permanganate and stdphuric acid is the most delicate,
and will detect O'OOl mgrni* of strychnine ; cerous hydroxide is, on
the other hand, most convenient, for cerous hydroxide ia white ; all
the others have colours of their own* Cerous hydroxide is prepared
by dissolving cerium oxalate in dilute sulphuric acid and precipitating
with ammonia, filtering and well washing the precipitate ; and the
atter may he used while moist, and responds well to ^^(^ mgrm. of
strychnine.
The influence of mixtures on the colour reactions of atrychnine have
been studied by Fiiickiger, who states; —
" No strychnine reaction appears with hiulphuric acid containing
chromic acid (made by dissolving Q-02 grm. of pot. bichromate in 10 c,c.
of water, and then adding 30 grms. strong sulphuric acid) when brucine
and strychnine mixed in equal parts are submitted to the teat; it
Huccceds, however, in this proportion with sulphuric acid containing
potass juni permanganate ("02 grm, pot. permanganate in 10 c.c. of
water, and 30 gnns. of strong sulphuric acid).
" If the brucine is only one-tenth of the mixture, the blue-violet
* 1 grm. of fttfychntne gave 1'280 gnus, of the chromate, — 78*1 i>cr cent, of
stiychmne ; 3 gavio 3*811 of the ohrptnate, —78 '77 per Oflnt. of itrych nine. —Afwiir.
1398.]
STRYCHMNK,
347
colour iH obtained. A large exyeHS of atropine does not prevent or
obeeure tho Btrychmoe reaotioiL A solution of 1 milligrm. atropine
sulphate evaporated to dryness, together with 5 c.c. of a sohitioa of
BtrychulDe (1 : IQOjOOO)^ has no influeDco on the reactloUj neither in the
proportion of 1 mgrni to 1 cc, of the game solution ; neither has
einchonine nor quinine mij effect,
** Morphine oli^eureB the retiction in the following proportions ; —
'*A aolution of 001 mgrm. Htrychuine evaporated with a solution of
1 mgrm. of morphine sulphute on a water-bath, yields a blurred strych-
nine reaction when the residue is diss^olved in sulphuric acid, and a
crystal of potass ie permanganate added* But still there is evidence
whereby to simpect the presence of strjxhnine,
^^ A solution of 2 mgrma. of morphine sulphate treated in like manner
with 0*01 ragrm. of strychnine yields like results*
**A solution of 3 mgrtiis* of morphine sulphate evaporated to
dryness, with a solution of 0*01 mgrm* strycbmue yielded results
with the potassic permanganate test the same aa if no etrychnine
was present.
** A solution of 1 mgrm. of morphine aulpliate, treated aa above, with
a solution of O'l mgrm. strychnine, ottered positive proof of the presence
of the hitter.'' *
Drageudorff was able to render evident *025 mgrm. mixed with
twenty times its weight of quin* sulphate j the same ohserrer likewige
recognised *04 mgrm. of strychnine in thirty three times its weight of
caffeine. Vera trine is likewise m>t injurious,
§398. The physiological test consists in administering the substance
to some small animal (preferably to tk frog)^ and inducing the ordinaiy
tetanic symptoms. It may Ijc at once observed that if definite chemical
evidence of strychnine has been obtained^ the physiological tost is quit©
unnecessary ; and, on the other hitnd, should the application of a liquid
or substance to & frog induce tetanus, while chemical evidence of the
presence of strychnine was wanting, it would be hazardous to assert that
^^. strychnine was present, seeing that caffeine, carbolic acid, picrotoxin,
^H certain of the opium alkaloids, hypaphorine, some of the ptomaines, and
W many other substances induce similar symptoms* The best method (if
I the teat is used at all) is to take two ftog8,t and insert under the skin of
I the one the needle of a subcutanoous syringe, previously charged with a
^^K itotution of the substance^ injecting a moderate quantity^. The other frog
^H is treated similarly witli a very dilute solntiou of strychnine; the
W two are than placed under small glass shades, and the symptoma
* Fliicki^r^i Mmeii&iti, trftnskteil hy ^tigelvoorlj Detroit, 1893.
t A vc?ry pr««Hi>4l diBudvantAgu of the physiological te&t is the gnu^t difficulty of
ohuimng frogs eiually whuu w#uted.
JK^
548
P0IS0N8 : THEIR EFFECTS AND DETECTION, [g 399, 4OO.
observed and tsompared. It m uot t^b^olutely necessary to iujeot the
solutiuti Hiider the akin, for if applied to the surf ace the aame elfeets
are produced ; but, if ^lecustomed to raauipulatiou, the operator will find
the subcutimeouB application more certain, especially in dealing with
minute quantittcB of the alkaloid.^
g S99. Hypftpborinei^One substanf:^ in known which neither pliy biological test
Tior the colour Tcactiants auffice to diatiaguiah from strychnine^ Tiz», byiiftphoniiei+
the active matter of a papilionaceouB tree growing id Java— the ffypaphont^
subumbran^ ; u. smu.!! quantity of the dkaloid i& in the bark, 0 Ui^^r quaDlity is in
tho seed*
Hyimphorinu fonna colourless crystals which brown, without mflltiog, above 320'';
jLtid cxhalu a vapour HmclUiig like imphthykmin^. The free alkaloid Is soluble in
water, but has «a action on litmus. Tli« Malts arc less soluhle than the free alkaloid^
so that acids, such as iiitiic or hydrochloiiCi prodace in a short time |>recri|ntatcH on
standing. Solutions of the salbsi are not precipitated by alkalies ; chloroform, ether,
benzene, all fail Ut extract it from eitlicr alkaline ur acid f5olutioua. It gives no
precipitate with potassic ehtomate, but most general alkaloidal refigent*^ precipitate.
It gives a precipitate with iodine ti-ichloridcj and has therefore pi-obably a
pyridine nucleus, it may bo au acid anilide^t It gives the sam<] colours as strychnine
with sulphuric acid and |K)tasHic; [jcrniangauatti or potasaic cliromate ; it causes in frogs
tetanus, but the dose has to be much larger tljan that of strychnine. The duration
of life in dosi.^ ef 15 mgrins, may extend to five daya^ and frogs may even recover
after £tO mgrtim
The distinction between strychnine and hyf.>aphorin^ ts therefore easy ; l>eaide» it
will not occur in a chloroform extract, and it will not give a precipit*te with iHjtasaic
chroniate.
§ 400. Quantitative BBlimation of Strychnine — The best proems of estimating
the pTo;fsortion of each alkaloid in a mixture of stj-ychtitnc and brucine, Is Keller*]!
riiclhud. Th«y may also be prccipitat*5f3 ai^ picrates, and the brncltie picra to destroyed
by nitiic acid after obtaining the combined weight ot the mixed piorates ; then
weighing the uudcstroyed strychnine pi crate.
To carry out the lattei process, the solution of the mixed alkaloids must bo as
neutral as posaible, A saturated solution of picric acid ii^ added drop by drop to com-
plete pi-ecipitation. A filter^^iaf^er is dried and weighedj and the precipitate collected
on to this filter* paper ; the precipitato is wasiied with cold water, dried at 10&*i and
weighed. This weight gives the combined weight of both strychnine and brucine
pieratea.
The pn^ipitate is now detached from the fUter, washed into a fimall flask , and
heated on the water- l>ath for mime time with nitric aoid dilutee! to 1*056 gravity
{about 11 per cent* HNO^). TJiis process destroys the brucine iiicrate, but ]cavea
the strychnine picrate untouched ♦ The fl<!id liquid is new neutralised with ammottut
<>r soda, and a traoa of acetic acid added ; the procipitate of strychnine picrate is now
• Methyl atryohnine, as well as methyl briicine, has been shown by Brown and
Fiawr to have an effect exactly the opptrsite to that of strychnine, paralysing the
muscles like eurai^* In the ca^, there fore, of the methyl compounds^ a physiological
test would he very valuable, ainoe these compounds do not respond to the ordinary
ti^ts.
t Dr. a Flugge, ArrJuf. ej:p. rath. n. PK, Bd. xxxii. 31 iS.
% Juliiia Tafel (5<jr., 1390, 412) has shown that the colour reaction with HjSO^
and ozidlMiig agents are the oharactfristic testa of an aeid anilide.
§40i.]
BRtTOIKl.
349
(wlleoted fti^d wmghed, TUe weight at this sulitmcted froni the first weight, of course,
gives that of th(^ Ijiuciuu pic rate.
Oue part of sjtrychiiiu<> picrate itt equul to 0^5932 stiychnluu ; and one (lart of
brucinc picrate h l^na\ in 0*6324 liriicine.
From till' Btiychninc picnitc the picric acid iimy bu rceovoriMl und wcigtied by
dissatving the picmte iu a mincnil acid aod Bbaking out with eth«r ; froni the »cid
liquid thus depri vt^d ^i^ picric at^id the ulkalmd may be sup&ralatl hy alkaligLug with
atninonui mid shaking out with cblorofarm.
Keller's mvt hod is based on the conversion of the bnicine into diniti*0'hmcine,
which ia insoluhle in chloroform. From 0'2 to 0*3 gtm. of tho cmde alkaloids is
diaiiolved in 10 c*c, of 10 j#r cent. H^Oj ; wlicn cold, 1-5 c.c. of 50 (ler cent, nitnc
add (sp. gr. I *42) in add<^d. After one and a !iaM hours pour into a aeparatitig fnunol,
make alkaline with ammonia^ and slmke out with chluroform. Tlie chloiofonu Ukmt
up dinitmattychuinc hut not diuitro-bniciae,
§401. Brucme (033115^^504 + 41120) oceurg aeaociated with stiych-
Diiio in tbe plants already mentioned ; its best source is the ao-called
faine angusfura bark, which contains but little strychnine. Its action ie
similar to that of strychnine. If crystaUised out of dilute alcohol it con-
tains 4 moleculos of water, easily expelled either in a vacuum over sul-
phuric acid or by heat. CrystalUsed tints, it forms transparent four-sided
priania, or arborescent forms, like boric acid. If thrown down by
ammonia from a solution of the acetate^ it presents itself in needles or
iu tufte.
Brucine and sttychnine contain the same group Cj^H^-j^N^O^, but
brucine contains two methoxyl groups thus: —
u„H.,NA-CA
Strychnine,
Jj^Hj^NaO^
c^H,(oce,)2
Brucine.
The recently-cryBtallised alkaloid has a solubility different from that
which has effloresced, the former dissolving in 320 parts of cold, and
150 (wirts of boiling water ; whilst the latter (according to Felletier and
Gaventou) requires 500 of boiling, and 850 pirta of cold water for
solution. Brucine is easily soluble in absolute, as well as in onlinary
alcohtil ; I part dissolves in 1 "7 of chloroform, in 60*2 of benzetie, F^etro-
leum ether, the volatile and fatty oils aud glycerine, dissolve the alkaloid
slightly, amyl alcohol freely ; it is insoluble in anhyflrtjiis ether. The
behaviour of brucine in the subliming cell is described at p, 261. Anhy-
drous brucine melts in a tube at 178^ A solution of anhydrous brucine
in absolute alcohol dissolved in the proportion of 2^129 grms. in 100 c«c,
of alcohol has a specilio rotation [%>] at 20*= -80 1 {Tfjkmifm-). The
taste is bitter aud acrid. Soubeiran maintains that it can be recognised if
1 part is dissolved in 500,000 parts of water. If nitric trioxide be parsed
into an alcoholic solution of bnicine, first brucine nitrate is formed ; but
this passes again into solution, from which, nfter a time, a heavy,
gratuilar, blood-red precipitate separates : it cousiats of dinitro-bructne
350
POISONS r THKTR KFF1CT8 AND DETTCCTTON.
[8 402,
(Cg3H^4(NO,^)N20^). Bnicine fully neutralises acids, ami forms salta,
which are for the moat part orystalliDe. The neutral sulphate
(CggHq^N^O^SH^^Oi + SIH^O) is in long needles, easily soluble in water.
The acetate is not crystalline, thut of strychnine is so (p. 35^8).
Brucine is precipitated by ammonia, by the caustic and carbonated
alkalies, and by most of the group reagents. Ammonia doen not preci-
pitate brucinsj if in excess ; on the other hand, atrychnine comes down if
excess of amn^onia is added immediately* This has been proposed as a
method of separation ; if the two alkaloids are present in acid solution,
ammonia in excess is added, and the solution is immediately filtered j
the quantitative results are, however, not good, the strychnine precipitate
being invariably contaminated by brucine.
Chromate and dichronmte of potassium give no precipitate with neutral
salts of brucine; on the other hand, strychnine chromate h at once
formed if present. It might, therefore, be used to separate strychnine
from brucine. The authors and others have attempted this method, but
the results were not satisfactory.
g 402. Physiologic^ Action. — The difference between the action of
strychnine and that of brucine on man or animals is not great. Mays
states that strychnine affects more the anterior, brucine the posterior
extremities* In strychnine poisoning, convulsions occur early, and
invariably take place before death ; l)ut de^th may occur from brucine
without any convulsions, and in any case they develop late, Brucine
diminishes local sensibility when applied to the skin ; strychnine does
not.* In a physiological sense, brucine may be considered a diluted
strychnine. The lethality of brucine, especially as compared with
strychnine, has been investigated by F. A, Falck.f He experimented on
11 rabbits, injecting subcutaneoualy hrucine nitrate in doses of varying
magnitude, from 100 mgrms, down to 20 mgrms, per kilogram of body
weight. He found that brucine presented three stages of symptoms.
In the first, the respinition is quickened ) in 3 of the 1 1 cases a strange
injection of the ear was noticed ; during this period the pupils may be
dilated. In the second stage, there are tetanic convulsions, trismus,
opisthotonus, oppressed respiration^ and dilated pupils* In the third
stage the animal is moribund, Falck puts the minimum lethal dose for
rabbits at 23 mgnns. per kilo. Strychnine kills 3*06 times more quickly
than brucine, the intensity of the action of strychnine relative to that of
brucine being as 1 : 117*4. Falck has also compared the minimum lethal
dose of strychnine and brucuie with the tetanising opium alkaloids, as
shown in the following table: —
f Brti^'n u. Sttf/ehjiin s r.inf toxihtlo*jhchii Paralkic^ run Dr. V. A. R'alck.
§ 4O30
BRUCINE.
TABLE SHOWING THE LETHAL DOSES OF VAKIOXJS
TETANiHING TOISONS.
B try ch nine uitraUi, ,
ThebAine uitrikttij
Bruoitie nitrate,
Laudaninc nitrato^ .
Codemo nitrate,
Hydrocotaraino iiJtmt«,
0-8
14M
23-0
UMlft
If tbese views are correct, st follows thnt the least fatal dose for an
adult man would be rG4 grm* (about 24*6 grains) of brochie nitrate*
§403. Tests. — If to a solution of briiciiie in strong alcohol a little
methyl iodide is added, at the end of a few minutes circular rosettes of
crystal groups appear (see fig», p. 352) ; thej are composed of methyl
brucine iodide (CogH25(CH3)NjjO^Hl). Crystals identical in shape are also
obtained if an alcoholic solution of iodine, or hydriodie acid with iodinej
is added to an alcoholic solution of brucine, A solution of strychnine
giirea with methyl iodide no similar reaction. Strychnine in aloolioUe
fiohition, mixed with brucine, in no way interferes with the test. The
methyl iodide test may be confirmed by the action of nitric acid. With
that reagent it prod noes a scarlet colour, passing into blood red, into
yellow -red, and finally ending in yellow. This can be made something
more than a mere colour test, for it is possible to obtain a crystalline
body from the aotion of nitric acid oii brucine. If a little of the latter
be put in a test tube and treated with nitric acid of 1 '4 sjieeitic gravity
(immersing the test tube in cold water to moderate the action ), the red
colour is produced. On spectroscopic examination of the tilood-red
liquid a broad, well-marked absorption band is seen, the centre of which
(see page 58) is between E. and F. [W. L. about 500]. There is also a
development of nitric ojide and carbon dioxide, and the formation of
methyl nitrite, oxalic acid and kakotelin (GyjjRjflNgO^ + fjNHO^-i^
^^H^N^Oj, + N(CH3)02 + C^H^O^ + 2N0 + 2H,0), On dihiting abun-
dantly with water, the kakotelin separates in yellow flocks, and maj^ he
crystallised out of dilute hydrochloric or dilute nitric acid in the form of
yellow or orange*red ciystali, very insoluble in water, but dissolving
readily in dilute acid. On removal by dilution of the product just
named, neutralisation with ammoaia, and addition of a solution of
ohloride of calcium, the oxalate of lime is thrown down. The nitric acid
test is, therefore, a combined test, consisting of — the production by the
352
POISONS: THEIR KFFECTS AND DETKCTION,
[§ 403.
action of nitric acid (1) of a red colour ; (2) of yellow scales ar crystals
inaolublG 111 water; (3) of oxalic acid. No alkaloid save brucine is
known to give this reaction.
There are other methods of producing the colour test. If a few
drops of nitric acid are mixed with the aubstauco lU a test tube^ and
then sulphuric acid cautiously added, so as to form a layer at the bottom,
at the junction of the liquids a red ^one^ passing into yellow, is seen.
A solution of bninirje is also coloured red by chlorine gas, ammonia
changing the colour into yellow.
Fliickiger* has proposed as a test mercurous nitrate, in aqueous
soliitiou with a little free nitric acid. On adding this reagent to
x^Mii
*^i
Cryntols or Methyl brucitic ItKlidc, {From a pkt^igr^pk, )
a solution of brucine salt, and gently warming, a ^ne carmine colour
is developed.
In regard to the separation of brncine from organic fluids or tissues,
the proecfis already detailed for stryehuitie suffices. Tt is of very great
importaiice to ascertain whether both strychnine and brucine are present
or not — the presence of both pointing to nux vomica or one of its pre-
parations. The presence of brucine may, of course ^ be owing to impure
stryehuine ; but if fonnd in the tissues, that solution of the question is
impfoJmble, the commercial strychnine of the present day being usually
pure, or at the mo8t containing so email a quantity af hriiciue as would
hardly l>e separated from the tisBues.
• Arehirf. Pfuirm. (8). vi, 404.
§ 404-408.]
OfiLSEMlNB.
353
2. THE QUEBEACHO CROUP OF ALKALOIDS,
I 401* Tilt* bark of the Quebraeho Btaneo* {A^idojqm^ma quebracho) conUina,
ACCorrliDg to He£«o*8 researches, no fewer tliftn six alkaloids^ — Qnebrachine, Aspido-
ai>emiiDOj AspidoepermAtiae^ AK^rLdufiaminej and Hyjxiquabraoliiiie, Tho more
itniwrtant of these are A^pidosjycrmin^ and Qii6bra£kifiS,
§ 405. Aspldosp^rmtae (C25jHji(,jN.j03) forma colourless iitjefUoa wbkh melt at
206*. They dissolve in about SOOO parta of water at 14'— 48 jmrts of 90 per eent,
alcohol J and 106 |iArta of pure ether* The alkaloid givee a fine magenta colour with
perohloHc acid.
§ 406, Qnebracliiiie (GjiH-joNjOa) cryatallkee in colfiurleaa ni^edles, melUng-
poitit (with partial decoraposition) 215*» Thfl crystals are soluble in chloroform,
with difRculty soluble in cold alcohol , but easily iu hot, Thu olknloidj treated with
^Iphurto acid and {peroxide of lead^ strikea tk beautiful blue ctilour. It aliio gives
with BUlphurie acid and potasaic chromatc the strychnine col&ara. Quehrachina,
dissolyad in sulphuric acid contain lug iron^ liiaoomes viokt-bluB^ passing into brown*
The alknloid; treated with strong Htalphuric acid, b«6omea brown ; on abiding a
cryatal of j)oU8slc idtrate^ a blue colour is developed ; an now noutra1i.Hlng with
t^uatic soda no re*l coloratioQ is perceivijd. DragendorlT has studied the beat method
of extracting tbeae alkaloids for toxicological purposes. He r commends extraotton
of the substances with sulpluiric acid holding water, and shaking up with aol vents,
Aspidoepermiue is nut eitracted by petroleum ether or benzene from an aeid watery
extiaot, but readily hy chlorofonn or by antyl aloohoL It is also separat*^ from the
samo solution, alkalised by ammonia, by ether, amyl alcohol nr chlorc}fi>mi ; with
difficulty by yietroleum ether ; some is dissolved by benzene. Quebracbine may be
axtiaeted from an acid solution by chloroform, but not by petrolenm athcr. Alka*
Used by amuionia, it dissolves freely in idiloroform aud in amyl alcohol, Tmees am
taken up by petroleum, eorauwhat more by ban^ene, Aspidospennino is grailually
decomposed in the body, Init Qiiehracbine is more resistant, and has baen fmnd in
the stomachy intestines, blood, and urine. The toxioolojrlcal aation of the bark
tmnks it wit)i the tetanic class of itoisona. In this country it does not seem likely
to attain any LmportanDa as a poiaon.
3. PERBIRINE,
g 407. Pereirloe (Cj^H^NaO)— an araorpbous alkaloid from pereira bark --gives
a play of colours with snlphuno acid and potasaic biohromate similar to but not
identical with that of strychnine, Frcibdo^s reagient strikes with it a blue ccijour^
Dn diflsdving pereirino in dilute sulphuric acid, and precipitating by gold chloride,
tbe precipitate is a bt^itttiful red, which^ on standing and warming, hi deu|H;ned^
Pereirine may be exttacted from aii add solntion, afb>r alkalizing with ammonia, by
ether or ben;^ne«
4. GELSEMINE,
S 403, G«lAaniine (C^B^NgO|) and gf.dBeminine (C^HggNsO^) mn two ilkaloidi
which have tteen sejiarated from OeUviniuni 9emp(fnfiren»t tha Gattdbia Jttiaisiine, a
plant having alfinitieii with several natuml orders, and p!ac(^ by De Gandolle among
the Lo^nia^cem^ by Chapman among the Ki£biai^a\ and by Dcjcatsna anuing tlie
Apoqpi^ae^ss* It grows wild in Virginia and Florida,! Qelsemine is a strong base;
• Sea liabig'a dnwtl., ©cxi ^49-388 ; Ser. dm- d^utsch, chem. GtullAcK, %L
2189; xii,15S0.
t The following are its botanical characters t — OalyK five-ivirted, corolla funni?l»
sbaped, five'lob^, somewhat oblic|no; the lobes almost equal, the ^}ost«rior being
inn^rmoat in bud ; stunans five ; anthers oblong sagittate, style long and slender ;
23
354
POISONS: THEIR EFFECTS AND DETECTION, [8409,410.
it ifl yellowiah whoa Unpure, but 4 wliitc amorphotis powder wheu pure. It fttsee
bilow 100° into a traus[>ai:«nl idtrerjus lua^^ at liiglier tfrnipi^mturcs it condenses on
glasB in minute drops ; its taste is **xtrouiely bittor j it m soluble in 26 p&Ha of «th^r,
in ckloroformp biEuIpMde of carbon j beuzcne^ and in turpentine ; it ie nt.it very
soluble in alcohol, and still leas aolublo in water, but it freely diseiolves in ftcidulated
watei', Tbe caustic alkalies pn^ipitat<3 it^ the precipitate being iui^ijluble in uxce^a ;
it i» first white, but aften^-anls brick-red, Tantiiiij picric acid^ iodised pntAssic
iodide, platinic chloride, potaBsio-mcrcxiric ii^^idide, and mercuric cldoride all give
precipitatcis. Fruhde^s reugent gives with gel^^cmine a brown chungiag to green,
Sulpburic acid di^olvea gelsemine with a reddish or browniith colour; after a
time it assumes a pinkish hue^ and if warmed on the wtiter-bathi a mnr© or leas
ptir()k colour ; if a small cryntal of [»ota88ic bichromat't' be elowly stirred in the
Boiphuric acid solutjon^ reddish purjilc streaks are produced along the y>ath of the
crystal ; eerie oxide exhibiU this l^etUr and more promptly, so small a quantity fts
^001 grain sb owing the ruction. TUia reaction is something like that of strychnine,
but uitric ueid cauBea gel^'Ciine to assume a browniBb -green, qnioklj changing to a
dee] I green— a reaction which readily distinguishes gelaemine from attychuine and
other alkaloids.
I 409. Fatal Bose, — 10 mgrma, killed a frog witliln four hours, and 8 nigm^a, &
cat within lifteen minntoa. A bealtby woman totik an amount of concentrated
tincture, which was equivalent to 11 mgnns^ (| grain), and died in seven and a half
bonrx
§ 410. Effects on Animals— Physiologieal Action. —Gelsemino acts i>owerfully
on tlic respiration ; for exatnplc, Drs. Sydney Ringer and Murrell* found, on o] crating
on the frog, that in two minutes the biM^athin^ had become diatinotly slower ; in
three and a half minutes, It had been reduced by onc-ibir^I ; and in six minutes, by
one-half^ at the expiration of a quartet of an hour, it was only one-tbiixl of ite
original frequency ; and in twenty minuter ^ it was so shallow and irregular that it
could no longer be counted with accuracy. In all their ex|>erimenta they found
that the respiratory function was alK^lished before reflex and voluntary njoLion had
become extinct. In sererul instaneca the animals could withdraw their legs when
their toes were pinched, days after tbe most careful observations had failed to detect
tbe eiistenee of any respiratory movement. The heart was seen beating tlirough
the chest wall long after the comjiletc abolition of respiration.
In their experiments on warm-blood&d animals (cats), they noticed that in a few
minutes the respimtions were slowed down to 12 and even to 8, and there was
loss of power of the posterior extremities, wbih^ at short intervals the upper half of
the biwiy was convulsed. Id about half an hour paralysis of the bind limbs was
almost complete, and the respiratory movements so shallow that Ibi^y could not he
counted. In tbe case of a dog, after all r«apimtion liad ceased tracheotomy was
performed, and air pUTiiped in t the animal reooveriKi
Ringer and Murrell consider that gelseminc produees no primary quick<?ning of
the respiration, that it has no direct action on either the diaphragm or intercostal
mujicles, that it paralyses neither the phrenic nor the intercostal uprves, and that it
diminishcB the rate' of respiration after both vagi have been divided. They do not
atigmaa two, each two- parted, the divisions being linear ; frnit elliptical, flattened
contrary to the narrow partition, two^ct^Uctl, septic idally two-valvod, the ralves
keeled i seeds five to six in each celh large, fhit^ and winged ; embryo straight in
fleshy albumen ; the ovate flat^ cotyledons much shorter than the slender radicle ■
stem smooth, twiniug and shrubby j leaves opposite, entire, ovate, or lanceolate,
shining on short petioles, nearly persistent ; flowers large, shgwy^ very fragrant,
yellow, dne to five in the axil of tbe leayea,
* lant^, lere, vol. i, p. 41 S.
§4^1,412.]
GEtaKMlKB.
35 S
oonaiddr that gelseimiie acts on the cord throtigk Setsehenoiv^i inMbltor]^ cc^otre, btit
tUat it destroys reflex power by its direct action od the ooidg and tliEit probably it
hiia no lDflii<3Dce on the mot<»r nerrea^ Dr« Burdoii Sauderson haa gJtio tnreatigated
the action of gelaemin@ on the reapirattonj more €S|>ecial!y in relation to the moTB-
meutii of tbc diajihragm. He operated upon rabbita ; the auim&t being tmrcotised
by chloral^ a aiimU apatuhij shapfKl like a t^jaspoon, was introduced into the p^ti-
totteal cavity through an opening in the linea Alha^ aud pj^^aed upwitrd^ in front of
the liver until its convex stirfocD rented sgstnst the under dtle of thecentnim ttn-
dineurn. Th^^ ak^ni of the spatula was brought into corinectiou with u levf;r, hj
mejLfia of wiiich ita to-and-fro move m en ts (and consequently that of the diaphragm)
were in^^ribcd. The lirat elTect i^ to augment the depth but not the fr&quflney of the
rospinitory movements ; the next ia to dimiiiisb the action of th(? diaphragm both in
i^xUstit and fri^uency. Thiti happens in accordanoe with tlm general priiiaple
appliciLble to most cases of toxic action — viz., that pareaia of a contral organ ia
preo^ed by over-action* The diminution of movement ni>on the whol© is pro*
gresaivG, but this pn>grva3ion h intermpted, because the blood is becoming more and
more venoua, and, therefore ^ the phenomciua of asphyxia aro mixed up with the
toxical effects, Dr, Sandersoo concludes that the drug acta by paralysing the
automatic reapirattiry centre ; the pt-oceas of extiuction, whicli might he otherwise
ex fleeted to be gradual and progressive, is prevented from being so by the inter-
vention of disturbances of which the explanation is to be found in the imji^rfect
arterial tsatton of the ctrcnlating blood* Riugt^r and Mttn^ll have also experlmeiitdd
upon the aetii>n of gelsemlne on the frog's heart In all caaes it decreased the
numhor of beats ; a small fatal dom prrwlneed a white contracted heart, a large
fatal do^i a dark dilat^^d heart ; in either Gam arreat of the ciroulatiou of course
followed,
§ 411, Effects on Han.— The preiiaratioiis used in medtdne are the fluid exka«t
ftud the tincture of g^ihemine ; the latter appears to contain the reain of the root as
well as the active principle, Thf^re arc several caaes on record of gelsemtno, or the
plant itself, hadng been taken with fatal e^ect,* Besidea a marked elfect on the
reapimtion, there ta an elfect upon the oye^ better seen in man than in the lower
animals ; the motor nerves of tha eye arfi attacked jirat^ objects cannot he fixed,
Apparently dodging theu* position, the eyelids become {Aralysodi drofip, and cannot
be rai^d by an elfort of the will ; the pupils are largely dUated, and at the same
tinie a feeling of lightiie^ has be«n complained of in the tongue ; it aaocnda giwlnally
to the roof of the mouth, and the pronunciation ia slurred. There is aome partssis of
the f^xtremities, and thuy refuse to anpport the body j the respiration becomes
hibfiUHMJ^ and the pulse naes in frequency to 12D or 130 beats per minute, but the
mind remains clear. The symptoms o(!icur in about an hour and a half after taking
mn overdose of the drug, and^ if not excessive, aoon diaappeari leaving no unpleasant^
nesa hoblnd, If^ on the either hand, the case pnx^eeds to a fatal end, the respiratory
trouble incroasea, and there may be oonvnlBions^ and a conrae ve?y similar to that
8e«rn in ex|ierimenting on animals. Iiarge doses are esj^ally likely to produce
tetiinna, wbioh presents some clinical dilleteneea distingnishing it from strychnine
totanuM, Gelsi'miue tetanus Is always preceded by a loss of voluntary reflex power,
respiration ceaie;^ before the onset of convwlaiouj*, the posterior extremities are moat
alfected^ and irritation faUa to excite another paroxysm till tho lapKC of some flecond^,
as if tli*j exbiiusted coni required time to renew its energy ; finally, the cimvulaionB
only la«t a short time.
§ 412. Extraction from Organic Matters, or the Tisanes of the Body.— Dragen*
dortTstatoa tliat, from ah little as half a grain of the rcKit^ both gelsf^mine and geleMnnlo
* See Mfk:«i, 1873^ voL ii. jj. 476; Brti^ Med, (tnd Sur^. JoKra*, Ajirtl 1860 ;
PkU. MM, and Surg. Htpatt^t, \%ii^,
356 POISONS: THKIR EFFECTS AND DETECTION. [§413-
acid may be eztraotod with acid water, and identified. On extracting with water
acidified with snlphuric acid, and shaking up the acid liquid with chloroform, the
gelsemic acid (sesculin ?) is dissolved, and the gelsemine left in the liquid. The
chloroform on evaporation leaves gelsemic acid in little micro-crystals ; it may be
identified by (1) its crystallising in little tufts of crystals ; (2) its strong fluorescent
properties, 1 part dissolved in 15,000,000 parts of water showing a marked fluores-
cence, which is increased by the addition of an alkali ; and (3) by splitting up into
sugar and another body on boiling with a mineral acid. After separation of gelsemic
acid, the gelsemine is obtained by alkalising the liquid, and shaking up with fresh
chloroform ; on sei)aration of the chloroform, gelsemine may bo identified by means
of the reaction with nitric acid, and also the reaction with potassic bichromate and
sulphuric acid.
6. COCA ALKALOIDS-COCAINE.
§ 418. The leaves of Erythroxylon coca contain a number of alkaloids, of which
the following have been investigated : —
Cocaine, CiYHaiN04.
Cinnamyl cocaine, C]gH,3N04.
o-TruxUline (0uHa3N04)2.
i3-Truxilline (Ci9Ha3N04V
Benzoyl ecgonine, CigH,,N04.
Tropa-cocaine, CigHigNOj.
Hygrine, CgHigNO.
Cuscohygrine, Ci3H94NOa.
All these alkaloids are esters of ecgonine, and on saponification they yield ecgonine,
methyl alcohol, and an aromatic acid.
Cocaine, O^iUa^O^, is the only coca alkaloid of any great present importance, and
the other alkaloids are commercially converted into cocaine by first obtaining ecgonine
from them, treating this with benzoic anhydride which converts it into benzoyl ecgo-
nine, benzoyl ecgonine being converted into cocaine by treating its methyl alcohol
solution with HCl. Thus—
CiyHjiNO. 4- 2H2O -> OHibNO, + C^H^Oa 4- CH,OH
Cocaine. Ecgonine. Benzoic Methyl
acid. alcohol.
2aH„
Ecgoi
15NO3 + {C^UfiO)fi -> 2CgH,4N08(COCeH8) 4- H^O
>nine. Benxoic Benzoyl ecgonine.
anhydride.
C1QH19NO4 4- CHjOH -> C,7HjiN04 4- H2O
Benzoyl Methyl Cocaine,
ecgonine. alcohol.
Cocaine crystallises from alcohol in prisms melting at 98^ Not very soluble in
water, soluble in ether, alcohol, benzene, chloroform, and CSg. Natural cocaine is
bitter, alkaline to methylorauge, and levorotatory ; the specific rotatory power of its
hydrochloride in water - - 71 95**, and it yields lecgonine. From d-ecgonine may
be prepared d-cocaine which melts at 46-47* C. , and from inactive ecgonine may be
prepared inactive cocaine, melting at 80"* C. ; this variety is soluble in alcohol and
ether, and is probably a racemic variety of natural cocaine. Also from a-ecgonine
may be obtained a-cocaine, melting at 305** C, insoluble in ether, not very soluble in
alcohol, and a little more soluble in water. Eucalne^ which is n-mdhyl benzoyl
triacetone aUamine carboxylie acid methyl ester, is used as an artificial substitute for
cocaine ; it crystallises in pnsms melting at 104** C, and has similar properties to
natural cocaine, as also have (2-cocaine and t -cocaine. On the other hand, a-cocaine
has no aniesthetic properties. If in the reaction forming cocaine from ecgonine
§4i4-4«6.]
COCAINE.
357
higher alcohols bo salwiiliiled for methyl alcohoU tiigher homotagiicaof cocaine Are
formed , having mach tEkA suae |ihyBiologic4il propertieji &a cucame.
The coDiititutiou of eegoQiiie and {t-ocgoalDe may bo re^i^i^nted as follows ; —
CH,-0H-CH-CO0H
N— CHjNcHOK
EcepniDe.
CHg— CH-OR>
/ V yCOOH
\ / \000H
CH, ClI GHg
a'Ecgonine.
§414. Cocaiae Hydi'ochloi-ate (Ci^H^iKO^HCl).— CryBtallised from
ftlcoliol, cocaine hydrouhlorate apjjeara in prismatic crystals ; thcae
crystals, according to Hesac,* whesj perfectly pure, sbould melt at
186*, although the meUing-polnt b generally given as 200" or even
202°, Cocaine hydrochlorate is soluble in half its weight of water,
insolnble in dry ether, but readily soluble iu alcohol, amyl alcohol,
or ohloroform.
§415. Pharmaceutical FreparatioBS. — Cocaioe bydrgehlorate m
officinal. Gelatine disca, weighiug 1'31 mgrmfi. {^^ ETB,in\ and each
containing 0*33 mgrm. (^^ grain) of the ealt are ol:!icinal, and
used by ophthalmic surgeons. A solution of the hydroclilorate, con-
taining 10 per cent, of cocaine hydrochlorate and (for the purposes
of preserving the solution) 0'15 per cenU of salicylic acid is also
officinal. Stronger solntiona may also be met with ; for instance, a
20 per cent, solution in oil of cloves fur external application in cases
of neui^lgia.
§ 41G. Separation of Cocaine and Teats. — Cocauie may be shaken
out of solutions made slightly alktiUiie by ammonia by treatment with
benzene ; it also passes into petroleum etber under tbc same circum-
stances. The beat method is to extract a solution, made feebly alkaline,
thoroughly by ethers and then shake it out by benzene and evaporate
the separated benzene at the ordinary air temperature. The property
of the alkaloid to melt at or below the temperature of boiling water ^ and
the ready decompoBition into benzoic acid and other pruduota, render
cocaine easy of identification^ If, for instance, a small particle of cocaine
is put in a tube, a drop of strotig aulpliuric acid added and warmed by
the water-bath, oolourlesa crystals of benzoic acid sublime along the tube^
and an aromatic odour is produced i
Fliickiger has recommended the production of benssoate of iron as a
iisofal test both for cocaine and for cocaine hydrochlorate.
One drop of a dilute solution of ferric chloride added to a solution of
20 mgrms, of cocaine hydrochlorate in 2 c.o. of water, gives a yellow
fluid, which becomes red on boiling from the production of iron henzoate^
This reaction is of little use unteas a solution of the same strength of
* 0. Hmm^ AnHokn^ c«hcjcvi« 342-344.
358 POISONS: THEIR EFFECTS AND DETECTION. [§417-
ferric chloride, but to which the substance to be tested has not been
added, is boiled at the same time for comparison, because all solutions of
ferric chloride deepen in colour on heating.
A solution of the alkaloid evaporated to dryness on the water-
bath, after being acidulated with nitric acid, and then a few drops
of alcoholic solution of potash or soda added, develops an odour of
benzoic ethyl ester. Cocaine hydrochlorate, when triturated with
calomel, blackens by the slightest humidity or by moistening it with
alcohol. Cocaine in solution is precipitated by most of the group
reagents, but is not affected by mercuric chloride, picric acid, nor
potassio bichromate.
Added to the tests above mentioned, there is the physiological
action; cocaine dilates the pupil, tastes bitter, and, for the time,
arrests sensation ; hence the after-effect on the tongue is a sensation
of numbness.
Cocaine may be estimated in fairly strong pure solutions (1 per cent.)
by adding a N/10 iodine until the iodine is in excess; the hydriodide
periodide is filtered off and the excess of iodine in the filtrate determined
by N/10 sodium thiosulphate. The iodine compound formed is
Ci.H^iO.NHII^.*
§ 417. Symptoms. — A large number of accidents occur each year
from the external application of cocaine ; few, however, end fatally.
Cocaine has thus produced poisonous symptoms when applied to the eye,
to the rectum, to the gums, to the urethra, and to various other parts.
There have been a few fatal cases, both from its external and internal
administration; Mannheim, for example, has collected eleven of such
instances.
The action of cocaine is twofold ; there is an action on the central
and the peripheral nervous system. In small doses cocaine excites the
spinal cord and the brain ; in large it may produce convulsions and then
paralysis. The peripheral action is seen in the numbing of sensation.
There is always interference with the accommodation of vision, and
dilatation of the pupil. The eyelids are wider apart than normal, and
there may be some protrusion of the eyeball.
The usual course of an acute case of poisoning is a feeling of dryness
in the nose and throat, difficulty of swallowing, faintness, and there is
often vomiting ; the pulse is quickened; there is first cerebral excitement,
followed usually by great mental depression. Occasionally there is an
eruption on the skin. HypersBsthesia of the skin is followed by great
diminution of sensation, the pupils, as before stated, are dilated, the eyes
protruding, the eyelids wide open, the face is pale, and the perspiration
profuse. Convulsions and paralysis may terminate the scene. Death
* W. Garaed and J. N. Oollie, Jour, Chem, Soc., Izzix., 1901.
§4i8-42a]
COHYDALLNK.
359
takes place from pamlyBiB of tbe breatbiug ceDtre ; itiereforc the Iioart
beat^ after the cessation of respiratiou. Ae au antidote^ uitrite of amyl
haa apparently been nse4 with succeBa.
There is a form of chronic poisoning produced from the taking of
fim&ll doses of cocaine daily, Tbe symptoms are v<3ry various, and are
referable to disturbance of the digestive organs, and to tbe effect on tbe
nervons system- The patients become extremely emaciated, and it secDis
to pro<lnce a special form of mania.
g 418, Post-mortem Appearances. — The Bppearaiices found in acute
caaea of poisoning bave been hypersemia ot tbe Ever, spleen, and kidneys,
as well as of the bmiu aud spinal cord*
In the experimental poisoning of mice with cocaine Ehrlich * found
a considerable enlargement of the liver,
§ 419, Fatal Dobc. — The fatal dose, according to Mannheim, f must
be considered as about 1 grm. (154 grains); tbe smallest dose known to
have l^een fatiil m 008 grm. (1*2 grain) for an *idult, and 0*05 grm. (0-7
grain) for a child.
0. COKYDAblNE.
I 420. From the root of Ci/rtjdaiis cavii^ eight alkaloids have h&tn ii^lated, vi^^,
Oorydaline, C^^^it^O^ Gtirybulbia©, C^H^NO^t Iftocorybulbiae GaH^^NOi, Bulbo-
eapiiine, Oi^Ha,N04, Corytuberine, OuH^HO^, Cofycanne, Cnll^iNOo, CorycaFaijiine,
C^H^NOa, aud Corydine, Ca.HsaNO^.
Thc^e alkaloLds are oot of any great to^icological itDportanoe, but corydalius lu
Urge dimes cauiea epileptifonu convulaioiiH. Deafch takesi pUc^ from r^plmtory
paralysis.
Corydaline crystallised id tlio cold And away from light, cjut of A mixturo of
ftbaoluta alcohol aud ether, forms colourlt^ss, Aat^ prtsuLatic ci^^atiLls, which quickly
turn yollow on ex£»osurQ to light or heat. It i& bitter to the taste nud ita tsolutloDfl
ifQ dextro-rotatory. Vutti coryduUuo (;hat3gea colour at about 125"] softens it about
133', and melta findlj at 134* to 135'. It diaeolves in eth^fj chloroform, carbou
dmlphide, and beuzene, but uot so really In alii^ohol. It ia almost insoluble in cold
waterj and but alightly soluble in Ixiiling water. Water precipitates it from a
solution in alcohoK It is also soluble in dilute bydrochlorlc and sulphuric acids.
It gives a precipitatu with potikssiani itxlido if a solution of the hydrocbluride be uaed.
The pradpitiiioCTy^ili^esout of hot water in clusters of short lemon -yellow pria'
matic etystalfl, and has the foiTUula of Clgfl^NO^HL CkirydaUne pUtinoohloridc hati
the composition of (CpH^N04)^HaPtCl^, uoutaiiiiug Pt It* "94 per uont., aud 2 "44 per
cent of N,
An alcoholic somtioti of iodine oiddisea oorydaline to dahydrocorydaline
hyiriodidfi, C,jp»HjnNOJII, Dehydrcsoorj^daluio ia very like bi^rberinc. The lelatiou
of corydaline to berberiu« is furtlier shown hy the formation of oorydi^ldiue when
ooijdaiijie is oxidtsedi
CHgO. XO-NH
CH,(X * ^00 -NH
Corydaldlne.
* DmtUehem^, Woeh^ms., 1S80. No, 32,
t DmimA, Atdk^f, kU%. Med,, M, nil, 1891» SSO.
360 POISONS: THBIR EFFECTS AND DETECTION. [§421,422.
Dobbie and Lauder, as the result of a number of researches, have provisionally
adopted the following formula for corydaline,*
CH
HC
0
^\
C— OCHs
H.C /^^C
C-O CHj
CH HC
CHjO-C ^\/Vn'
CHCH3
CHoO-C
CHa
CH^CH,
v.— The Aconite Group of Alkaloids.
§ 421. The officinal aconite is the Aconitum napdlus — monkshood or
wolfsbane — a very common garden plant in this coimtry, and one
cultivated for medicinal purposes. The root of A, napellus is from 2 to
4 inches long, conical in shape, brown externally, and white internally.
The leaves are completely divided at the base into five wedge-shaped
lobes, each of the five lobes being again divided into three linear
segments. The numerous seeds are three-sided, irregularly twisted,
wrinkled, of a dark-brown colour, in length one-sixth of an inch, and
weighing 25 to the grain (Ouy). The whole plant is one of great beauty,
from 2 to 6 feet high, and having a terminal spike of conspicuous
blue flowers. The root has been fatally mistaken for horseradish, an
error not easily accoimted for, since no similarity exists between them.
§ 422. Phajmaceutical Preparations of Aconite. — The preparations
of aconite used in medicine are —
Aconitine, officinal in all the pharmacopoeias.
Aconite liniment (linimentum aconili), made from the root with
spirit, and flavoured with camphor; officinal in the British Pharma-
copceia. It may contain about 2*0 per cent, of aconitine.
Aconite tincture, officinal in all the pharmacopoeias.
Aconite ointment, 8 grains of aconitine to the oz. (i.e., 1*66 per
cent.) ; officinal in the British Pharmacopoeia.
Aconite extract, the juice of the leaves evaporated; officmal in
most of the pharmacopoeias. The strength in alkaloid of the extract
varies ; in six samples examined by F. Casson, the least quantity was
0*16 per cent., the maximum 0'28 per cent.t
♦ Jmtm. Chem. Sac. r., 1892, 244 ; 1896, 67 ; 1897, 71 ; 1901, 79 ; 1902, 145.
+ Pharm. Jaum., 1894, 901.
S 423]
AOONITi: GROUP OF ALKALOIDS.
361
Fleming's tincture of aconite is not officinal, bat is sold largely in
commerce, U ia from three to four times t^trotiger than the B.P.
tincture.
§ 4 2 J. The species of aconite are uumerous; the few that have been
iuvoatigated clearly indicate that the genus m rich iu poiBonous alkaloids
and that there are several acouHinesH,
Professor Duns tan,* who has been for tnany years investigating this
subject, summarises the results obtained up to the present somewhat aa
follows : —
The alkaloids of acouite plants may be divided iuto two groups ; the
ftrat) a toxio group, of which the type is ordbiarj aconitine, contains
alkaloids which are diacyl esters of a series of poly-hydric bases con-
taining four methoxyl groups, the aconines»
The members of this group are^ —
Actmitiue from Aconiium napdhia.
Japacoiiitiae from Acfmitum deinQrvhymm,
Bikhaconitine from Ai^onituiti spiceiut,
Indaconitme fmm Ae&nitum dtutsmmdhum.
All these are highly poisonous and exert a very similar physiological
action. When the acetyl group is removed by bydrolyats the resulting
bcuisoyl or veratroyl baae itj but feebly poisonous ; still hydrolyaing
leads to the splitting oif of the acoutues, basea not only destitute of
toxic power, but in some respects acting in an antjigonistJo way to the
aconitine parent.
The second group is the atisine group, which contains atisine from
AfXfnilum heterophijllum and palraatiiie from Aconitum palmatum j these
two alkaloids are not poisonous and therefore will not be deseribed.
The aconitine group of alkaloids is divided into (1) Acoui tines, (2)
Fseudaconi tines, and these may proviaionally be represented by the
following fornmlfe ; —
1, A00HITINK8,
Aconi tine (acety l-beussoy Uacon i ne ),
\00OC,»H*
J apaconi ti n e (ace ty 1-ben s&oy 1- j apaconin e) ,
XocO'cX
Indaconi ti ne (acety l-benxoy 1 -pseudaconi ne),
yOCOCH*
C«H«Oi^ = C^H^,N<
* W. K. Dutistftu, F»H.S,, &Dd T, AndereoD Heury, Jtmm. Ckem^ SiK. fVo^.,
362 POISONS : THEIR EFFECTS AND DETECTION. [§ 423.
2. PSEUDACONITINEB.
Pseudaconitiue (acetyl-veratroy l-pseudacon ine),
<0C0-CH3
(OCH,).
OCOCell8(0-CH3),
Bikhaconitiue (acetyl-veratroyl-bikhaconine),
yCCOCH,
C3eH„0„N = anH«ON4.(OCH3)4
XoOO-CeHaCO-CHs)^
Each of the aconitines contains four methoxyl groups, and on
hydrolysis furnish one molecular proportion of acetic and one of benzoic
acid ; thus aconitine should yield 18-9 benzoic, 9-3 per cent, acetic acids,
and 79*8 per cent, aconine ; similarly japaconitine breaks up into acetic,
benzoic acids and japaconine (C25H43O1QN). Indaconitine into acetic
and benzoic acids and pseudaconine, C25H41O8N. The pseudaconi tines
yield on hydrolysis acetic and veratric acids and a base ; pseudaconitiue
giving the base pseudaconine (CgsH^^OgN), and bikhaconitiue breaking
up into the organic acids already mentioned and the base bikhaconine
thus; —
Bikhaoouine. Acetic Veratric
Acid. Acid.
The saponification of the various aconite alkaloids is apparently best
effected by dissolving in alcohol, making the solution alkaline with soda
and digesting at ordinary temperatures for twenty-four hours, at the
end of which time the solution is neutralised by sulphuric acid, and the
alcohol got rid of by evaporation in a vacuum at a very gentle heat.
The aqueous solution can now be acidified again by sulphuric acid, and
the benzoic or veratric acid, as the case may be, shaken out with benzene.
The base is now liberated by alkalising with NaOH and shaking out
with ether, while the acetic acid can be distilled off, first acidifying with
sulphuric acid.
The ethereal solution of the base Dunstan appears to usually treat
with fused calcic chloride for some time in order to have a dry ether
solution.
The aconitines and pseudaconitines rotate a ray of polarised light to
the right ; on the other hand the salts, such as the hydrochloride and
the hydrobromide, are laBvo-rotatory.
The melting-points and specific rotations of the alkaloids are as
follows : —
Melting-point.
Specific Rotation.
Aconitiue .
196M9r
12*82 in alcoholic solution
Jai)acoiiitino
204 •2"
28-86
Indaconitine
202*'-203'
18-17
Pseudaconitine .
2ir-212''
18-6
Bikliaconitine
118M16'
12-21
§ 424f 4^S*] ACONITINE. 363
The following are the melting-points of the gold salta : —
M&iliDg^polut of Cruld 3a] tl,
{{a) 136 -5"
Aconituie aaricljlonde * 1 ('0 ^^^*
lie) 176*
■"—""- (ISS
Ittdooouitine ,^ U7M52*
PBeudaconitmo,, 235°-236°
Eikhaconitino ,, ....... 235**^233"
§424. Acooitine. — Acoiiitine from the English A. TtapeUus m repre*
fteuted a3 CgyH^j^Oj^Nj Itaa a melting-point of ISS'o", and specific rotafcion
of [o]o + 10"47' - 1 1'l' In alcohoHo solution, aud the bydrobromide nielta
at 163'. Kngliah aconltiue is scarcely hi commerce now, having been
auppkntod by the German aconitine, which baa the meltii)g*poiut and
otber characters given in the preceding tables.
The behaviour of a sample of Merck*a aconitine in the subliming
cell, which haa a raeltiug- point of 184", was as described at pa^^e *2G(J.
Aconitine dissjolves in water at 22^ in the proportion of 1 in 4431
{DuHAtan); it is soluble in 37 of absolute alcohol, 64 of anhydrous ether,
5 5 parts of chloroform and lieiizene (A. Jurrjefts) ; it has basic pro-
perties! and a cold watery solution haa au alkaline reaction to cochineal,
hut not to litmus nor to phenol-phthaleln. Aconitine is not precipitated
by mercuric potassium iodide, but gives a voluminous precipitate with
an aqueons solution of iodine in potaasium iodide and a crystalline
compound with gold chloride.
Aconitine is best extracted from the plant, or from organic maitera
generally^ by a 1 per cent, sulphuric acid ; this strength is stated not to
hydrolyse aconitine if acting in the cold ; after purifying the acid liquid
by shaking it with amyl alcohol^ and then with chloroform, always
ojtej^atinf/ in the rohl^ the liquid is precipitated by ammonia in very
slight excess, and the liquid shaken with ether ; the ether is removed,
dehydrated by standing over calcium chloride, and then evai>orated
spotitaneously ; should the aconitine be mixed with the other alk^iloida,
advantage can be taken of the method of separating aconitine by con-
verting it into hydrobromide, as described under ** Benzoyl-aconine/*
§ 425. Tests for Aconitine. — The most satisfactory and the most
delicate is the physiological U^t ; the minutest trace of an aconite-holdiug
liquid, applied to the tongue or lips, causes a peculiar numbing tingling
sensation which, once felt, can readily be remembered*
An alkaloidal aubstance which, heated in a tube, melfca approiimately
near the melting-point of aconitine, and gives off an acid vapour, would
render one suspicious of aconitine, for most alkaloids give off alkaline
vapours, Aconitine also niay» by heating with dilute acids, be made to
364 POISONS : THEIR EFFECTS AND DETECTION. [§ 426.
readily yield benzoic acid, an acid easy of identification. Aconitine dis-
solved in nitric acid, evaporated to dryness, and then treated with
alcoholic potash, gives off an unmistakable odour of benzoic ester.
Should there be sufficient aconitine recovered to convert it into the
gold salt, the properties of the gold salt (that is, its melting-point, and
the percentage of gold left after burning) assist materially iu the
identification.
A minute quantity of aconitine dissolved in water, acidified with acetic
acid, and a particle of KI added and the solution allowed to evaporate,
gives crystals of aconitine hydriodide, from which water will dissolve
out the KI. Iodine water gives a precipitate of a reddish-brown colour
in a solution of 1 : 2000.*
The chemical tests are supplementary to the physiological; if the
alkaloidal extract does not give the tingling, numbing sensation, aconitine
cannot be present.
§ 4'J6. Benzoyl-aconine (" isaconitine "), CajH^jNOii, is obtained
from aconitine by heating an aqueous solution of the sulphate or hydro-
chloride in a closed tube at 120''-130*' for two or three hours, a molecule
of acetic acid (9*3 per cent.) being split off, and benzoyl-aconine left.
It may be separated from the mixed alkaloids of the Aconitum
napdlus by dissolving in a 5 per cent, solution of hydrobromic acid
(excess of acid being avoided), precipitating with a slight excess of
ammonia, and shaking out with ether. The residue left after the ether
is evaporated chiefly consists of aconitine; it is dissolved in just suffi-
cient hydrobromic acid and the exactly neutral hydrobromate solution
allowed to evaporate spontaneously in a desiccator ; crystals of aconitine
hydrobromide separate out, the mother-liquor containing some beuzoyl-
aoonine and " homonapelline." The aqueous solution which has been
exhausted with ether is now shaken out with chloroform. This chloro-
form solution contains most of the benzoyl-aconine, and on separation
the residue is dissolved in just sufficient hydrochloric acid to form a
neutral solution ; this solution is concentrated on the water-bath with
constant stirring, crystals of the hydrochloride form, and are filtered ofi^
from time to time and washed with a little cold water, the washings
being added to the original liquid; the different fractions are mixed
together, and the process repeated until they have a melting-point of
268^ Benzoyl-aconine is obtained from the hydrochloride by precipi-
tating the aqueous solution by the addition of dilute ammonia, and
extracting the solution with ether ; the solution in ether is washed with
water, dried by means of calcium chloride, and then distilled ofif.
Benzoyl-aconine is left as a transparent colourless non-crystalline varnish
of a melting-point near 125*.
• A. Jurgens, Arch. Pharm, (8), xxiv. 127, 128.
§ 42?.]
ACOKITINE.
36s
The sohition in water is alkaline to Htmus* Tho base is readily
soluble in alcohol, in chloroform, and in ether. The alcoholic solution
18 dextrorotatory. The solutions aro hitter, hut do uot give the tingling
sensation characteristic of aeon it in©. The hydrochloridej the hydro-
bromide, the hydriodide, and the nitrate have been obtained in a
crystalline state. The most characteristic salt is, however, the aurochlor
deriTative, When aqueous solutions of bensM>jl-aconine chloride and
anno chloride are mixed, a yellow precipitate is thrown down, which
(dissolved in alcohol, after being dried over calcium chloride, and slowly
evaporated in a desiccator) deposits colourless crystals entirely diiferent
from the yellow crystals of aconitine gold chloride. These crystals have
the composition G32H4j(AnCl2)NOn, and therefore, by theory, should
yield 22 '2 per cent of gold, and 8 per cent, of chlorine. Professor
Duns tan * found^ aa a means of two determinations, 21*6 per cent, of
gold, and 7 "8 per cent of chlorine.
By hydrolysis benzoyl^aconine yields benzoic acid, which can be
shaken out of an acid solution by ethor and identified; one molecule of
benzoic acid is formed from one molecule of ben'^oyl-aconine. 1 9*7 per
cent of beuzoic acid should, according to the formula, be obtained ;
Professor Dunstan found 18*85 per cent.
Benzoic acid in the subliming cell begins to give a cloud at about
7 7 '-80'*, and at or near 100* sublimes most rapidly*
Benzoic acid, recovered from an acid solution by shaking out with
ether, may be recognised as follows : — To the film left on evaporating
off the ether add a drop of H^SO^, and a few crystals of sodic nitrate,
and heat gently for a short time ; pour the clear liquid into ammonia
water, and add a drop of ammonium sulphide- A red-brown colour
indicates benzoic acid. The rationale of the test is as follows : — Dinitro-
benzoic acid is first formed, and next, by the action of ammonium
sulphide, this is coa verted into the red-brown ammonium diamidoben-
TOEbe.— K Mohlor, BidL Soc, Chem. <3), iii. 414-416,
§ 427. The Lethal Dofie of Aeooitlnee. — Commercial aconitine haa
in the past varied in appearance from that of a gummy amorphons
mass up to a purer kind in white crystals.
Professor Dunstan t examined in 1B93 fourteen samples, some of
them of considerable age, and only found two samples (one of English^
another of German make) which approached in melting-point and
crystalline appearance pure aconitine ; the one, the English, melted at
1S6'-187°, and contained about 3 per cent, of benaoyl-aeouine j the
other, a German specimen, was almost pure ; the melting*point waa
187 '5'. At the present time, however, fairly pure crystalline aconitine
• JmifiL Chem, Soc. (Traftf.), 1893.
t Op. eU,, 4»1.
366 POISONS : THEIR EFFECTS AND DETECTION. [§ 428.
may be obtained and assayed accurately by determining the proportion
of acetic and benzoic acids. The physiological action of commercial
aconitiue is, however, in all cases the same, the difference being in
quantitative, not qualitative action ; in the small doses usually adminis-
tered, the physiological action depends wholly upon the toxic bases
present.
Cash and Dunstan give the lethal doses for cats per kilo, of body
weight as follows : —
Aconitine, 0*134 mgrm.
Diacetylaconitine, 4-5 ,,
Benz-aconine, *24'5 ,,
Aconine, 160-400 „
It is difficult to say what would be the minimum fatal dose of pure
aconitine for a man ; the more so, since there is reason for believing that
human beings are more sensitive to aconitine than dogs or cats ; prob-
ably it would be about ^ mgrm. per kilo, of body weight ; and taking
the average weight of an adult at 70 kilos, this would mean 7 mgrms.
or about y^^ of a grain ; but such calculations can only be applied to
the pure crystalline substance, the lethality of commercial tinctures
and pharmaceutical preparations generally is best settled by recorded
cases.
In 1863 a' woman took 70 minims of Fleming's tincture, and a
grain of acetate of morphine, and died in about four hours ; but as this
was a complex case of poisoning, it is not of much value. Fifteen
minims of the tincture caused very serious symptoms in the case of a
woman under the care of Dr. Topham,* the effects lasting many hours.
Probably the smallest quantity of the tincture recorded as having
destroyed life is in the case of Dr. Male, of Birmingham.! He died
from the effects of 80 drops taken in ten doses, extending over a period
of four days — the largest dose at any one time being 10 drops, the
total quantity would perhaps equal '08 grain of aconitine.
With regard to the root itself, 3*8 grms. (60 grains) have been known
to produce death.
§ 428. Effects of Aconitine on Animal Life. |— There are few sub
* Lancet, July 19, 1851, p. 56.
t Med. Gaz,f vol. xxxvi. p. 861, quoted by Taylor, Prin. of Med, Juris, ^ vol. i.
p. 426.
X GiULiNi, p. — ExperimerUelle Unterstiehungen ucber die Wirhing des Aeonitins
aufdm NervensysUm, das Jferz, u. die Athmungf 8vo, Erlangen, 1876.
Harlet, Dr. John,— -**0n the Action and Uses of Aconitia," St. Thos. Hosp.
Reports, 1874.
V. ScHKOFF, C. Jr.^Beitrag zur KenrUniss des Aconit,, 8vo, Wien, 1876.
Pluooe, p. C. — "Untersuchungen ueber die physiologische Wirkuiig verachio-
dcner Handelssorten von Aconitin, u. Pseudoaoonitin auf Muskeln u. Nerven," Virch.
Archiv, Bd. Ixxxvil, 1882, S. 410.
§ 428.]
AGONiriNB.
367
stances which have beeo experimented upon in such a variety of ways
and upon no many classes of animuls as aconitlne in differeDt forms ;
but tliere does not seem to be any eiseenttal difference jn the symptoms
produced in ditforent animals save that which is explained by the
organisation of the life-form under experiment.
Insects.— The senior author has made exi>eriments with the active
principles of aconite upon blow-flies. An extract was made by allowing
the ordinary tincture to evaporate spontaneously at the temperature of
the atmosphere. If a minute dot of this is placed upon the head of a
blow-fly, absorption of the active principle takes place in from fifteen to
thirty minntea, and marked symptoms result. The symptoms consist
essentially of muscular weakness^ inability to flyi and to walk up per-
pendicular surfaces ; there is also, in all cases, a curiouR entanglement
of the legs, and very often extrusion of the proboscis ; trembling of the
legs and nmsculur twitohings are frequent. A progressive paralysis
terminates in from four to five hours in death ; the death is generally
so gradual that it is difhcidt to know when the event occurs, b\jt
in one case there were violent movements of 'the body, and sudden
death.
Fish, — The action on fish has been studied by Schnk and Praag.
There is rapid loss of power and diminished breathing ; the respiration
seems difficult, and the fish rapidly die.
Beptiles — Frogs.— PI ugge, in experiments on frogs, found no
qualitative diflerence in the action of any of the commercial samples of
aconitine. This fact gives the necessary value to all the old experiments^
for we now know that, although they were performed with impure or
weak preparations, yet there is no reiison to believe that the symptoms
described were due to any other but the alkaloid aconitine in varying
degrees of purity or dilution. Frogs show very quickly signs of weak-
ness in the muacnhir power ; the respiration invariably becomes laboured,
and ceases after a few minutes; the hearths action becomes slowed,
irregnlarp aod then stops in diastole. The poisoned heart, while still
pulsating, cannot be arrested either by electrical stimulation uf the
vagus or by irritation of the sinus, nor when oTioe arrested can any
further contraction bo excited in it* Opening of the mouth and
apparent efforts to vomit, Plngge observed both with I^ana esmdenta
and Rana temjioraria. He considers them almost invariable signs of
aeonitine jjoisoning* A separation of mucus from the surface of the
body of the frog is also very constantly observed. Dilatation of the
pupils is frequent, but not conntanl ; there may be convulsions, both of
a clonic and tonic character, before death, but fibrillar twitchiugs are
seldom.
368 POISONS : THEIR EFFECTS AND DETECTION, [§ 428.
Action of Aconitine on the Heart.
Bohm ^ has made researches on the action of aconitine on the frog's
heart. After a subcutaneous injection of 5 mgrms. the heart beats
quicker owing to stimulation of the motor ganglion ; then, as the motor
ganglion begins to be paralysed and simultaneously the brake-apparatus
(Hemmungs-vorrichtungen) stimulated, the beats are slowed and
become irregular as in the action of the digitalis group. There is finally
arrest in diastole ; at first removed by atropine, but in the next stage
atropine has no effect, for there is complete paralysis of the brake
nervous centre as well as the vaso-motor centre ; if, however, the vagus
is stimulated the beats may recommence^ to be followed by final com-
plete arrest.
This sequence is not always easy to follow because the least overdose
obscures the successive stages by almost at once paralysing the nervous
centres. Durdufif has shown that, contrary to the poisons of the
digitalis group, the extensibility of the heart is diminished, that is to
say, its volume is lessened.
The mammalian heart is similarly affected to that of the frog.
With small doses of aconitine, the relation of pulse frequency and
blood-pressure varies somewhat according to the particular aconitine, as
it affects the central origin of the nerves of the vessels and the vagus.
Thus sometimes the pulse slows without sinking of the blood-pressure,
and sometimes there is increase of pulse and rise of blood-pressure.
Matthews has registered by means of a myocardiagraph the movements
of the exposed heart of a dog after aconitine had been introduced into
the circulation, and seen arhythmic beats and fibrillar contractions of
the ventricle, results of exalted sensibility and excitability of the heart
muscle. All researches show that aconitine is extremely poisonous to
the mammalian heart ; so minute a quantity as 1 part of aconitine to 5
million of the blood notably quickens the pulse even up to 109-131,
the pulse at once sinking to normal if unpoisoned blood is allowed to
replace the blood containing aconitine. Doses of 1 of aconitine to 1^
million of blood are fatal within 7 minutes by arrest of the heart beat.
In fatal cases the enormous rise of frequency of heart beat is followed by
sudden arrest of the left ventricle, whilst the right auricle and ventricle
may continue to beat for a quarter to half an hour. In this condition
the beat of the left ventricle cannot be restored by normal blood or by
any stimulating means whatever.
The effects of indaconitine t are strikingly similar to those of aconi-
♦ Studien ilber EerzgifU. t Archwf, Exper, Path,, Bd. xrv.
X The "Pharmacology of Indaconitine," by J, Theod. Cash, M.D., and
Wyndham R. Dunstan, M.D,, Proc. Roy, Soe,, vol. Ixxvi
1 428.]
ACOHITIKB.
369
tine ; the phases of alowing of the pulse and marked quiokeumg and
enbfteqiient arhythmia due to inoo-ordinate aotiOD of auricles and yen- '
toioles are all present *06 mgrm. adaiinistered to etherised cats subcu-
tancKDuBly cverj forty-five minutes was fatal seventy minutes after tbo
third dose,
1st injection. Temporary acceleration, then slowing of the pulse
and respiration, moderate fall of arterial pressure*
2Dd injection. Similar effect^ but no aeoeleratton of pulse or re<
spiration,
3rd injection. Great acceleration of heart heats. Immediately
before death, when Mood- pressure ^ 28 mm., the rhythm l>ecame regular.
In the earlier part of this period vagus stimulation coordinated the
action of the auricles aud ventriclcsg temporarily raising the blood-
prcssaro, hut this effect was It^t later. Splanchnic reaction waa ne?er
entirely abolished.
Artificial respiration prolonged life for over twenty minutes; O'Ol
mgrm, per kilo, of atropine sulphate fully antagonised 0*09 rngrm. per
kilo, of indaconitiue.
Bikhaconitine acts quite similarly, save that its action on the respira-
tion is stronger than that of aconitiuei
Birdfi. — There is a discrc]mncy in the descriptions of the action of
aconitine on liirds. L, v. Praag thought the respiration and circulation
but little affected at first ; while Ach^charumovr witnessed in pigeons
dyapnooa, dilatation of the pupils^ vomiting, shivering, and paresis. It
may be taken that the usual symptoms observed are some difficulty in
breathing, a diminution of temperature, a loss of muscular power
generally (but not constantly), dilatation of the pupils, and conndsions
before death.
Mammals. — The effects vary somewhat, according to the dose. Very
krge doses kill rabbits rapidly. They fall on their sides, are violently
convulsed, and die in an asphyxiated condition ; but with smaller doeee
the phenomena first observed are generally to be referred to the respira-
tion. Thus, in an experiment on the horse, l)r* Harley found that the
subcutaneous administration of *6 mgrm, ('01 grain) caused in a weakly
eolt some acceleration of the pulse and a partial paralysis of the dilator
narium. Double the cjuantity given to the same animal some time
after caused, in six hours and a Imlf, some muscular weakness, and an
evident respiratory trouble. The horse recovered in eighteen houm,
2 '7 mgrms, (t/^ grain) given in the Bamo way, after a long interval of
UmBf caused, at the end of an hour, more prouounced symptoms ; the
pnlse, at the commencement 50, rose in an hour aud a half to C8, then
the respiration became audible and ditBcult. In an hour and three-
quarters there were groat restlessneBS and diminution of muscular power,
24
370 POISONS: THEIR EFFECTS AND DETECTION. [§429-431.
Two hours after tho injection the muscular weakness increased so much
that the horse fell down ; he was also convulsed. After eight hours he
began to improve. In another experiment, 32*4 mgrms. (J grain) killed
a sturdy entire horse in two hours and twenty minutes, the symptoms
commencing within the hour, and consisting of difficulty of breathing,
irregularity of the heart's action, and convulsions.
The general picture of the effects of fatal, but not excessive, doses
given to dogs, cats, rabbits, etc., resembles closely that already described.
The heart's action is at first slowed, then becomes quick and irregular ;
there is dyspnoea, progressive paralysis of the muscular power, convul-
sions, and death in asphyxia. Vomiting is frequently observed, some-
times salivation, and very often dilatation of the pupil. Sometimes
the latter is abnormally active, dilating and contracting alternately.
Diarrhoea also occurs in a few cases. Vomiting is more frequent
when the poison is taken by the mouth than when administered
subcutaneously.
§ 429. Statistics. — During the ten years ending 1903 there were
recorded in England and Wales 25 accidental deaths from the various
forms of aconite (22 males, 3 females) ; and 23 suicidal deaths (16 males,
7 females) from the same cause, which makes a total of 48.
§ 430. Effects on Man. — Eighty-seven cases of poisoning by aconite
in some form or other, collected from European medical literature, com-
prise only 2 cases of murder, 7 of suicide, and 77 which were more or
less accidental. Six of the cases were from the use of the alkaloid
itself ; 10 were from the root ; in 2 cases children eat the flowers ; in
1, the leaves of the plant were cooked and eaten by mistake ; in 7, the
tincture was mistaken for brandy, sherry, or liqueur; the remainder
were caused by the tincture, the liniment, or the extract.
§ 431. Poisoning by the Boot. — A case of murder which occurred
some years ago in America, and also the Irish case which took place in
1841 {Reg, v. M*Con7cey), were, until the trial of I^mson, the only
instances among English -speaking people of the use of aconite for
criminal purposes ; but if we turn to the Indian records, we find that it
has been largely used from the earliest times as a destroyer of human
life. In 1842 a tank of water destined for the use of the British army
in pursuit of the retreating Burmese, was poisoned by intentional con-
tamination with the bruised root of Aconitum ferox; it was fortunately
discovered before any harm resulted. A preparation of the root is used
in all the hill districts of India to poison arrows for the destruction of
wild beasts. A Lepcha described the root to a British officer as being
** useful to sportsmen for destroying elephants and tigers, useful to the
rich for putting troublesome relations out of the way, and useful to
jealous husbands for the purpose of destroying faithless wives." From
§ 431]
ACONTTrNE.
^7^
the recorded cases, the powdered root, miKod with food, or the same
substanee Bteeped tn spirituous liquor, is usually the part ohoseii for
administnitioii. In M^Conkej^Bcasc, the man^s wife purchrtaed powdered
aconite root, mixed it with pepper^ and strewed it over some greens^
which she cooked and gave to him. The man comphiined of the sharp
taste of the greens, and soon after the meal vomited, and sufferod from
purging, hecanie delirious with lockjaw, and clenching of the hands;
lie died in ahout three hours. The chief noticeable post-mortem
appearance was a bright red colour of the mucous membrane of
the stomach.
The symptoms in this ease were, in some respects^ different from those
met with in other caaea of poisoning bj the root. A typical case is given
by Dr, Che vers {op. ciL\ in which a man had taken by mistake a small
portion of aconite root. Immediately after chewing it he felt a sweetish
taste, followed immediately by tingling of the lips and tongue, numbness
of the face, and severe vomiting. On admission to hos[iital he was
eitremely restless, tossing ins limbs about in all directions and constantly
changing his position. He complained of a burning sensation in the
stomacb, and a tiughng and numbness in every part of the liody,
excepting his legs. The tingling was specially marked in the face and
tongue — so much ao that he waa constantly moving the latter to and fro
in order to scratch it against th^teeth, lletcliing and vomiting occnrred
almost incessantly, and ho constantly placed hh hand over the cardiac
region. His face w^ia anxious, the eyes an tl used, the lips pale and
exsanguine, the eyelids swollen, moderately dilated, and in^^enslble to
the stimulus of light ; the respiration was laboured, 64 in a minute ; the
pulse 66, small and feeble. There was inability to walk from loss of
muscular power, but the man was perfectly conscious. The stomach-
pump was used, and albumen and milk administered. Three and thiee-
quarter hours after taking the root the Hjmptoma were increaaed in
severity. The tongue was red and swollen, the pulse intermittent, feeble,
and slower The tingling and numbness had extended to the legs, On
cKaminiug the condition of the I'lternal sensibility with a pair of scissors,
it was found that, on fully sepamting the blades and bringing the points
in contact with the skin over the arms and forearms, he felt thorn as
one, although they were A inches apart. But the sensibility of the
thighs and legs was less obtuse, for he could feel the two points distinctly
when they were 4 inches apart, and continued to do so until the distance
between the points fell short of !3| inches, Hci began to improve about
the ninth hour, and gradually recovered, although he auftered for one
or two days from a slight diarrhoea. Ass in the case detailed (p, 373),
no water was passetl for a long time, as if the bladder early lost
its power.
372 POISONS : THEIR EFFECTS AND DETECTION, [§ 432.
§ 432. Foisomng by the Alkaloid Aconitine. — Probably the earhest
instance on record is the case related by Dr. Golding Bird in 1848.*
What kind of aconitine was then in commerce is not known, and since
apparently a person of considerable social rank was the subject of the
poisoning, the case has been imperfectly reported. It seems, however,
that, whether for purposes of suicide, or experiment, or as a medicine,
two grains and a half of aconitine were swallowed. The symptoms were
very violent, consisting of vomiting, collapse, and attacks of muscular
spasm ; the narrator describes the vomiting as peculiar. " It, perhaps,
hardly deserved that title ; the patient was seized with a kind of general
spasm, during which he convulsively turned upon his abdomen, and with
an intense contraction of the abdominal muscles, he jerked out, as it
were, with a loud shout the contents of his stomach, dependent appar-
ently on the sudden contraction of the diaphragm.'' On attempting to
make him swallow any fluid, a fearful spasm of the throat was produced ;
it reminded his medical attendants of hydrophobia. The patient recovered
completely within twenty-four hours.
One of three cases reported by Dr. Albert Busscher,t of poisoning
by aconitine nitrate, possesses all the exact details of an intentional
experiment, and is of permanent value to toxicological literature.
A labourer of Beerta, 61 years of age, thin, and of somewhat
weak constitution, suffered from neujpalgia and a slight intermittent
fever ; Dr. Carl Meyer prescribed for his ailment : —
R Aconiti Nitrici, 2 grm.
Tr. Chenopodii Ambrosioid., 100 grms. M.D.S.
Twenty drops to be taken four times daily. The patient was instructed
verbally by Dr. Meyer to increase the dose until he attained a maximum
of sixty drops per day.
The doses which the man actually took, and the time of takitig them,
are conveniently thrown into a tabular form as follows : —
7 P.M., 5 drops equal to aconitine nitrate, *4 mgrm.
^ 1-6 ,.
1-6 „ ^
1-6 „
1-6 „
,, 7. March 16, 10 p.m., 10 ,, „ „ '8 „
In the whole seven doses, which were distributed over forty-eight hours,
he took 9-2 mgrms. (-14 grain) of aconitine nitrate.
On taking dose No. 1, he experienced a feeling of constriction
* Laneclf vol. i. p. 14.
t IjUoxicfUumafdllc dnrch Aconitin Nitricum Gallicufiif nebst Sections Beriehi,
von Dr. Albert Busscher ; Berl. klinischc Wochenschrift, 1880, No. 24, pp. 388, 856
No.
1. March 14,
7 P.M.
5
2. „
9 P.M.
20
3. March 15,
8 a.m.
20
4. ,,
11 A.M.
20
5. „
4 P.M.
20
6. „
9 P.M.
,20
§ 432]
ACONITINE.
373
{Zusammemiehtinif)^ aud burniug spreading fi'oui the tiioiitli to the
atomaclij but this after n, little while eubsided. Two houra afterwards
be took No. 2, four times the quantity uf No* L This produced the
Banio ituniediate symptoms, but soon he became cold, aud felt very ill.
He had an anxioua opi>ressive feeliug about the cheat, with a buruiug
feeUug about the throat ; the whole bocly waa covered with a cold
sweat, his sight failed, he beeatue giddy, there was excessive muscular
weakuesu, he felt us if he had lost ];K)wer over hia limlm, he iiad great
difficulty in breathing. During thii night he passed no water, nor
felt a desire to do bo» About half an hour after he hiul takcu the
medicine, ho began to vomit violeutly, whieh relieved him mu€h ; he
then fell asleep.
Dose No, 3, equal as before to I "6 mgrm.^ he took in the morning,
Ue experienced almoat exactly the same symptoms as before, but con-
vulsions were added, especially of the face ; the eyes were also prominent;
twenty minutes alter he had taken the dose vomiting came ou^ after
which he again felt better.
He took dose No. 4, and had the same repetition of symptoms, but
in the interval between the doses he felt weaker and weaker ; he had no
energy, and felt as if piralysed. Ko, 5 was taken, and produced, like
the others, veniiting, after which he felt relieved. Neither lie nor his
wife seemed all this time to have had any suspicion that the medicine
was really doing harm, but thought that the effects were due to its
constant rejection by vomiting, so, in order to prevent vomiting with
No. 6, he drank much mAd water. After thus taking the medicine,
the patient seemed to fall into a kind of slumber, with great restlessness ;
about an hour and a half afterwards he cried, ** 1 am chilled ; my heart,
my heart is terribly cold- I am dying; I am poisoned/* Hia whole
body was covered with perspiration j he was now couvulned, and lost
sight and hearing ; his eyes were shut, his lips cracked and dry, he
could scarcely open his mouth, and he was extremely cold, and thought
he was dying. The breathing was difficult aud rattling : from time to
lime the muscular apa^ms came on. His wife now made a large quantity
of hot strong black tea, which she got him to drink with great difficulty ;
although it waa hot, tie did not know whether it was hot or cold. About
five minutes afterwards he vomited^ and did so several timea; this
apparently relieved him, and he sank into a quiet sleep; during the
night he did not urinate. In the morning the wife went to Dr. Carl
Meyer, described tlie symptoms, and accused the medicine. So convinced
was Dr. Meyer that the medicine did not cause the symptoms, that he
poured out a quantity of the same, equal to 4 mgrms, uf aconitlae
nitrate, aud took it himself m some wine, to show that it waa harmlesa^
and ordered them to go on with it* The mihappy physician died of
374 POISONS : THEIK EFFECTS AND DETECTION. [§ 433.
aconitine poisoning five hours after taking the medicine.^ In the
meantime, the woman went home, and her husband actually took a
seventh, but smaller dose, which produced similar symptoms to the
former, but of little severity ; no more was taken.
The absence oi diarrhma, and of the pricking sensations so often
described, is in this case noteworthy. Both diarrhoea and formication were
also absent in a third case reported by Dr. Busscher in the same paper.
§ 433. The most important criminal case is undoubtedly that of
Lamson: — At the Central Criminal Court, in March 1882, George
Henry Lamson, surgeon, was convicted of the murder of his brother-
iu-law, Percy Malcolm John. The victim was a weakly youth of 18
years of age, paralysed in his lower limbs from old standing spinal
disease. The motive for perpetrating the crime was that Lamson,
through his wife (Malcolm John's sister), would receive, on the death of
his brother-in-law, a sum of £1500, and, according to the evidence, it is
probable that there had been one or more previous attempts by Lamson
on the life of the youth with aconitine given in pills and in powders.
However this may be, on November 24, 1880, Lamson purchased 2
grains of aconitine, came down on December 3 to the school where the
lad was placed, had an interview with his brother-in-law, and, in the
presence of the headmaster, gave Malcolm John a capsule, which he
filled then and there with some white powder, presumed at the time to
be sugar. Lamson only stayed altogether twenty minutes in the house,
and directly after he saw his brother-in-law swallow the capsule, he left.
Within fifteen minutes Malcolm John became unwell, saying that ho
felt as if he had an attack of heartburn, and then that he felt the same
as when his brother-in-law had on a former occasion given him a quinine
pill. Violent vomiting soon set in, and he complained of pains in his
stomach, a sense of constriction in his throat, and of being unable
to swallow. He was very restless — so much so that he had to be
restrained by force from injuring himself. There was delirium a few
minutes before death, which took place about three hours and three-
quarters after swallowing the fatal dose. The post-mortem appearances
essentially consisted of redness of the greater curvature of the stomach,
and the posterior portion of the same organ. In one part there was a
little pit, as if a blister had broken; the rest of the viscera were
congested, and the brain also slightly congested.!
• The symptoms suffered by Dr. Meyer are to be found in Neder, Tijdschrift van
Cfeneeskwide, 1880, No. 16.
t To these cases of poisoning by the alkaloid aconitine may be added one recorded
in Bouchardat's Annuaire de TkdrapeiUie, 1881, p. 276. The case in itself is of but
little Importance, save to illustrate the great danger in permitting the dispensing of
such active remedies of varying strength. A gentleman suffering from *' angina
pectoiis" was prescribed ** Hottot's aconitine" in granules, and directed carefully to
§ 434-436.]
ACONITIHK.
375
§ 434, The symptoms of poisoning by the tincture, extract, or other
preparation, do not ditfor from those detailed. As uuuauul effectai,
occasioually seoti, niaj be noted profound uneonsciousness lasting for two
houra (Topham's case)^ violent twitching of the muBcles of the face,
opisdiotonoa^ and violent convulsions. It h important to distinguish
the sj^mptomi} which are not cons tan t from those wliich are eonBtaul, or
nearly so* The tingling and creupjng sensations about the tongue,
throat, lips, etc,, are not constant : they certainly were not present in the
remarkable German case cited at p. 373. Speaking generally, they seem
more likely to occur aft«r taking the root or the ordinary medicinal pre-
parations. A dilated state of the pupil is by no means constant, and
not to be relied upon. Diarrhoea is t^en after taking the root or tincture
by the stomach, but i^ often absent. In short, the only constant eymp-
toma are difficulty of breatlnng, progressive musoular weakoeea, generally
vomiting, ami a weiik intermittent pulse.
§ 435. Physiological Action. — Ac on i tine, acconiing to Dr. S. Ringer,
is a protoplasmic poison^ destroying the functions of idl nitrogenous
tissue— first of the central nervous aystem^ next of the nerves, and last
of the nniaclea. Aconitine without doubt acts powerfully on the heart,
ultimately paralysing it ; there is iirst a slowing of the pulse^ ascribed to
a central excitation of the vagus ; then a quickening, due to paralysis of
the peripheral termination of the vagus in the heart ; lastly, the heart*a
action becumes slow, irregular, and weak, and the blood-pressure ainkB.
The dyspncoa and convulsions are the usual result, seen among aU warm-
blooded animals, of the heart atfection, Plugge found that the motor
nerves, and more especially their intra-muscular terminatitms, were
always paralysed; but if the dose was small the paralysis might be
incomplete. Bu^hm and Wartmann, on the other hand, considered that
the motor paralysis had a central origin, a view not supported by recent
research. The action of aconitine in this way resembles curare. The
muscles themselves preserve their irritability, even after doses of aconi-
tine which arc five to ten times larger than those by which the nerve
terminations are paralyjaed,
§ 4^ti. Post-mortem Appearaucee.^ — Among animals (mammak) the
appearanee^ most constantly ohaerved have been hypersemia of the
iucreafifl the di:»s(! nji to f*jar grAiiulo^, according to thi* elf cat jiroducoii. The pro-
scrvpticm was tnkeu to n phamiiicifit, who, lustetui i>f aupiilying Hottj>tH oconitine,
Bapplicd wms other of unknown origin. T!ii> medidne was t&ken daily, &nd tho
dose raided Ui foojr granuks, which wi^ro taken wiUi heoefit until tlie whole wae
eihAUtited. He then went to Uottot^s f^at&hliiilinii'tit, »ud IimI o, freah aupply, pi^e*
samnbly of thi^ same fluh»tano€, but a very little time art€r he hM t&kf>u hii^ ustial
dose of four granules, he aTi!!t!i'i?d ffona symptoms tif aconititi*» poisouingj hfAdachc,
vertigo^ feeblenesa of the v^icc, and musduUr wt^akues-?^ and was darminj^Iy ilh He
recoyeriKl afUr Hami houn of lUiMdii^ul treatment.
376 POISONS : THEIR EFFECTS AND DETECTION. [§ 437.
cerebral membraues aud brain, a fulness of the large veins, the blood
generally fluid — sometimes hypersemia of the liver, sometimes not.
When aconitine has been administered subcutaneously, there have
been no inflammatory appearances in the stomach and bowels.
In the case of Dr. Carl Meyer, who died in five hours from swallow-
ing 4 mgrms. of aconitine nitrate, the corpse was of a marble paleness,
the pupils moderately dilated. The colour of the large intestine was
pale; the duodenum was much congested, the congestion being most
intense the nearer to the stomach ; the mucous membrane of the stomach
itself was strongly hyperasmic, being of an intense red colour ; the spleen
was enlarged, filled with much dark blood. The liver and kidneys were
deeply congested, the lungs also congested ; the right ventricle of the
heart was distended with blood ; in the pericardium there was a quantity
of bloody serum. The brain was generally blood-red ; in the cerebral
hemispheres there were several large circumscribed subarachnoid extra-
vasations. The substance of the brain on section showed many red
bloody points.
In a case recorded by Taylor, in which a man died in three hours
from eating a small quantity of aconite root, the only morbid
appearance found was a slight reddish-brown patch on the cardiac end
of the stomach, of the size of half a crown ; all the other organs being
healthy.
§ 437. Separation of Aconitine from the Contents of the Stomach
or the Organs. — It would appear certain thai in all operations for the
separation of aconite alkaloids (whether from the organic matters which
make up the plants or from those constituting animal tissues), mineral
acids and a high heat should be avoided. A 1 per cent, sulphuric acid
does not, however, hydrolyse, if acting in the cold, so that the process
already given, p. 363, may be followed.
The chemical examination in the Lamson case was entrusted to Dr.
Stevenson, assisted by Dr. Duprd, and was conducted on the principles
detailed. The contents of the stomach were treated with alcohol, and
digested at the ordinary temperature of the atmosphere ; the contents
were already acid, so no acid in this first operation was added. The mix-
ture stood for two days and was then filtered. The insoluble portion
was now exhausted by alcohol, faintly acidulated by tartaric acid, and
warmed to 60'' ; cooled and filtered, the insoluble part being washed again
with alcohol. The two portions — that is, the spirituous extract acid
from acids pre-existing in the contents of the stomach, and the alcohol
acidified by tartaric acid — were evaporated down separately, exhausted
by absolute alcohol, the solutions filtered, evaporated, and the residue dis-
solved in water. The two aqueous solutions were now mixed, and shaken
up with ether, which, as the solution was acid, would not remove any
§438.]
ATROPtNK
m
alk&loid; but niiglit rcanivo various iDipiiritie^t \ tho ruBidue^ after being
tliim i^a [tidily purilicd by otber, wluj iilkiLlisod bj sudit^ carbonate, and tho
alkaloid ij attracted by a uibtturc uf cldurulomi aiid ether. Oil OTiiponi-
tion of tbe chloroform and etberj fchij resultiug extract waij tested
pliyaiologically by tttsthig, and also by mjectiona hi to mice. By ineaiiB
anulogoufi to those duUiiled^ tlie exjiertd ii^ulated atouithiu from the vomit,
the stomachy liver, spleen, and tiriue, and aliio a minute tiuantity of mor-
phine, which bad been administered to the pationt to tjubdue the pain
during hia fatjil attack. When taetetl, thu i>ecuhar uumbin^% tingling
sensation lajstcd many houra. Tliese extracia svere relied upon im e vide nee,
for their physiological effect was identical with that produced by aconi-
tine. For exam pi o, the ei tract obtain t-d from the urine caused symp-
toms to commence in a moui^e in two iinuutes, and death in tliirty
minutes, and the symptoms observed by injecting a mouse with known
aconitine coincided in every particular with the symptoms produced by
the extraction from the urine.
With regard to the manner of using '* lif^ imt$^^ since in most cases
extremely small quantities of the active principle will have to be identi-
fied, the choice is limited to small arnmals, and it is better to use mice or
birds, rather than reptiletj. In the Lanison case, subcutaneous injeetions
were employed, but it is a question whether there is not less error m
admin istoriug it by the month. If two hoaltby mice are taken, and the
one fed with a little meat, to which u weighed quantity of the extract
under experiment has been added, while to the other some meal mixed
with a supposed equal dose of aeon i tine is given, then the symptoms
may be compared ; and several olijections to any openitive proceeding
on such small animals are obviated. It Is certain that any extract which
causes distinct nombness of the lips will couUiu enough of the poison to
kill a small bird or a mouse, if admitiistered in tho ordinary way**
VL— The Mydriatic Group of Alkaloids— Atropine—
Hyoscyamine— Solanine— Cytisine.
g 438, The family of the Solanacem contaios several plants which
yield certain alkaloids having very similar properties, the chief amongBt
which are the following : —
Atropine, Uyoscy amine, Pse\^dohyaflcyamitie, Hyoscine, all haviiig
* Dr. A. Langoard has dc^rihed iks\^im of aconite root, anmod by the Japftneoe
K(tM^-mU. Fixtm his a£|M?ritiii}tiiB on frogB Aiid mUljititf its pb jiiologioftl. Msttoa
BBDiiiB not to dilf^r hum tlm.i at ifcouitiltn^ ^aUf^mWy.— Uibtr €im AH i/bpafit«cJU
Aktmii-kn<en, KUaa-BsSi tjatannit u, iiher daa m defudbeA Viftk&fnmffnd* AkimUin*
Firehowi Archie, B. l^uix. p. 229, 1880.
378
POISONS: THBIB EFFECTS AND DBTECTION.
[§ 439-
the formula Ci^HggNOg; Atropamine, CJ7H21NO.2; Belladonnine,
C17H21NO2 ; and Scopolamine, Cj^HgiNO^.
§ 439. Atropine (Daturine), C17H23NO3. — This important alkaloid
has been found iu all parts of the Atrapa belladoima^ or deadly night-
shade, and iu all the species of Datura,
The Atropa helladomia is indigenous, and may be found in some parts
of England, although it cannot be said to be very common. It belongs
to the Solanaceo}, and is a herbaceous plant with broadly ovate entire
leaves, and lurid purple axillary flowers on short stalks ; the berries are
violet-black, and the whole of the plant is highly poisonous. The juice
of the leaves stains paper a purple colour. The seeds are very small,
kidney-shaped, weighing about 90 to the grain ; they are covered closely
with small round projections, and are easily identified by an expert, who
may be supposed to have at hand (as is most essential) samples of different
poisonous seeds for comparison. The nightshade owes its poisonous
properties to atropine.
The yield of the different parts of belladonna, according to
Gunther,* is as follows : —
TABLE SHOWING THE ALKALOIDAL CONTENT OF VARIOUS PARTS
OF THE BELLADONNA PLANT.
Leaves,
sulk,
Ripe fruit.
Seed,
Unripe fruit,
Root,
, Quantity of Alkaloids in the
Fresh Substance, per cent.
(a) By
Weighing.
I
0*2022
0*0422
0-2128
0-26676
0-1870
0-0792
(6) By
Titration.
0-20072
0-20268
0-i930
Quantity of Alkaloids in the
Dry Substance, per cent.
(a) By
Weighing.
0-838
0-146
0-821
0-407
0-955
0-210
(6) By
Titration.
0-828
0-805
0-955
Atropine appears to exist in the plant in combination with malic
acid. According to a research by Ladenburg, hyoscyamine is associated
with atropine, both in the Belladonna and Datura plants. t
From a research by W. SchUtte,| it appears that the younger roots
of wild belladonna contain hyoscyamine only, whilst the older roots
contain atropine as well as hyoscyamine, but only in small proportion ;
the same was observed to be the case i]j^ the older cultivated roots.
* Pharm. Zeitschr. /. Rmsl, Feb. 1869 ; Dragendorff, Die ch^miscJie Werth
bcstimmvng einiger stnrkwirkcndcn Drogucn, St. Petersburg, 1874.
t Bcr, der dentsdi. chem. Ocs.y Bd. xiii.
t Arch, Pharm, f ccxxix. 492-531 ; Joum. Chem. Soc, (abstract), February
1892, 231.
§ 440.]
DATUKA STRAM0I3IUM.
379
Tiie ripe berries of Airojm heJlxMhmia nujra and aiha contain
chiefly atropine, hyosjcyamine and & little acopulumine ; aeeda of Datura
BlramonimH also contain atropine, Uyoscjamine, and a little acopolaruine.
^ 440, The Battira Stramomum or Thorn apple is ako indigenous
in tlio British Lslandij, but, like belhidoniia, it cannot be coniiderctl a
common plant. Datura belongs to the Solanacete ; it grows from 1 to
2 foet in height^ and i^ found in wa^te plauei. The leaves arc suiooth,
the flowers white ; the fruit is densely spinous {hence the naniu thorn-
apple )j and is divided into four dissepiuieuts below, two at the top, and
containing many seeds.
The DalurUj or the i>/£^t^ra- plan ts» of India have in that oonntry a
great toiicological significance, the white-flowered datura, or Datura
alba, growing plentirully in wast© places, especially alwut Madras,
The purple-coloured variety, or Daiura J'astumat is also common in
certain parts. There is a third variety, the Datura iU'roit^ found about
the coast of Malabar, The seeds of the white datura have been mis-
taken in India for those of capsicum. The following are some of the
most marked differences ; —
Seki>3 of the Common or
White Daitjra.
(1) Outline angular.
(2) Attached to the placenta by
a large, white, fleshy mass separat-
ing easily, leaving a deep furrow
along hair the length of the seed's
concave border.
(3) Surface scabrous, almost
reticulate, except on the two com-
pressed sides, where it has become
almost glaucous from pressure of
the neighbouring seeds.
(4) Convex border thick and
bulged with a longitudinal depres-
sion between the bulginga^ caused
by the compression of the two sides,
(5) A snitable section shows the
embryo curved and twisted in the
fleshy albumen*
(G) The taste of the datura seeds
ia very feebly bitter. The watery
decoction causes dilatation of the
pnpih
Sebds of Cai^icum.
Outline ronnded,
Attadied to the placenta by a
cord from a proniinonce on tlie
concave border of the seed.
Uniformly scabrous, the sides
being equally rough with the
borders.
Convex border thickened, but
uniformly rounded.
The embryo, exposed by a suit-
able section, is seen to resemble in
outline very closely the figure 6*
The taste of cttj>aicum is pungent;
a decoction irritates the eye much,
but does not cause dilatation of the
pupil.
380 POISf>NS : THEIR EKKECTS AND DETECTION. [§441,442.
The identity of the active principle in both the datura and bella-
donna tribes is now completely established.*
§ 441. Pharmacentical Preparations. ^(a) Of the leaves. Extract
of BelladonncL — This contains, according to Squire, t from 0-73 to 1*7
per cent, of total alkaloids. Belladonna Juice (succus beHadcnme). —
Strength in alkaloid about 0*05 per cent. Tincture of Belladonna. —
Half the strength of the juice, and therefore yielding about 0*025 per
cent, of alkaloid.
(b) Belladonna Boot, — Belladonna plaster contains 20 per cent of
alcoholic extract of belladonna. Alcoholic Extract of Belhtdonna, — This
extract, according to Squire^* contains from 1*6 to 4*45 per cent, of
alkaloid. Belkulonna liniment is an alcoholic extract with the addition
of camphor ; its strength is about equal to 0*2 per cent of alkaloid.
Belladonna ointment contains about 10 per cent, of the alcoholic extract.
(c) The Alkaloid, — Atropine Discs {lamellw atropine), — These are
discs of gelatine, each weighing about ^ grain, and containing for
ophthalmic use ^^^q grain of atropine sulphate. Similar discs are
made for hypodermic use, but stronger; each containing ^hs gv^^*
SoltUion of Atropine SulpJuxte. — Strength about 1 per cent. Atropine
Ointment. — Strength about 1 in 60, or 1*66 per cent, of atropine.
(d) Stramonium. — An extract of the seeds is officinal in Britain;
the alkaloidal content is from 1*6 to 1*8 per cent. There is also a
tincture which contains about 0*06 per cent, of alkaloid.
§ 442. FropertieB of Atropine, C17H23NO3. — Atropine, hyoscyamine,
and hyoscine have all the same formula, but differ in their molecular
constitution. Atropine on hydrolysis, either by heating it with hydro-
chloric acid or baryta water, is decomposed into tropine and inactive
tropic acid : —
CnH23N03 + H,0 = CgHj^NO + C.H.oO,
Atropine Tropine. ''^^
On the other hand, by heating tropic acid and tropine together,
atropine is regenerated.
Tropic acid crystallises in prisms which melt at in^-llS**.
Dehydrating agents convert it into atropic acid (a-phenyl-acrylic
acid),
<CHaOH x,CHo
-> CeHB-Cf +H2O
COOH ^COOH
Tropic acid. Atropic acid.
• See a research by Ernst Schmidt, '* Ueber die Alkaloide der Belladonna- Wurzel
a. des Stechapfel-Samens," JDu;&. Annl., Bd., ccviii. 1881.
t Camjpaniou to the British Fharmacopanaf 1894.
§ 443] ATROPINE. 381
Atropic acid is an isomer of cinnamio acid ; it crystallises in tablets
which melt at 106•5^
Tropine is a white crystalline strongly alkaline substance, melting
at 63**, and boiling at 233**. It has no action on polarised light. It
is soluble in water, alcohol, and ether, and gives precipitates with tannic
acid, iodised hydriodic acid, Mayer's reagent, gold chloride, and
mercuric chloride.
As a result of the researches of Ladenburg, Merling, and Willstatter,
tropine has been found to contain the pipcridine, pyrrolidine, and hepta-
methylene nuclei united thus : —
H.
H H
-C C
N-CHs ^CHOH
H2C C C
H H2
Tropine.
Thus the constitutional formulae of atropine (as well as hyoscyamine)
may be represented as follows : —
H.
H H
^ ^ CHaOH
/ \ I
/N-CH3 \CH— O— CO— CH
\ / I
H Ha
Atropine.
Atropine forms colourless crystals (mostly in groups or tufts of
needles and prisms), which are heavier than water, and possess no
smell, but an unpleasant, long-enduring, bitter taste. The experiments
of K Schmidt place the melting-point between 115' and IIS'S". It is
said to sublime scantily in a crystalline form, but we have been unable
to obtain any crystals by sublimation ; faint mists collect on the upper
disc, at about 123", but they are perfectly amorphous.
Its reaction is alkaline ; one part requires, of cold water, 300 ; of
boiling, 58 ; of ether, 30 ; of benzene, 40 ; and of chloroform, 3 parts
for solution. In alcohol and amyl alcohol it dissolves in almost every
proportion.
§ 443. Tests. — Atropine mixed with nitric acid exhibits no change
of colour. The same is the case with concentrated sulphuric acid in
the cold ; but on heating, there ensues the common browning, with
development of a peculiar odour, likened by Gulielmo to orange flowers,
by Dragendorff to the flowers of the Prunus padus, and by Otto to the
Spircea vlmaria — a sufiicient evidence of the untrustworthiness of this
382 POISONS : THEIR EFFECTS AND DETECTION. [§ 443.
as a distinctive test. The odour, indeed, with small quantities, is
certainly not powerful, nor is it strongly suggestive of any of the
plants mentioned. A far more intense odour is given off if a speck of
atropine is evaporated to dryness with a few drops of strong solution of
baryta, and heated strongly ; the scent is decidedly analogous to that
of hawthorn-blossom, and unmistakably agreeable.
By heating a small quantity of atropine, say 1 ragrm., with 2
mgrms. of calomel and a very little water, the calomel blackens, and
crystals may be obtained of a double salt; this reaction is, however,
given also by hyoscyamine and homatropine. Mercuric potassium
iodide solution, and mercuric bromide solution give amorphous pre-
cipitates, which, after a time, become crystalline, and have character-
istic forms.
A solution of iodine in potassium iodide gives a precipitate with
acidulated solutions of atropine in even a dilution of 1 : 10,000.
Tannin precipitates, and the precipitate is soluble in excess of the
reagent. If atropine be dissolved iu dilute hydrochloric acid, and a 5
per cent, of gold chloride solution be added, a precipitate of a gold
compound (CiYHgjNOgHClAuClg) separates. The precipitate is in the
form of rosettes or needles; melting-point 137°. On boiling it with
water, however, it melts into oily drops, and this peculiar behaviour
distinguishes it from the analogous salt of hyoscyamine, which does
not melt in boiling water. The percentage of gold left on a combustion
of atropine gold chloride is 31*35 per cent. 100 parts of the gold salt
are equal to 46*2 of atropine. A platinum salt may also be obtained,
(Ci7H2jN08HCl)2PtCl4, containing 29*5 per cent, of platinum.
Vitali's test is important ; it consists in the production of a violet
colour with alcoholic potash after oxidation.
The test may be applied as follows : — Equal parts, say 1 mgrin., of
nitrate of sodium and of the substance to be tested, are rubbed together
with a glass rod on a porcelain slab, and to this mixture 1 drop of
sulphuric acid is added ; the mixture is spread out in a thin film ;
upon this is strewn a little powdered potassium hydrate, and finally
1 drop of alcohol added ; a violet colour is produced which passes into
a fine red ; according to the author of the test, 0*001 mgrm. of atropine
sulphate can by this test be detected. Strychnine obscures this
reaction.
Atropine, homatropine, and hyoscyamine show an alkaline reaction
with phenolphthalein : atropine and homatropine give a precipitate
with HgClg. Hyoscyamine, not cocaine, precipitates HgClg, and is
alkaline to litmus, but not to phenolphthalein. Atropine behaves as
follows: — (I) Sodium nitrate, sulphuric acid, and afterwards sodium
hydroxide, gives a violet colour ; (2) the test as before, but with nitrite
§443-1
ATROPINK.
383
instead of nitrate, givee an orange colour, which, on dihition with sodium
hydroxide solution, changes to red, violet, or lilac ; (3) when heated
with glacial acetic acid and etilphuric acid for a sufticient time, a
green ish'je! low fluorescence is produced. — Fliickiger, Pkamh Joum,
Tmm, (3), vol. xvl p. 6OK602.
Vrewen {^eit, /. Musdand^ xxxvi. 723) distinguishei between
hjroaeyamine and atropine by ohtaitiing a crystalline precipitate with
MarmiVg reagent (10 grms. KT and 5 grma CdT, dissolved in 100 ex.
water). A drop of a aolution weakly acidified with sidphnric acid of
either alkaloid tested with a tmee of Marmi'^s reagetit develops a
crystalline precipitate. The form of tlie crystals of the Lyoscyatnine
compound diflfera entirely from that of the atropine compound.
The two alkaloids, strychniue and atropine, are not likely to he
often together in tlio human bofly, but that it may sometimes occur
is shown by a caae recorded by h. Fabris.* A patient in the hospital
at Padua had for some time been treated with daily injections of 3
mgrms. of strychnine nitrate ; unfortunately, one day, instead of the
3 mgmis. of strychnine, the same quantity of atropine sulphate was
injected, and the patient died after a few hours, with symptoms of
atropine poisoning*
On chemical treatment of the viscera , a mixture of alkaloids was
obtained which did not give either the reactions? of strychnine or of
atnipirie. To test the |>08stbility of these alkaloids obscuring each
nther*s reactions, mixtures of 3 per cent solutions (the strcngtli of the
injections) of atropine suljihate and strychnine nitrate were mixed
together, and strychnine tested for by the dichromate and sulphuric
acid test.
A mixture of equal parts gave the strychnine reaction very clearly ,
but the atropine rea^stian not at all ; 1 strychnine with 3 of atropine
gave atrychniuo reaction, but not that of atropine ; 1 strycbnine with
4 atropine gave indistinct reactions for both alkaloids; 1 of strychnine
with 5 of atro]>ine gave a momentary atropine reaction, the violet was,
however, almost immediately replaced by a red colour, Vi tali's reaction
was not clearly shown until the mixture was in the proportion of 1> of
atropine to 1 of strychnine, but mixtures in the proportion of 3 strych-
nine and I atropine will give distinct mydriasis.
In such a case, of course, the strychnine should be separated from the
atropine ; this can be effected by precipitating the strychnine as chroma te,
filtering and recovering from the filter the atropine by alkalising and
shaking it out with other.
The atropine may be farther purified by converting it into oxalate,
dissolving the oxalate in as small a qnantity of alcohol as pfjssible, and
• GaxzrUfi^ ixii., i, 347-350.
384 POISONS : THEIR EFFECTS AND DETECTION. [§ 444.
precipitating the oxalate out with ether ; the precipitate is collected,
dissolved in as small a quantity of water as possible, the water made
alkaline, and the base shaken out with ether.
The most reliable test for atropine, or one of the mydriatic alkaloids,
is its action on the iris; a solution of atropine, even so weak as
1 : 130,000, causing dilatation.* This action on the iris has been
studied by Ruyter,t Donders, and von Graefe.
The action is local, taking effect when in dilute solution only on the
eye to which it has been applied ; and it has been produced on the eyes
of frogs, not only in the living subject, but after the head has been
severed from the body and deprived of brain. The thinner the cornea,
the quicker the dilatation ; therefore the younger the person or animal,
the more suitable for experiment. In frogs, with a solution of 1 : 250,
dilatation commences in about five minutes ; in pigeons, seven minutes ;
and in rabbits, ten minutes. In man, a solution of 1 : 1 20 commences
to act in about six to seven minutes, reaches its highest point in from ten
to fifteen minutes, and persists more or less for six to eight days. A
solution of 1 : 480 acts first in fifteen to twenty minutes, and reaches its
greatest point in twenty minutes ; a solution of 1 : 48,000 requires from
three-quarters of an hour to an hour to show its effect. Dogs and cats
are far more sensible to its influence than man, and therefore more
suitable for experiment. If the expert chooses, he may essay the proof
upon himself, controlling the dilatation by Calabar bean; but it is
seldom necessary or advisable to make personal trials of this nature. |
§ 444. Statistics of Atropine Foisomng.— Since atropine is the active
principle of belladonna and datura plants, and every portion of these —
roots, seeds, leaves, and fruit— has caused toxic symptoms, poisoning by
any part of these plants, or by their pharmaceutical or other preparations,
may be considered with strict propriety as atropine poisoning. Our
English death statistics for the ten years ending 1903 record 95 deaths
(45 males and 50 females) from atropine (for the most part registered
under the head of belladonna) ; 29 (or 35 per cent.) were suicidal, the
rest accidental.
The greatest number of the accidental cases arise from mistakes in
pharmacy ; thus belladonna leaves have been supplied for ash leaves ;
the extract of belladonna has been given instead of extract of juniper ;
* De Actione Atropos Belladonna; in Iridenit Traj. ad. Rhen., 1852.
t Arch, Ophihal., ix. 262, 1864.
t A. Ladenbnrg {Compt. Re^vd.^ xc. 92), having succeeded in reproducing atropine
by heating tropine and tropic acid with hydrochloric acid, by substituting various
organic acids for the tropic acid, has obtained a whole series of compounds to which
he has given the name of iro^teines. One of these, hydroxytoluol (amygdalic)
tropeine, he has named homatropijie. It dilates the pupil, but is less poisonous
than atropine.
§445]
ATROPINE.
3SS
the alkaloid itself has been dispensed in mistake for theine ;* a more
curJouB aud marvellously stupid mistake ia one in which it was dispensed
instead of asafoetida (Schauenstein, op. cii.j p. 652)* Further, valerian-
ate of atropine has been accidentallj substituted for quinine Valeriana to,
and Bcbaaensteiu relates a case in which atropine sulphate was admtuiS'
tered Bubcutaneously instead of morphine sulphate ; bnt the result was
not lethal. Many other instances might be cited. The extended use of
atropine as an external application to the eje naturally gives rise to a
few direct and indirect accidents. Serious symptomB have arisen from
the solution reaching the pharynx through the lachrymal duct and nose.
A curious indirect poisoning, caused by the use of atropine as a colly-
rium, is related by Schauenstein.t A person suffered from all the
symptoms of atropine poisoning ; but the channel hy which it had
obtained access to the system was a great mystery, until it was traced
to some coffee, and it was then found that the cook had strained this
coffee through a certain piece of Hnen, which had been used months
before^ soaked in atropine solution, as a colly rium^ and had been cast
aside as of no value.
§ 445. Accidental and Crmiinal Foisoning by Atropine. — ^Extemal
applications of atropine are rapidly absorbed ; e.g.^ if the foot of a rat be
steeped for a little while in a aolntiun of the alkaloid, and the eyes
watched, dilatation of the pupils will soon he observed. If the skin ia
broken, enough may be absorbed to cause death* A case is on record
in which *21 grm, of atropine sulphate, applied as an ointment to the
abraded skin, was fatal.} Atropine has also been absorbed from the
bowel ; in one case, a clyster containing the active principles of 5'2 grms.
(80 grains) of belladoniMi root was administeroil to a wonmn 27
years of age, and caiLsed death. Allowing the root to have been
carefully driedj and to contain *3 1 per cent, of alkaloid^ it would seem
that so little as 10^9 mgrms, (16 grain) may even prove fatal, if left in
contact with the intestinal mucous niemhrano, Bclladoima berries and
stramonium leaves and seeds are oaten occasionally by children. A
remarkable series of poisonings by belladonna berries occurred in London
during the autumn of 1840.
Criminal poisoning by atropine in any form is of excessive rarity in
Europe and America, but in India it has been frightfully prevalent.
In all the Asiatic case^ the substance used has been one of the various
sfjeoies of datura, and mostly the bruised or ground seeds, or a decoction
of the seeds. In 120 eases recorded in papers and works on Indian
toxicology, no less than 63 per cent, of the cases were criminal, 1 9 per
ctnt suicidal, and 18 per cent accidental. In noting these figures,
' Hohl, De Sfftdti Airopini. Dus. i/alk, 1SS3,
t Mnaolikfi's fftiridbttck t Plo«is, BeiiHhn /. CAjV,, 18^,
25
386 POISONS : THEIR EFFECTS AND DETECTION. [§ 446, 447.
however, it must be borne in mind that known criminal cases are more
certain to be recorded than any other cases. The drug has been known
under the Sanscrit name of dhcUoora by the Hindoos from most remote
times. It was largely used by the Thugs, either for the purpose of
stupefying their victim or for killing him ; by loose wives to ensure for
a time the fatuity of their husbands; and, lastly, it seems in Indian
history to have played the peculiar rdle of a state agent, and to have
been used to induce the idiocy or insanity of persons of high rank,
whose mental integrity was considered dangerous by the despot in power.
The Hindoos, by centuries of practice, have attained such dexterity in
the use of the *^ datura" as to raise that kind of poisoning to an art, so
that Dr. Che vers, in his Medical Jurisprudence for India^* declares
that 'Hhere appears to be no drug known in the present day which
represents in its effects so close an approach to the system of slow
poisoning, believed by many to have been practised in the Middle Ages,
as does the datura."
§ 446. Fatal Dose. — It is impossible to state with precision the
exact quantity which may cause death, atropine being one of those
substances whose effect, varying in different cases, seems to depend on
special constitutional tendencies or idiosyncrasies of the individual.
Some persons take a comparatively large amount with impunity, while
others scarcely bear a very moderate dose without exhibiting unpleasant
symptoms. Eight mgrms. {\ grain) have been known to produce
poisonous symptoms^ and '129 grm. (2 grains) death. We may, there-
fore, infer that about '0648 grm. (1 grain) would, unchecked by
remedies, probably act fatally ; but very large doses have been recovered
from, especially when treatment has been prompt.
Atropine is used in veterinary practice, from 32*4 to 64*8 mgrms.
(^ to 1 grain) and more being administered subcutaneously to horses ;
but the extent to which this may be done with safety is not yet
established.
§ 447. Action on Animals. — The action of atropine has been
studied on certain beetles, on amphibia (such as the salamander, triton,
frogs, and others), on guinea-pigs, hedgehogs, rats, rabbits, fowls,
pigeons, dogs, and cats Among the mammalia there is no essential
diflference in the symptoms, but great variation in the relative sensi-
bility; man seems the most sensitive of all, next to man come the
camivora, while the herbivora, and especially the rodents, offer a
considerable resistance. According to Falck the lethal dose for a rabbit
is at least '79 mgrm. per kilo. It is the general opinion that rabbits
may eat sufficient of the belladonna plant to render their flesh poisonous,
and yet the animals themselves may show no disturbance in health ; but
* Dr. Chever's work contains a very good history of datura criminal-poisoning.
§ 448]
4fB0HMK
387
thia mtist not be considered adcKitiately established. Speaking verjr
geneitiny, the higher the animal organisation the greater the BonBibility
to atropme. Frogs are affected in a peculiar manner. Aecording to
the researches of Fra^er,* the auiroal is first paralysed, and some hours
after the admin istratiou of the poison lies motionless, the oulj i^igns of
life being the existence of a slight movement of the heart and muscular
irritability. After a period of from forty- eight to seventy-two hours,
the fore litnbs are seized with tetanic spasnis, which develop into a
strychnine-like tetanus,
I 448. Action on Man, — When atropine is injected subciitaneoufilyj
the symptoniB, as in usually the case with drugs adminii^tered in this
manner, may come on immediately, the pupil not unfreqtiently dilating
almost before the injection is finished. This is in no way surprising;
but there are instances in wliich decoctions of datura seeds have been
administered by the stomach, and tbe commencement of symptoms has
been as rapid as in paisoiiing by oxal lu or even prusaic add. In a case
tried in Indi^i in July 1852, the prosecutor declared that, while a ^lerson
was Imnding him u lota of water, the prisoner snatched it away on pre-
tence of freeing the water from dirt or straws, and then gave it to him.
He then dnink only two mouthfiils, and, comphitniug of the iutter ta^te,
fell down insenisible within forty yards of the spot where he had drunk,
and did not recover bis senses until the third day aften In another
case, a man was struck down so suddenly that Urn feet were scalded by
some hot water which he w*as carrying. — Chevertf.
When the seeds^ leaves, or fruit of atropine-holding plants are eaten,
there is, however, a very appreciable i>eriod l>efore the symptoms con*-
meuce, and, as in the case of opium poisoning, no very definite rule can
be laid down, but usually the efix^cts are experienced within half an hour.
The first aensation is dryness of the mouth and throat; this continues
increasing, and may rise to nucb a degree that the swallowing of liquids
ie an im|»ossibility. The difficulty in swallowing does not seem to be
entirely dei>eudent on the dry sbite of the throat, but is also due to a
apiasmodic contraction of the pharyngeal muscles. Tissore t found in
one case such constriction that he could only introduce emetics by piss-
ing a catheter of small diamfcter. The mucous membrane is reddened,
and the voice hoarse.l The inability to swallow, and the changed voice,
• Trantact, 0/ Edin, Iio}f, Soe^^yah JOtV, p. 449. Jaurn. o/An^l, aw( Phyniel,,
Miy 1S6&, p* 35?,
t Qaz. hsbiL, 1856,
t A Mend nf the aeuinr autlior'» wrh given, by atniAtttke in dispenaitig, IS minims
(if » solation of atropine sulphute, <H|uivulent to f grain of atnipine (or 9"^^ mgrmSv),
Ten minuUia after Lalving tUti tfo^e Ui**tl* Vfan dilatatiort of the Jiupil, iiidiatinctueiifi of
vision, with gr&ki dry ncfA of thi* thri>at and difficulty ia swallowiiig ; he ottc-mptod to
eat tt biscuit, but, oft^r cfteivitig U, he wua ablJged to q»Lt it out, »s it waa udI
388 POISONS : THEIR EFFECTS AND DETECTION. [§ 448.
bear some little resemblance to hydrophobia — a resemblance heightened
to the popular mind by an inclination to bite, which seems to have been
occasionally observed ; the pupils are early dilated, and the dilatation
may bo marked and extreme ; the vision is deranged, letters and figures
often appear duplicated ; the eyeballs are occasionally remarkably
prominent, and generally congested ; the skin is dry, even very small
quautities of atropine arresting the cutaneous secretion ; in this respect
atropine and pilocarpine are perfect examples of antagonism. With the
dryness of skin, in a large percentage of cases, occurs a scarlet rash over
most of the body. This is generally the case after large doses, but
Stadler saw the rash produced on a child 3 months old by '3 mgrm. of
atropine sulphate. It appeared three minutes after the dose, lasted
five hoars, and was reproduced by a renewed dose.* The temperature
of the body with large doses is raised ; with small, somewhat lowered.
The pulse is increased in frequency, and is always above 100 — mostly
from 115 to 120, or even 150, in the minute. The breathing is at first
a little slowed, and then very rapid. Vomiting is not common ; the
sphincters may be paralysed so that the evacuations are involuntary,
and there may be also spismodic contractions of the urinary bladder.
The nervous system is profoundly affected ; in one case there were clonic
spasms,! in another | such muscular rigidity that the patient could with
diflBculty be placed on a chair. The lower extremities are often partly
paralysed, there is a want of co-ordination, the person reels like a
drunken man, or there may be general jactitation. The disturbance of
the brain functions is very marked ; in about 4 per cent, only of the
recorded cases there has been no delirium, or very little — in the majority
delirium is present. In adults this generally takes a garrulous, pleasing
form, but every variety has been witnessed. Dr. H. Giraud describes
the delirium from datura (which it may be necessary to again repeat is
atropine delirium) as follows : — " He either vociferates loudly or is
garrulous, and talks incoherently ; sometimes he is mirthful, and laughs
wildly, or is sad and moans, as if in great distress ; generally he is
observed to be very timid, and, when most troublesome and unruly, can
always be cowed by an angry word, frequently putting up his hands in
a supplicating posture. When approached ho suddenly shrinks back as
if apprehensive of being struck, and frequently he moves about as if to
avoid spectra. But the most invariable accompaniment of the final
possible to swallow ; the throat was excessively sore, and there was a desire to pass
urine, but only a few drops could be voided. In forty-five minutes he was unable to
stand or walk. There was a bright rash on the chest. In two hours he became
insensible, and was taken to the Middlesex Hospital, recovering under treatment in
about eight hours.
• Med. Times, 1868. t Lnncel, 1881, vol. i. p. 414.
X Ibid., 1876, vol. i. p. 846.
§449-]
ATIIOPINB.
389
Btage of delirium, an J frequently al«o that of mpor, ie in the incessant
picking at real or imaginary objects. At one time the patient Beiaes
hold of partd of his clothes or bedding, pulla at bis fingers and toea,
takes up dirfc and etooaj from the groundi or as often snatches at
imaginary objects in the air, on his body, or nnything near Him- Very
frequetitly he appears aa if amuBin^ himself by drawing out imaginary
threads from the ends^ of his tmgers, and occasionally his an tics are so
varied and ridiculous, that I ha^e seen his near relatives, although
apprehensive of danger, unable to restrain their laughter-*'* This
t'M^tive dolirium passes into a BOnmolent state with muttering, catching
at the bedclothes^ or at Hoating i^pectra, and in fatal cases the patient
dies in this staple. As a rule, the sleep is not like opium coma ; there
is complete insensibility iu both, but in the one the sleep is deep,
urithout muttering, in the other^ ftxrm atropine^ it is more like the
stupor of a fever. The course iu fatal cases is rapid, death generally
taking place within six hours. If a person live over seven or eight
hours, he usually recoTora, Ijowevor serious the symptoms may appear.
On wakiug^ the patient remcmhcrs nothing of his illness ; mydriasiB
remains some time, and there may be abnormality of speeeh and weak-
ness of the limbs, but within four days health is reestablished. In
cases where the seeds have been swallowed, the Hvmptoms may be much
pruloiiged, and they seem to eontiuue utitil all tlie seeds have V>eea
voided — perhaps tins ts due to the ijnperfect but continuous CEtroetton
of atropine by the inteatiual juices*
Chronic poisoning by atropine may, from what has been stated, be of
great importance in India. It is probable that its couiinuous effect
would tend tg weaken the intellect, and there is no reason for any
incredulity with regard to its power as a factor of insanity. liossbach
has ascertained that if dogs are, day after day, dosed with atropine, they
become emaciated ; but a certain tolerance is estaiilished, and the dose
has to be raised considerably after a time to produce any marked
physiological cilect.
§ 449. Physiological Action of Atropine.— Atropine as well as
muscarine exercises a profound influence on the nervous apparatus of the
heart ; the innervation effected may be clearly appreciated by referring
to the accompanying iignref which is a representation of Schmiedeberg'S
diagrammatic *' schema,^' F is the heart muscle ; M the vaso-rnotor
centre j H the brake or skid centre (Hemmungazentrnm); B^ the
aeceleratiog centre ^ V the inhibitory nerve (vagus) ; A the accelerating
nerve {sympathetic) ; Z the connection between H and the ** skid '*
* In an Etigliah e&s» of buUndoaita poisoaiugi the patieutj & tailur, a&t fc^r four
houn^ moving lii!» huadi^ und ftt-m& as if aewing, mid his Hpa 03 if talking, bat with-
out uttering a word*
390 POISONS: their effects and detection. [§ 450-452.
muscular fibres; H is also connected with B, M, A, and V, but not
directly with the muscular fibres.
Atropine paralyses the end apparatus of H, hence the heart beats are
quickened ; if in an animal poisoned by atropine, electrical excitement of
the vagus is tried, the heart's action
is no longer slowed as would be the
case in the normal animal. Atropine
paralyses H, but leaves M intact.
Atropine given to dogs for several
days, first in small doses, 3 mgrms.
*per kilo., then increasing up to 110
mgrms., causes pathological changes
in the nervous ganglion cells of the
heart, the protoplasm darkens, the
nucleus is not so sharp in contour,
and the chromatin disappears more
or less — these changes have not been
observed in single fatal doses.
§ 450. Diagnosis. — The diagnosis of atropine poisoning may be very
difficult unless the attention of the medical man be excited by some
suspicious circumstance. A child suffering from belladonna rash, with
hot dry skin, quick pulse, and reddened fauces, looks not unlike one
under an attack of scarlet fever. Further, as before mentioned, some
cases are similar to rabies ; and again, the garrulous delirium and the
hallucinations of an adult are often very similar to those of delirium
tremens^ as well as to mania.
§ 451. Post-mortem Appearances. — The post-mortem appearances
do not seem to be characteristic, save in the fact that the pupils remain
dilated. The brain is usually hypersBmic, and in one case the absence
of moisture seems to have been remarkable. The stomach and intes-
tines may be somewhat irritated if the seeds, leaves, or other parts of
the plant have been eaten ; but the irritation is not constant if the
poisoning has been by pure atropine, and still less is it likely to be
present if atropine has been administered subcutaneously.
§ 452. Treatment. — The great majority of cases recover under
treatment. In 112 cases collected by F. A. Falck, 13 only were fatal
(11*6 per cent.). The greater portion of the deaths in India are those
of children and old people — persons of feeble vitality. The Asiatic
treatment, which has been handed down by tradition, is the application
of cold water to the feet ; but the method which has found most favour
in England is treatment by pilocarpine, a fifth of a grain or more being
injected from time to time. Pilocarpine shows as perfect antagonism
as possible; atropine dries, pilocarpine moistens the skin; atropine
§ 453. 454.]
HYOSCY AMINE.
391
accelemteg, pilocarpine slowj^ the reapimtton. Dr, Sydney Ringer and
otliers have published a remarkable series of cases (^bowing the efficacy
of this treatment, which , of courHe^ m to be combined where necessary
with etuetica, the use of the stonmch-pump, etc.*
§ 403. Separation of Atropine from Organic Tissues, etc.— From
the contents of the atomach, atropine mny be separated by acidulating
strooyly with sulphuric acid (15 to 20 c.c. of dlhite H^jSO^ to 100 c.c),
digesting for aome time at a temperature not exceeding 70', and then re-
ducing any solid matter to a pulp by frictiony and filtering, which can
genernlly be effected by the aid of a filter-pump. The liver, muaclea,t
and coagulated blood, ctc.^ may also be treateil in a precisely similar vvay.
The iteid liquid thus obtained, ii first, to remove impurities^ shakeu up
with amyl alcohol, anil after the separation of the latter in the usual
maunerj it is agitated with chloroform^ which will take up any of the re-
maining amjl alcohol, I and also serve to purify f urtlier. The chloroform
is then removed hj a pipette (or the separating Hask before described)^
and the iiuid made alkaline, and shaken up with ether, which, on re-
moval, is allowed to evaporate apoutaneously. The residue will contain
atropiue^ and this may be farther purified by converting it into o^ate,
as suggested, page 383.
From the urine, ,^ atropine may l>e extracted by acidifying with
sulphuric acid, and agi tuition with the same series of solvents. Atropine
has been separated from putrid matters long after death, nor does it
appear to sutler any decomposition by the ordinary analytical operations
of evaporating solutions to dryuess at 100', In other wordti, there
seems to be uo necessity for operations in viieuo, in attempts at separate
ing atropine.
9. HYOSCYAMINK.
§ 454. This powerful alkaloid is contained in small quantities in
datura and belladonna, and also is found in the common lettuce ('001
per cent.), || and in Seopola t^Hrmolica^ a solanaceous plant indigenous to
Austria and Hungary % ; but its chief source is the Hf/fMct/amus nitjer
• See, for Dr. Riiigttr*a cttses, Lai^^i^ 1876, V(*L i. \k 346. Rofer alao to BrU.
M^. Jmm.t 1B31, voL i. p. mi ; iL, p. 659.
t Neitker arnyl alcohol nor elilorofomi rpmovea alropin© from nn actd ^jlation*
t Atropine ^ufs& into Ihi: blotKi^ liiid af)|i«4ikrs to be pri^iteut in tlit; diJferc&t orgiLua
ia diraat proportioti to tli^s; (juiiutity of blood ih«y ctmtuiii. DrogeudortT hm found
in the tnoecles of rabbits fed apoa beUadonim aulBsient Atropine for qaitntitative e»ti«
matioa,
§ Drogendord' ha«foandatTopiue in the uriue of rabbits fed with belkdonna ; tbe
separation by the pouoa is so rapid that it o(iPU mn only bv reioogimed in the uriue
dmiDg the tlhat hour ^fter the [>oison has boeu lakea.
It T. S. Dymoud, Jmtm, Ckcm. 6W», Tra$is., 1892. DO.
U W. R. Dunst&n &nd A. tl Chaston, limrm. Ji^itm. Tmm. (3)i xx 401-494.
392
F0I80NS: THKIB EFFECTS AND DETECTION.
[§45+
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§ 455]
HYOSCVAMISK,
393
aud Hyo^Cfjiunm albtia (black and white heubmne) : it is alio found in tbe
Dufmma inyoporoidm. Duimtan and Brown * have fouud that Hyoscij-
amm mtUieus conUinB only hjo^yaminef and that the platit grown in
Egypt is much richer in the tilkaloid tlian is tliu European variety;
further, they fiud that the Datura di'amomum grown in Kgypt also
contuiuis only hyoscyaraiuo, and i^ uot accompanied by other alkaloids.
The following table gives the pereentage of alkaloid (hyoscjamine) fouud
by them iu various planta.
PEECENTAGK OF TOTAL ALKALOID.
1
BwA^
L«AVt!a,
SfifidK.
Btem.
KotJre
Aht^jiA BellttdoniiA
Datum Stmmouium
Hyoscyamiis iiiger
(hietuiml)
(ftiinuiil) .
Hyoficyuaiui muticu^
0-21-0*41
0*15
0*15^0*17
9'3(K0^y0
0-49
0-039-069
0*OtlJ-0 07
O'le^os?
0"46
008
Hyoflcyaimne (O^^H.^gN* \), as separated in the course of atialyiia,
is a reuinoid, sticky, amorphous mn^^ dilBouU to dry, and poa^esaiug a
tobacco-like odour. It can, however, be obtaiuod iu well-tuarked odoui^
los» crystals, which melt ut 1 08*-* 109"", a portion subliming unchanged.
It liquefies under boiling water without crystaliisation. According to
Thorey,t hyuscyamine cryatuUbea out of chlorofonu in rhouibic Uvblea,
and out of benzene in fine needle ; but out of etber or amy I alcohol it
retuaius amorphoue. When perfectly pure, it dissolves with diiliculty
in cold, but more readily iu hot, water; if impure, it ia hygroscopicj and
its Bolubility is much increased. In any cs^se, it dissolves easily in
alcohol, ctber^ chloroform, amyl alcohol, benzene, and dihite acids.
HyoBcyamine neutralises acids fully, and forms crystallisable salts, which
assume for the moat part the form of needles. It is isomeric with
atropme, and is converted into atropine by lieating to 110" without air,
or by allowing to stand in weak alkaline solution. It is the Itevo-rotatory
modification of atropine. 1 ^t^hydrating agents convert it into belladonnine
(atTopamine), Ci^H^^NO^, Hyoacyiiraine saponified with hot water gives
liBTO'tropio acid and tropine, but if saponified by ncids or alkalies this
l^vo-tropic acid ia converted into the racemic or inactive form. The
gold salt melts at 159', aud does not melt in boiling water like the
atropine gold salt.
§455. Fbarmaceutical and other Preparations of Henbane. — The
• Jmtrn. Chrm, Sr^e., 1899, T, 72 ; 1901, T, 79.
t I'hann, Zi.ii$ckr,/, UuitiiL, I8fl9*
394
POISONS : THStB BFFBOTS AKD DSTECIION.
t§ 455.
laaveB are alone officinal in the European pharmacopreias ; but the ieede
aud tlio root, or the liowcrs, may be met with occasionally, especially
among herbalists. The table ♦ (p. 392) will give an idea of the alkaloidal
content of the different parts of the plant.
In order to ascertain the percentage of the alkaloid in any part of
tlie pUnt, the pFoces-s followed Ijy Tliorey hiis the merit of simplicity.
The substance is first exhausted by petroleum ether, which frees it from
fat ; after drying, it is extracted with 85 per cent, alcohol at a tempera-
ture not exceeding 40*, The alcoholic extracts are then united, the
akohol distilled off, and the residue filtered. The filtrate in now first
purified by agitation with petroleum ether, then saturated by ammonia,
aud shaken up with chloroform. The latter, on evapt^ration, leaves the
alkaloid only slightly impure, and^ after washing with distilled watoFj
if dissolved in dilute sulpliimo acid, a ctystalline sulphate may bo
readily obtained.
A tincture and an extract of henbane Leaves and flowering tope
are officinal in moat pharmacopooiaa ; an extract of the seeds in that of
France.
An oil of hyoscyamua is officinal in all the Continental pharma-
cop(£ia% but not in the Britieh-
Henbane juice is recognised by the British pharmaoopceia ; it is
about the humii^ strength m the tincture.
An ointment, made of one part of the extract to nine of simple
oiutmcfut, is offioinal in the German pbarmacopcpia.
The tincture {after distilling oil' the Hpirit) and tbe extracts (on
proper solution) may be conveniently titrated by Mayer'a reagent (p. 264),
which, for this purpose, sliould be diluted one- half ; each c.c. then,
according to Dragendortf, eqmilling 6'98 m^'rms. of hyoacyamine, Kruse
foiiud 0'042 per cent, of by oscy amine in a Russian tincture, and 0"28
por cent, in a Russian extract. Any preparation made with extnict of
henbane will be found to contain nitrate of potash, for Attfield has shuwn
the extract to be rich in this &ubst;ince. The ointment will require ex-
traction of the fat by petroleum other ; this accomplished, the determina-
tion of its stretjgth is easy.
The oil of byoscyamna is poisonous, and contains tlm alkaloid. An
exact quantitative research is difficult ; but if 20 grms. of the oil are
shaken up for some time with water acidified by atilphnric acid, the
fluid separated from the oil, made alkaline, shaken up with chloroform,
and the Utter remove J and evaporated, sufficient will bo obtained to
test successfully for the preaeuce of the alkaloid, by its action on the
pupil of the ©ye-
• ThiRUble, taken fhim Driij^cndorirs C/«mi»£A« IVtrihUstnnmunff ehii^r stark'
vdrhsndon Brogmn^ mxha^xm tlio rcicArchoe of Thorey.
§ 456-45^^]
SCOPOLAMINE.
395
§ 456, Dose and BfTects, — The dose of the uncryataUine hjoacjamine
la 6 mgrraa, {^^ grauj). The senior author has seeti it exteoaively
used io jisjlums to calm viol*int or ttoubleeome maniaes. Thirty-two
mgrms. (| ^^rain) bo^in to act within a quiirter of an hour; the face
flushefi, the piJpil« dilate^ there la no excitementj all muscular motion
is enfeebled, and the patient rctnams quiet for many hours, the effects
from a aiiigle do3G not uii commonly lasting two days. 6i*8 mgrnii,
( 1 grain) would be a very large, and possibly fatal, dose. The absence
of delirium or excitement, with ftill doses of hyoscyamine, is a striking
contrast to the action of atrojiine, in exGry other respect ao closely
allitKl ; yet there are cases oti record showing that the he u bane root
itself has an action similar to that of belladonna, unless indeed one root
has been mistaken for another ; e.^., Sonnenschein relates the following
ancient wise of poisoning ; — -In a certain cloister the monks ate by error
the root of henbane. In the night they were all taken with hallucina-
tion^, so timt the pious convent was like a madhonse. One monk sounded
at midnight the matins, some who thereupon came into chapel could not
read, others read what was not in the book, others sang drinking songs —
in short, there was the greatest disturbance.
g 457. Separation of Eyoscyamine from Oi^anic Matters. ^Tbe
isolation of the alkaloid from organic tissues or fluids, in cases wliei^e a
medicinal preparation of henbane, or of the leaves^ root^ etc., has been
taken, is possible, and should be carried out on the principles already
detailed- Hyoscyamine is mainly identjlied by its power of dilating the
pupil of the eye. It is Bidd that so small a quantity as '0083 mgrm,
(luVff ^•'^^'i) *ilJ ^^ fifteen minutes dilate the eye of a rabbit It is true
that atropine also dilates the pupil ; but if sufficient of the sulistauce
should have been isolateti to ajjply other tests, it can be distinguished
from atropine by the fact that the latter gives no immediate precipitate
with platinic chloride^ whilst hyoscyamine is precipitated by a small
quantity of platinic chloride, and dissolved by a larger amount, by the
characters of the gold salt, and by the diSerent form of the crystak in
the precipitate by Marmu^s reagent (see p, 251),
3. SCOPOLAMmE.
I 458 » SeoftolaiiHfte, C^iUjf^Q^ Accofding to Schmidt,* tttid more ktely to
Mcn?kt Li»!(!t)burg*& f hyosGlite CirH^HO^ do«ii uot t^xlftt. Mid h nothing hut ini[iUF0
s^pQlaminr* Sct^polamiue cryaUUbee with oue molecule of water. It h suluhle in
alcohol^ iithir^ chlorafi>rm, ulc., but tmt very lioluble tu wiiter. gco^ioUmiue has o
meUutg-jiQiut of &9", givcfi jkii nurochlonde crystallising iti needlea^ melting at
2 1 T-tl i^ The hypctbrvtaide ]ii4$ «i apqciJic ratatioa of - 25* 4 1'. It is a tert i&ry ba^
* ^ftiA, I*harttt., oaxxs^ 2Q7-^h
t Jtiurtk. JSiiCt Chem. /ni,^ xvi, 515*
396 POISONS : THEIR EFFECTS AND DETECTION. [§ 459-46 1.
containing an a-methyl group. Boiled with baryta water it yields tropic acid and
scopoline.
C,7H2iN04 + H20->C9Hio03 +C8H13NO2
Scopolamine. Tropic acid scopoline.
Scopoline forms an aurochloride melting at 223''-225'', and a platinochloride melting
at 228**-230**. By the action of alkalies and alkaline carbonates, scopolamine may be
oonverted into an inactive crystalline derivative — isoscopolamine, C17H21NO4 + H2O ;
m.p. 66^
By warming isoscopolamine to 54*-55° an anhydrous isoscopolamine may be
obtained, m.p. 82''-83^ Hesse* has fouud an inactive alkaloid in conmiercial
scopolamine hydrobromide which he called a^ro5cin<;, C17H21NO4 + 2HaO ; m.p. 87°-38*.
WolfTenstein proposes to call these different derivatives i-scopolamine, i-scopolamine
monohydrate and dihydrate. Thus we have
Scopolamine, CJ7H2JNO4 + H2O, laevorotatory ; m.p. 59**.
i-scopolamine, Ci7HaiN04, inactive ; m.p. 82*-83°.
i-scopolamine monohydrate (or isoscopolamine), C17H21NO4 + H2O, inactive ; m. p. 56**.
i-scopolamine dihydrate (or atroscine), C17H21NO4+2II2O, inactive ; m.p. 37'*-38*.
According to experiments on animals, the heart is first slowed, then quickened ;
the first effect being due to a stimulation of the inhibitory nervous apparatus, the
second to a paralysing action on the same. The temi)erature is not altered. The
pupils are dilated, the saliva diminished. The irritability of the brain is lessened.!
§ 469. Pseudo'hyoscyamine^ CiyHajNOj, isolated by Merck * from Duhoisia
myoporoideSf crystallises from ether and chloroform in needles, melting at 133*-134**.
Tjaevorotatory. Soluble in alcohol and chloroform. A little soluble in ether and water.
Saponified with baryta water, it yields tropic acid and a base of the same formula
as, but not identical with, tropin e.
Not a very active poison, but causes dilation of the pupiL
§ 460. AtropaminCf C17H23NO2, occurs in roots of belladonna, and may be formed
by dehydrating atropine or hyoscyamine with sulphuric acid. On heating it forms
belladonnine.
Crystallises from ether in prisms melting at 60'*-62''. Soluble in alcohol, ether,
and chloroform ; a little soluble in water and methyl alcohol. It is optically inactive,
and has no mydriatic action.
On saponification with baryta it first forms belladonnine, then splits up into
atropic acid and tropine.
§ 460a. Belladonnine, C]7H2iN02, is found in the belladonna ; it is a yellow
resinous mass; a little soluble in water, and readily soluble in alcohol, ether,
chloroform, etc
4. SOLANINE.
§ 461. Distribution of Solanine. — Solanine is a poisonous nitrogenised glucoside
found in all parts of the plants belonging to the nightshade order. The English
common plants in which solanine occurs are the edible potato plant (Solanum
tuberosum) f the nightshade {Solanum nigrum), and the Solanum, dulcamara, or
bitter-sweet. The berries of the Solanum nigrwn and those of Solanum dulcamara
contain about 0*3 per cent. Mature healthy potatoes appear to contain no solanine,
but from 150 grms. of diseased potatoes G. Kassnert separated 80 to 50 mgrms.
Albert Hilger and W. Markens {Ber., 1903) have purified crude solanine by
extraction with boiling absolute alcohol, and precipitation with acetic acid, water and
• Liebig's Ann. der Oumie und Pharm,, ccxxi. 100.
t ParloflF, St, Petersburg Med. Chem. ^owi. Dissert, No. 9, 1899-90.
::: Arch, Pharm, (3), xxr. 402, 403.
§ 462, 463}
90L&NIKK.
397
ammonia. Tho produot m re-cry stul Used from ftlwhol ; tlicso observers give th*
formula AS CjjII^Oj^N, a^id state that on hydrolysis with 2 iierCPiit. sulphuric ftold,
era ton -aldehyde, de^ctrosd utid solanldinc arc formt^ according to tho reiicti<m —
2Ck2H^O,8N-3^30oHi20^^2CiH«0 + aCasHeiOaN + 22HaO.
This research is criticised by Simon Zeisel and J« Wittman (Bcr,, 1303), who st&tA
that onJy metbylformaldehydfl is fonued in small quantity, that the sugar produced
OontaLns a largf^ projKirtion of rliamnosc &s well as uome othgr carbohydrate^ but that
from the mixture of siigars no cryatullino dcsxtroae con bs obtainech
§ 4(i2. Propertiea of Solanine, —The reaction of the cry 3 tab la weakly alkdltie ;
the taste is somewhat bitter and pungent. Solanine is soluble in 80OO jHirta of
boiling water, 4000 parts of ether, 500 parta of cold, and 125 of boiling alcohoU
It dissolves well in hoi amyl alcohol, but is scarcely soluble in benzene* An
oqueons aolutiou froths on abaking, but not to tho degree po^Eogsed by sat>oi]iiie
iolmtionii.
The amyl alcohol solution haa the property of gelatinising when cold* It does
this if even so little as 1 part of snlanine \» dissolved in 2000 of hot amyl alcohoL
The jelly is m firm that the vessel may ho inverted mthout any loas. This
pecnliar pro]ht?rty is one of the most important teats for the presence of ioltininei,
The hot ethylic alcohol solution will^ on canllng, also gelatinise, but a stronger sol utioii
U F^nired, From very dilute alooboUc solutions (and especially with slow oooling)
solanine may be obtain{^d in crystals In dilute muieral acids solanine disaolvM
f^ly, and forms salts, which for the most part have an aeid roaotion and are iolnblo
in alcohol and in water, but with difficulty in ether. The comjiouudfl with the
adds are not very ^tabkj and seveml of them are bnikeu up on warming the s^thition,
solan Ine sf^pamting out fmm the aqueous solntions of the aolanine aalta. The
alkaloid may be preeipitatM by the fixed and volatile alkalies, and by the alkaline
earths* SoUnine will stand boiling with strongly alkaline solutions without deoom*
position ; but dilute acids, on wannifig, bydrolytite. By heating salanim^ in alcKiHolie
solution with ethyl iodide in closed tubes, and then treating tho liquiil with ammonia,
ethyl aijlanine in well -formed crystolfi can be obtained. Sulanine is (irecipitated by
pbosjibomolybdic ocid^ but by very few other aubstanct's. It givL-^a, fur example, no
precipitate with the following reagents: — Platinic chloride, gold chloride, mercuric
chloride, jju Lassie bicbromAte, and picric acid. Tun n in precipitates it only afttir a
timflt Sodie phosphate gives a crysUlline precipitate of solan ine phosphate, if
added to a Sfilution of solanine sulphate. Both sola nine and solanidmo give with
nitric acid at hrst a colour] eaa solution, which, on gentle warmings passes into blnei
then into light red^ and lastly bf^coinos weakly yellow. Stilanine, dissolved Ln strong
anlphuric aejfl, to which a little Friihde's reagent ia addetl, at lirst ccjIoutb the lluid
light brown ; after standing some time the orlgos of the drop bt^omc reddish yellow,
and finally the whole a heantiful eherry-reil, which gradually paases into dark vi^ilet
when violet-coloured docks teparate.
g 403. SolanJdine.— Solanidtne has stronger basic projierties than aft1anin<\ Iti
Tonnnla is G^U^KO^ It Is obtained from an alcoholic fiolntion in amoriihoua
masses tnters|K?r<>je4l with needles ; m.p. 19V. It dii^solvea readily in hot ak'ubol,
with dilhculty in ether. With hydrochlorie acid it forms a bydrocbioride —
3(Cj»Ha,NOanCllHCUH.O or liWfi. This hydrochloririle is a slightly ye!low
powder^ only sparingly soluble In water, and enrbrmbiug without melting whes
h*-atLHi U> 28/ ". JSohmidine also forms a sulphate, S[C^ll«,NO-jH3SOJH3pSO< + SHjO ;
tluH salt is in the form of scaly plates, molting at 247°; it dineolves readily
in water.
The sugar obtained from the hydrolysis of aolanidine m a yellow amcn^ihoui
moss dissolving readily in water and wcknI spirit, and has a s[ieoilic rotatory jMiwer
of [it}0= +2S'd23, With phenyl hydrazine hydrochloride and eodium acetate in
398 POISONS : THEIR EFFECTS AND DETECTION. [§ 464-466.
aqueous solution it forms a glucosazone, melting at 199''. It is probably a mixture
of sugars.
Solaneine is the name that has been given to an am9r])hous substance accom-
panying solanine ; according to Hilger and Merkens {Ber,, 1903) it is solanine
minus 5H2O.
§ 464. Poifloning from Solanine. — Poisoning from solanine has been, in all
recorded cases, induced, not by the pure alkaloid (which is scarcely met with out of
the laboratory of the scientific chemist), but by the berries of the difTerent species of
solanum, and has for the most part been confined to children. The symptoms in
about twenty cases,* which may be found detailed in medical literature, have
varied so greatly that the most opposite phenomena have been witnessed as
effects of poisoning by the same substance. The most constant phenomena
are a quick pulse, laboured respiration, great restlessness, and hyperaesthesia
of the skin. Albumen in the urine is common. Nervous symptoms, such as
convulsions, aphasia, delirium, and even catalepsy, have been vritnessed. In some
cases there have been the symptoms of irritant poison — diarrhoea, vomiting,
and pain in the bowels : in many cases dilatation of the pupil has been observed.
Rabbits are killed by doses of 0*1 grm. per kilo. The symptoms commence in
about ten minutes after the administration, and consist of apathy and a low tem-
perature ; the breathing is much slowed. Convulsions set in suddenly before death,
and the pupils become dilated. The post-mortem appearances in animals are intense
redness and injection of the meninges of the cerebellum, of the medulla oblongata,
and the spinal cord. Dark red blood is found in the heart, and the kidneys are
hypersemic. The intestinal mucous membrane is normal.
§ 465. Separation of Solanine from the TisBnes of the Body. -Dragendorff has
proved the possibility of separating solanine from animal tissues by extracting it from
a poisoned pig. The best plan seems to be to extract ¥rith cold dilute sulphuric acid
water, which is then made alkaline by ammonia, and shaken up with wanu amyl
alcohol. This readily dissolves any solanine. The i>eculiar property possessed by
the alkaloid of gelatinising, and the play of colours with Frohde*s reagent, may then
be essayed on the solanine thus separated.
5. CYTISINE.
§ 466. The Cjrtisus Laburnum. — The laburnum tree, Gyttstis
laburnum, so common in shrubberies, is intensely poisonous. The
flowers, bark, wood, seeds, and the root have all caused serious
symptoms. The active principle is an alkaloid, to which the name of
Cytisine has been given. Cytisine has also been found in many plants
belonging to the Leguminosex, such as Ulex eurapditiSy Sophora tomeniosa
and speciosa, Baptisia iinctoria, etc. The best source is the seeds of
laburnum. The seeds are powdered and extracted with alcohol con-
taining hydrochloric acid, the alcohol distilled off, the residue treated
with water and filtered thi-ough a wet filter to remove any fatty oil,
the filtrate treated with lead acetate; and, after separating the pre-
* See "Death of Three Children by S, nigrum'*-, Hirtz., Gaz, M6d. de Stras-
bourg, 1842; Maury, Oaz, des S6p,, 1864; J. B. Montane, Chim. Med., 1862;
Magne, Gaz. des U6p., 1869 ; Manners, Edin. Med, Joum., 1867. Cases of poison-
ing by bittersweet berries are recorded in Lancet, 1856 ; C. Bourdin, Gaz. des
UdpUauxi 1864 ; Boumeville, the berries o{ S, tuberosum, Brit. Med. Joum., 1895.
§ 467-]
CYTISINE,
399
cipitated colouring nmtter, made alkaline with catjatic potaah, and
shaken with amjl ulcohoL The aoijl alcohol ts shaken with dilute
hydrochloric acid, the solution evaporated, the crude crystala of
hydrochloride thus obtained treat^^d with alcohol to remove colouring
matters, and recrystalliaed several times from water; it then forma
well-developed J eolourleasp transparent prisms* From the hylrochloride
the free ba«e is readily obtnined.
Gytisiiiej CjjIIi^NjO, — To cytisine used to be ascribed the formula
C^HpjyNgO, but a study of the salt and new determinations appear to
prove that it is identical with ulexine, Cytisine is in the form of white
radiating cry stats, conaiBting, when deposited from abaohite alcohol, of
anhydrouB prisms^ which melt at from 152° to 153\ Cytisine has a
atrtmg alkaline reaction ; it is soluble in water, alcohol, and chloroform,
leas so in Vjen^eue and amyl alcohol, almost insoluble in cold light
petroleum, and insoluble in pure ether. The specific rotatory power in
solution is[a],.17'= - 119*67.
It is capable of sublimation in a current of hydrogen at 164*5'; the
sublimate is in tbe form of very long needles and small leaHets; at
higher temperatures it raclli to a yellow oily fluid, iigain becoming
crystalline on cooUng. Cytisine is a strong lni«e; it precipitates the
earths and oxides of the heavy metals from solutions of the chlorides,
and, even in the cold, eipels ammonui from its combinations,
Cytisine fonns numerous crystalline salts, among which may be
mentioned two platinochloridea, CjiH,4N30H2PtC)^ + 2|H^O and
(Cj|Hj4N20)2H2ptClflt crystallising iti golden yellow needles, which are
tolerably soluble in water; and the aurocbloride, CjiHi^NjOHAuCI^,
crystatlising in short, red-brown, book -shaped oeedlea ; m.p. 212"^ to 213*,
without evolution of gas,
Cytisine foruis at ordinary temperatures a condensation product
with formaldehyde, viz., methylene dicytkine, CH2{CjiH^3t>N2y^. This
may lie crystallised from a solution in toluene; the m,p. of tbe crystals
is 212"* (Freund and Friedmann, Ber,^ 1901).
% 467. Reactiong of Cytisme. ^Concentrated sulphuric acid dis-
solves cytisine without colour; if to the solution is added a drop of
nitric acid^ it becomes orange-yellow, and on addition of a crystal of
potassic bichromate, first yellow, then dirty hrown, and lastly green.
Concentrated nitric acid dissolves the base in the cold without colour^
but, on warming, it becomes orangc-yeUow. Picric, tannic, and
phosphomolybdic acids, potaasic, mercuric, and potass, cad mi i mi iodides,
and L<:>dine with potassic iodide, nil give precipitates. Neither potassic
bichromate nor mercuric chloride precipitates cytisine, even though
tbe solution 1m? concentrated. Tbe best single teat appears to l>e the
reaction discovered by Magelhaes ; this consists in adding thymol
400 POISONS : TireiK ITFECTS AND DKTKCTION. [§ 468, 469.
to a solution of cjtisine in concentrated sulphuric acid, when a
yellow colour, finally passing into an intense red, is produced. The
reaction with formalin (formaldehyde) may be useful for purposes
of identification.
§ 468. Effects on Animalii. — ^W. Marm^ found subcutaneous doses
ci tem 30 to 40 mgrms. fatal to cats ; death was from paraljsis of the
respiration, and could be avoided by artificial respiration. Cattle are
sometimes accidentally poisoned by laburnum. An instance of this is
recorded in the Veterinarian (vol. Iv. p. 92). In Lanark a storm had
blown a large laburnum tree down to the ground ; it fell into a field
in which some young heifers were grazing, and they began to feed on
the leaves and pods. Two or three died, and three more were ill for
some time, but ultimately recovered.
The laburnum, however, does not always have this effect, for there
is a case related in the Gardeners' Chronicle^ in which five cows browsed
for some time on the branches and pods of an old laburnum tree that
had been thrown aside. Rabbits and hares are said to feed eagerly, and
without injury, on the pods and branches.
§469. Effects on Man. — The sweet taste of many portions of
the laburnum tree, as well as its attractive appearance, has been
the cause of many accidents. F. A. Falck has been able to collect
from medical literature no less than 155 cases — 120 of which
were those of the accidental poisoning of children : only 4 (or 2*6
per cent.), however, died, so that the poison is not of a very deadly
character.
One of the earliest recorded cases is by Christison.'* A servant-
girl of Inverness, in order to excite vomiting in her fellow-servant
(the cook), boiled some laburnum bark in soup; very soon after
partaking of this soup, the cook experienced violent vomiting, which
lasted for thirty -six hours; she had intense pain in the stomach,
much diarrhuca, and great muscular weakness; she appears to have
suffered from gastro-intestinal catarrh for some time, but ultimately
recovered.
Yallance t has described the symptoms observed in the poisoning of
fifty-eight boys, who ate the root of an old laburnum tree, being allured
by its sweet taste. All were taken ill with similar symptoms, differing
only in severity ; two who had eaten half an ounce (nearly 8 grms.)
suffered with especial severity. The symptoms were first vomiting, then
narcosis, with convulsive movements of the legs and strange movements
of the arms : the pupils were dilated. This dilatation of the pupil
Sedgwick also saw in the poisoning of two children who ate the root.
On the other hand, when the flower, seeds, or other portions of the
• JSa. Med. JouTfL, 1843. f BrU. Med. Joum., 1876.
§ 470] ALKALOIDS OF THE VERATRUMS. 4OI
laburnum have been eaten, the symptoms are mainly referable to the
gastro-intestinal tract, consisting of acute pain in the stomach, vomiting,
and diarrhoea. On these grounds it is therefore more than probable
that there is another active principle in the root, differing from that
which is in those portions of the tree exposed to the influence
of sunlight.*
The post-mortem appearances are, so far as known, in no way
characteristic.
VII.— The Alkaloids of the Veratrums.
§ 470. The alkaloids of the veratrums have been investigated
by Dr. Alder Wright, Dr. A. P. Luff, Bozetti, Merck, and other
chemists, t
From the seeds of Veratrum sdfKidilla^ Retz, a white amorphous
powder has been isolated which constitutes the commercial alkaloid
veratrine ; it contains at least three alkaloids, viz., GevarHne or crystalline
veratrine, CjjH^oNOg, Veratridine or amorphous veratrine, C37H53NO11,
and SahadUline or cevculilline, Cj^H^^NOg, as well as small quantities of
Sabadtne, CggHg^NOg, and Sahcidinine, C^H^^O^.
From V. allmm and F. viride a number of active principles have
been isolated.
The method which Wright and Luff adopted to extract and separate
the alkaloids from the root of V. album and V, viride^ essentially con-
sisted in exhausting with alcohol, to which a little tartaric acid has
been added, filtering, distilling off the alcohol, dissolving the residue in
water, alkalising with caustic soda, and shaking up with ether. The
ethereal solution was next separated, and then washed with water
containing tartaric acid, so as to obtain a solution of the bases as
tartrates : in this way the same ether could be used over and over again.
Ultimately a rough separation was made by means of the different
solubilities in ether, pseudo-jervine being scarcely soluble in this medium,
whilst jervine, veratralbine, veratrine, and cevadine are very soluble
in it.
The yield of Wright and Luff's alkaloids was as follows : —
* See also a case related by Dr. Popham, in which ten children ate laburnum
seeds ; the pupils were dilated. They nil recovered. B. and F, Med, Chir, Review^
Ap. 1868 ; also a case reported by H. Usher, Med, Times and Gazette^ Sept. 16,
1862.
t *'The Alkaloids of the Veratrums," by C. R. Alder Wright, D.Sc., and A. P.
Luff, Joum, Chem, Soc., July 1879 ; "The Alkaloids of Veratrum viride,** by C.
R. Alder Wright, D.Sc., ib., 1879. Bozetti, Arch, Pharm,^ ccxxi. 81 ; Merck, iWdL,
Qcxi^ix. 104.
26
402
POISONS : THEIR EFFECTS AND DETECTION.
[§ 470.
TABLE SHOWING THE ALKALOIDS IN THE VERATRUMS.
Jervine,
Pseudo-jervine
Rubi-jervine, ....
Veratralbine, ....
Veratrine,
Cevadine,
r. altnim.
PerKUo.
V.viride.
Per Kilo. .
rSgrm.
•4 „
•25 „
2-2 „
•05 „
Absent.
•2 grm.
•15 „
•02 ..
Traces.
Less than '004 grm.
•43 „
From whence it appears that V. album has only a very small quantity
of veratrine, that it is almost absent in V, viride ; on the other hand,
V, viride contains a fair quantity of cevadine, an alkaloid absent in
V, (dlmm.
Besides the six principles enumerated, G. Salzbergcr has separated
two other crystalline substances, to which he has given the names of
protoverairine and protoveratridine, and Pehkschen has also separated a
ninth substance, to which he has given the name of veratroidine.
The formulae of the nine bo<iies which have been separated from
hellebore root are as follows : —
1. Veratridine (or amorphous veratrine), CjyHgaNOn,
2. Cevadine (or crystalline veratrine), C52H49NO9,
3. Proto vera trine, C32H51NO1], .
4 Pseudo-iervine /^^^«^^7(^rii7^^). •
4. rseuao jervine, ^ q^h^j^q^^ {Pehkschen)
6. Veratralbine, C29H43NOB,
6. Protoveratridine, Ca8H45N08, .
7 Rubi-iervine i ^aeH^NOa ( H^right and Luf),
/. KUDi jervine,-^ (.Safc6(fr(7«r), .
8. Jervine, Ca8Hj„N032H20, ...
9. Veratroidine, OsjHjjNOp,
Melting-point.
isr
205*-206'
245'-260'*
209--300"
265'
236-
240"-246'
287'-289'
149'*
Three of these alkaloids possess powerful sternutatory properties, the
least quantity applied to the nostrils exciting sneezing ; the three are
veratridine, cevadine, and pro to veratrine.
Protoveratrine, CggHg^NOu, has been obtained by G. Salzberger *
from powdered veratrum root, by the following process : —
The powdered root is first freed from fatty and resinous matters by
treatment with ether, and then the fat-free powder is exhausted with
alcohol. The alcohol is evaporated off in a vacuum, the extract mixed
with much acetic acid water, filtered from the insoluble residue, and
treated with metaphosphoric acid ; the voluminous precipitate contains
much amorphous matter, with insoluble compounds of jervine and
* Arch. Pharm., ccxxviii. 462-483.
I47I-]
ALKALOIDB OF THE VERATRUM8,
403
rubi-jervine. The precipitate is filtered off, and the filtrate treated
with eicesa of ammonia and shake a up with other On separatiDg
the ether and distilling, proto vera trine crystallises out, and can be
obtainod pure by recrjstallisation from strong alcohol.
Protovemtriue crjRtaUisos m four-sided platea, which melt with
chairiug tit 245' to 250', The base is insolublo in water, benxone, and
li*;ht [letroleum ; chlornfono and lidiling 96 per cent, alcohol dissolve it
somewhat ; cold other scarcely toucht^s lU tx^iliiig ethor dissolves it a little.
Cone en tra tod Hulplniric acid dissolves the alltaloid slowly with the
production of a greenish colour, which passes to cons flow er-bluei and
after some hours becomes violet. Sulphtu-io aeid and sugar gives a
different colour to that prodnced by commercial veratrine. There is
first a green colo\ir which darkens into olive-green, then be4:;ouies dirty
greeD, and Hnally dark brown. When warmed with strong sulphuric,
hydrochloric, or phosphoric acids, there is a strong odour of iaobutyric
acid de velope<i* Dil ute solutions of the salts are preei [n bated by ammonia,
Nesslcr's reagent, gold chloride, i>otassinm mercury iodide, cadmium
iodide^ phosphotuogstic acid, and picric acid ; no precipitate is produced
by taunio, platiuuiu chloride, or mercuric chloride.
§ 471. Veratridine (Cg^H^NOjj) is an amorphous alkaloid, which is
a powerful irritant of the sensory nerves of the mucous membrane, and
excites violent sneezing. Treated with concentrated sulplmrie acid, it
dissolves with a yellow colour, deepening into orange, then into blood-
red, and (inally passing into carmiue-red. If the freslily -prepared sul-
phuric acid solution is now treated with bromine wator, a beautiful
purple colour is produced. Concentrated hydroehlorie /icid ilissolves
veratridine without the production of colour, but, with careful warming,
it beeomes beautifully red* This reaction ia very delicate, occurring
with '17 mgrm. On saponification veratridinu yields veriue, GjgH^j^NOj,,
and veratric acid, 0^11^,0^.
Veratric acid, dimethylether of prott>catechuic acid, has the cf>nstitu-
tion&l fornuda,
CHgO
/X
COOH
Veratric acid forms colonrlcsss needles and four-sided prlsuia, which have
a markixl acid reaction; it melts at 180' to a colourlt^s fluid, and
sublimes without deeomposition ; it is e^isily soluble in hot alcohol, but
insoluble ia etber« If dissolved in nitric acid, water separates iiitro-
veratric acid, C0ng{NO,,)O^, which crystallises out of alcohol iu small
yellow scales. Veratric acid unites with bases foraiing erystalline salts ;
the silver salt has the iximposition ol CgH^AgO^ = 37 37 per cent, silver,
404 POISONS : THEIR EFFKCTS AND DETECTION. [§ 472-474.
and may assist in identification. It is crystalline, with a melting-point
of 206* to 206\
Oevadine, or crystalline veratrine, C82H4gN09. — It has powerful
sternutatory properties, and, under the influence of alcoholic potash,
yields tiglio * acid and cevine, C27H43NO8.
According to Ahrens, angelic acid is first formed, and then converted
into tiglic acid. When the alkaloid is boiled with hydrochloric acid,
tiglic acid is formed, and a ruby red mass. Nitric acid oxidises cevadine
completely ; with potassic permanganate it yields acetic and oxalic acids ;
with chromic acid it forms acetaldehyde and carbon dioxide.!
The Continental authorities always give to cevadine the name
of veratrine. Cevadine forms a crystalline aurochloride, a crystal-
line mercurochlorido, CgaH^gNO^HHgClg, and a crystalline picrate,
CgjH^gNOgCgHgNgOy. Thc mercury salt crystallises in small silvery
plates, and melts with decomposition at 172**. The picrate forms stable
crystals blackening at 225** ; both of the latter salts are but little soluble
in water, but are soluble in alcohol. Cevadine also unites with bromine,
forming a tetrabromide, an amorphous yellow powder insoluble in water
but readily soluble in alcohol, ether, and chloroform.
§472. Jervine, (C2gH37N032H20) (Wn^/ht and Luff), C^^HajNOj
{Pehk8chen),l crystallises in white needles, and when anhydrous, melts
at 237*7'*. It is slightly Icevorotatory. At 25" one part of the base
dissolves in 1658 benzene, 268 ether, 60 chloroform, and 16*8 absolute
alcohol. It is insoluble in light petroleum, and but slightly soluble in ethyl
acetate, water, or carbon bisulphide. It forms a very insoluble sulphate,
and a sparingly soluble nitrate and hydrochloride. Jervine gives, with
sulphuric acid and sugar, a violet colour, passing to blue. Treated with
strong sulphuric acid it dissolves to a yellow fluid, which becomes succes-
sively dark yellow, brownish-yellow, and then greenish. The green shade
is immediately developed by diluting with water. Jervine does not
produce sneezing.
§ 473. Pseudo-jervine, CjgH^NOy ( Wright), m.p. 299* ; CagH^gNO,^,
m.p. 259*" {Pehkschen), may be obtained in a crystalline state. One part
is soluble in 10*9 parts of light petroleum, 372 parts of benzene, 1021
parts of ether, 4 of chloroform, and 185 of absolute alcohol. The pure
base gives no colour with sulphuric, nitric, or hydrochloric acids. It does
not produce sneezing.
§ 474. Protoveratridine, Cj^H^^NOg, is probably derived from proto-
veratrine. Salzberger§ isolated it from powdered veratrum roots by
* Tiglic acid, (\Tifi^ is a volatile acid, nxp. 64*, boiling-point 198*5* ; it forms
a soluble barium salt, and an insoluble silver salt.
t Ber,, xiiiL 2700-2707. t Jottm. Pharm, (5), xxii. 265-269.
§ ArcK Pharm., ccxzriii. 463-488.
475*477-] ALKALOIDS OF THE VKEATRUMS,
40s
treating the powder with barium hydroxide and water, and eattractuig
with ether. Tlio ether extnict was Bepamted and freed from ether hi a
Qurretit of hydrogen at a low temperature.
From the dark green syrup ohtahied jerviue crystalUsed out, and from
the mother-hquor ultimately profcoveratridmc was separated.
Protovenitridine crystalhses in colourless^ four-sided plates, which melt
at 265°. It is almost insoluble m alcohol, chloroform^ methyl alcohol,
and acetone, and itisotuble in benzene, light petroleum, and ether. Con-
centrated Bulphurio acid gives a violet, then a cherry-red colour. Its
solutiou iQ concentrEitod hydrochloric acid becomes light red on warming,
and there is an odour of isobutyrtc acid. It m readily soluble in dilute
mineral acid^ and the solution, on the addition of ammonia, yields the
alkaloid in a crystalline condition. The sulphuric acid solution gives
precipitates with phosphotungstic, picric, and tannic acids, and with
potaasium mercury iodide ; but gives no precipitate with platinum
chloride, potaasium-cadmium iodide, or with MiUou^s reagent.
It forma a platinum salt (C2gH|fjNOg)gH2PtCl^ + 6HjO, which is pre-
cipitated in large six-sided plates 011 adding alcohol to a mixed solution
of platinum chloride and a salt of the base.
Frotoveratridine ia not poisonous^ aad does not cause sneering. Its
solutions are veiy bitter.
I 475. Rubi-jervine, CgcH^gNO^, is a cryetalliFaljIe base wholly dif-
ferent from jorvine, yet probably closely allied to it. Melting-point 237*
(Wriijht and Luf), 240"-246* (^Wrtert^er). It forms a light yellow,
indistinctly crystalline gold salt {Cj^HigNO^tHCljAuClg) : it gives a dif-
f eren t play of colo u rs from j er vln e wi t b s u I ph u rlc ac id . The cou ce nt ra ted
acid dissolves rubi-jervine to a clear yellow fluid, becoming successively
d&rk yellow, brownish-yellow, and brownish blood- red, changing after
several hours to a brownish-purple. On diluting slightly with water the
brownish-red liquid, it becomes successively crimson, purple, dark
lavender, dark violet, and ultimately light indigo. Its hydrochloride and
sulphate are both more soluble than either of the correspond in g salts of
jervine or pseudo-jervine.
g 476* Veratralbine, CggHuNO^ an amorphous non-stenmtatory
base, gives, when a speck of the substauce is dissolved in sulphuric acid,
& play of colours, becoming successively yellow, dark yellow, brownish-
orange J and browniah blood-red, with a strong green fluorescence. It
yields no acid on saponiScation,
g 477. Veratroidine, C^^H^^^NO^j is another base which has been
separated by G. Pehkschen.* Its uielting-poiot is 149*. One part dis^
iolves in 13 of benjsene, 59 of chloroform, and 9 of ether. It yield
amorphous salts with the miner kii acids, and with oialic and acetic acida*
* Op. cU.
406 POISONS : THEIR EFFECTS AND DETECTION. [§ 478, 479.
It is precipitated by most of the group reagents. With 1 1 per cent,
solution of hydrochloric acid it gives a beautiful rose colour.
§ 478. Commercial Veratrine. — Commercial veratrine is a mixture of
alkaloids, and has usually fairly constant properties, one of which is its
intense irritant action on the nostrils. Placed on moist blue-red litmus
paper it gives a blue spot. It is but little soluble in water, 1 : 1500 ; but
readily dissolves in alcohol and chloroform ; it is but little soluble in
amyl alcohol, benzene, and carbon disulphide.
When a very small quantity is treated with a drop of sulphuric acid,
the acid in the cold strikes a yellow colour; on warming, the colour
becomes violet, slowly changing to orange and cherry-red. Sensible to
100th of mgrm. If this test is performed in a test tube, a green-yellow
fluorescence is also seen on the sides of the test tube.
Commercial veratrine strikes a pink-red colour with hydrochloric
acid in the cold if a long time is allowed to elapse, but it at once
appears if the acid is warmed, and is permanent. The solution becomes
fluorescent if two drops of acetic acid are added.
If a small quantity of commercial veratrine is added to melted oxalic
acid and the warming continued, a blood-red colour is obtained.
Veratrine, warmed with syrupy phosphoric acid, develops an odour
of butyric acid.
A dark green colour, followed by reddish-purple and blue colours, is
obtained by adding a sprinkling of finely powdered sugar to a solution
of veratrine in sulphuric acid. This is best seen with a solution of
1 to 10,000; if in dilution of 1 to 100,000 a grass-green colour is
produced, followed by purple and blue colours, quickly changing to
brown or black.*
When two or three drops of sulphuric acid and furfuraldehyde
(5 drops to 10 c.c. of acid) are added to minute particles of alkaloids, a
more or less characteristic colour makes its appearance ; this is parti-
cularly the case with veratrine. A few particles rubbed with a glass
rod, and moistened with the reagent, gives first a yellowish-green, then
an olive-green mixture, the edges afterwards becoming a beautiful blue.
On warming, the mixture gradually acquires a purple-violet colour. The
blue substance obtained in the cold is insoluble in alcohol, ether, or
chloroform. The least amount of water decolorises the solution, and,
on adding much water, a fairly permanent yellow solution is obtained.!
§ 479. Pharmaceutical Preparations. — The alkaloid is officinal in
the English, American, and Continental pharmacopoeias. There is also
an unguentum veratrinm — strength about 1*8 per cent. In the London
pharmacopoeia of 1851 there used to be a wine of white veratrum, the
* Fliickiger's JieactionSf 1893.
t A. Wender, Chem, ZeUung, xvii. 960, 951.
I 480-482.] ALKALOIDS OK Tim VKtU'miTMS,
407
active principle of 20 parts of the root by weight being coiitaiiied iu
100 jmrts hy measure of tho wine. 8uch u. wini^ would cod tain about
0*OB4 per oeut. of total alkaloids. Of the green veratrum there id a
tincture {tmciura veratri vindia)^ t*> make which four jjarts by weight
of the root are cstliaueted by 20 parts by measure of spirits ; the strength
varies^ but the average is 0*02 per cent, of total alkaloidi.
§ 480. Fatal Bofie, — The maximum dose of the oommen^ia! alkaloid
m laid down as 10 mgrms. (*15 grain), which can bo taken safely in a
single dijse, but nothing suflioieiitly definite h known as to what ia a
lethal dose. I'd grms, of the piiwdered rhizome have caused death^ and,
on the other hand, ten ttm**8 that quantity has been taken with impunity,
BO that at present it la quite an opi^n question.
§ 48L Effects on Animalfi— Physiological Action.— Experiments
on animals have proved that the veratrunia act on tlie aeuHory nerves of
the skin, and thoiie of the mucijus membranes of the no^e and intestinal
canal ; Ujey are lirst excited, afterwards paralysed. When administered
to frogs, sugar and lactic acid appear in the urinary excretion.* It
exercises a peculiar influence on voluntary muscle ; the contractility is
changed, so that, when excited, there ia a long-continuing contraction,
and from a single stimulus more heat is disengaged than with healthy
muscle ; the motor nerves are alau affected. The respLriition, at first
quickened, is then slowed, and finally paralysed. The heart's action
is also drat qutckened, the blood -pressure at the same time is raised, and
the small arteries narrowed in calibre ; later follow sinking of the
pressure, slowhig of the heart, aud dilatation of the veaselS) and the
heart beeomea linally paralysed.
§ 482. Effects on Man, ^Poisoning by veratrum, s^ibadilla, or phar-
maceutical prejiaratiuijs containing veratriue, is not common. Flenk
witnessed a case in which tlie external apphcation of aabadJlla powder
to the head caused <ieliriuni, and Lentin also relates a case in which an
infant at the breast seems to have died from an extermU application
made for the purpose of destroying lice. In both instanctis, however,
there is a possibility that some of the medicament was swallowed.
Blaa recorded, iu 1861, the case of two children who drank a decoc^
tion of white hellebore, the liijuid being intended as an external applica-
tion to au animal. Tljcy showed serious symptoms, but ultimately
recovered.
A scientific chemist took 3*8 grma. (5B grains) of the tincture of
green hellebore for tho purpose of ex|>eriment, There followed violent
symptoms of gastric irritation,. vomiting, and diarrha*a, but he also
recovered, t
• £fiL Phi/M. Chcm.t 3tvL i5S-45».
t Med. 7"imt^ and Ga^^tk, Jim- 3, 1863.
408 POISONS : THEIR EFFECTS AND DETECTION. [§ 483-485.
Casper relates the poisoning of a whole family by veratnim ; from
the stomach of the mo.ther (who died) and the remains of the repast
(a porridge of lentils) veratrine was separated.
Faber * recorded the poisoning of thirty cows by veratrum ; eight
died, and it is noteworthy that violent poisonous symptoms were pro-
duced in animals partaking of their flesh and milk.
§ 483. The symptoms appear soon after the ingestion, and consist of
a feeling of burning in the mouth, spreading downwards to the stomach,
increased secretion of saliva, and difficulty of swallowing ; then follow
violent vomiting and diarrhoea, with great pain in the bowels, often
tenesmus ; there is also headache, giddiness, a feeling of anxiety, and
the pupils are dilated. The consciousness is ordinarily intact; the pulse
is weak and slow, and the breathing embarrassed ; the skin is benumbed.
There may be also formicating feelings, and twitchings in the muscles
with occasionally the. tetanic cramps, which are constantly seen in frogs.
In cases which end fatally, the disturbance of the breathing and circula-
tion increases, and death takes place in collapse.
Ad important case of slow poisoning is on record,! in which
two brothers, aged 21 and 22 years, died after nine and eleven
weeks of illness, evidently from repeated small doses of the powder
of Veratrum album. They became very weak and thin, suffered
from bloody stools, sleeplessness, disturbance of the intellect, and
delirium.
§ 464. The post-mortem signs do not appear distinctive ; even in the
cases just mentioned — in which one would expect to find, at all events,
an extensive catarrh of the intestinal canal — the results seem to have
been negative.
§ 485. Separation from Organic Matters. — The method of Stas (by
which the organic matters, whether the contents of the stomach or the
tissues, are treated with alcohol, weakly acidified by tartaric acid) is to
be recommended. After filtering, the alcoholic extract may be freed
from alcohol by careful distillation, and the extract taken up with water.
By now acidifying gently the watery extract, and shaking it up with
ether and chloroform, fatty matters, resinous substances, and other im-
purities are removed, and it may then be alkalised by soda or potash,
and the veratrine extracted by ether. The residue should be identified
by the hydrochloric acid and by the sulphuric acid and bromine re-
actions; care should also be taken to ascertain whether it excites
sneezing.
A ptomaine, discovered by Brouardel, J was described by him as both
chemically and physiologically analogous to veratrine. A. M. Deleziniere§
* Zcitschr,/, StcuUsartneik., 1862. f Nivet and Geraud, Oaz. ffebdom.^ 1861.
X MoniUur Scient. (3), x. 1140. § BiUL Soc. Chim. (3), i 178-180.
§ 486. 487^]
PHYSOSTTGMINE.
409
hat) since iuveBtigated this substanc-e. Oulj wbon in contact with mr
does tho aimlogy to veratriue obtain, and DuloKiniere, to ascertaiu its
raactiona, studied it when in an atoiosphere of nitrogen. It appears to
be a secondary monaniine, C^^HgiNj and is iu the form of a colourless,
oily liquid, with an odour like that of the hawthorn. It ia iusoluble In
water, but alcohol, ether, toluene, and benzene diaaolve it readily. It
ostdiBes in the presence of air. The salts are deliquesceut.
VIII.— Physostigroine.
I 48G, The ordeal bean of Calabar {Phymstitjma faha) is a largtJ, all
but tasteless, kidney-shaped bean, about an inch in length, and iialf an
inch thit-'k ; its convex edge has a furrow with elevated ridgcsj and is
pierced by a small bole at one extremity. The integuments are coffee-
brown in colour, thin, hard, and brittle; they enclose two white coty-
ledons, easily pulverisahle, and weighing on an average 3*98 grma,
(61 grains)* The seed contains at least one alkaloid, termed Phjmsiig-
mine (6nt separated in 1864 by Jobat and Hesse ), and possibly a second
according to Harnach and Witkowsky, who have discovered in association
with physostigmine a now alkaloid, which they call d^abarine^ and which
differs from physostigmine in being insoluble io ether and soluble in
water. It is also soluble in alcohol ; and further, the precipitate pro-
duced by potassium iodo-hydrar gyrate in calabarinc solutions is insoluble
in alcohol*
§ 487* PhyflOfltigmine, or eserine, ia not easily obtained in a crystal-
line state, being most frequently ejttracted as a colourless varnish, drying
into brittle masses. It ia, however, quite possible to obtain it in the
form of partially-crystal I it)e erustB, or even rhombic plates, by care being
taken to perform the evaporation, and all the n}>erations, at as low a
temperature as possible, and preferably iu a dimly dit room ; for, if the
temperature rises to 40*, much of the alkaloid will be decomposed.
Hesse rec-oramcnds that tlie beans be extracted by alcohol, the alcoholic
solution alkalised by smlic carbotiato, and the liquid shaken up with
ether, which will retaiu the alkaloid. The ether solution \& now sepamted^
and acidified slightly with very dilute sulphuric acid ; the fluid, of course,
separates into two layers, the lower of which contains tfie alkaloid as a
sulphate, the upper is tho ether, which is withdrawn, and the acid fluid
passed through a moist filter. The whole process is then repeated as a
purification.
Again, Vee, who has repeatedly obtaioed the alkaloid in a crystalline
condition, directs the eitraction of the beans by alcohol, the alcoholic
solution to be treated as before with sodic carbonate, and then with ether j
410 POISONS : THEIR EFFECTS AND DETECTION. [§ 488.
the ethereal solution to be evaporated to dryness, dissolved in dilute acid,
precipitated by sugar of lead, and the filtrate from this precipitate alkalised
by potassic bicarbonate, and then shaken up with ether. The ethereal
solution is permitted to evaj)oratc spontaneously, the crystalline crusts
arc dissolved in a little dilute acid, and the solution is lastly alkalised
by potassic bicarbonate, when, after a few minutes, crystalline plates are
formed.
The formula ascribed to physostigmine is CigHgiNgO^. It is strongly
alkaline, fully neutralising acids, and forming tasteless salts. It crystal-
lises from benzene in large flat prisms which melt at a temperature of
105°-106°. It dissolves easily in alcohol, ether, chloroform, and bisul-
phide of carbon, but is not easily soluble in water. The sp. rotatory
power in chloroform is (a)^ = - 82*. The benzoate * crystallises in hard
white prisms melting at 115°-118' ; the majority of the other salts are
very hygroscopic.
If CO2 is passed into water containing the alkaloid in suspension, a
clear solution is obtained; but the slightest warmth decomposes the
soluble salt and reprecipitatcs the alkaloid. The hydrarg-hydriodide
(Ci5H.^jN302lII,2HgI) is a white precipitate, insoluble in water, becoming
yellow on drying, soluble in ether and alcohol, and from such solutions
obtained in crystalline prismatic groups. A heat of 70** melts the
crystals, and they solidify again in the amorphous condition.
It gives a precipitate with gold chloride, reducing the gold ; also one
with mercuric chloride, easily soluble in hydrochloric acid. It gives no
precipitate with platinum chloride.
§ 488. Tests. — Da Silva'sf test for eserine is as follows : — A minute
fragment of eserine or one of its salts is dissolved in a few drops of
fuming nitric acid; this makes a yellow solution, but evaporated to
complete dryness it is pure green. The green substance, called by others
chloreserine, dissolves to a non-fluorescent green solution ; in water and
also in strong alcohol it shows a band in the red between X670 and X680,
a broader but more nebulous band in the blue and violet between X400
and X418, and a very feeble band in the orange.
J. B. Nagelvoort J has recommended the following tests: — (a) An
amorphous residue of a permanent blue colour is obtained if a trace of
the alkaloid, or one of its salts is evaporated in the presence of an excess
of ammonia ; this blue alkaloid dissolves in dilute acids with a red colour ;
sensitiveness 0-00001 gm. (1 : 100000). The solution has beautiful red
fluorescence in reflected light ; when evaporated, it leaves a residue that
is green at first, changing to blue afterwards, the blue residue being
* Petit and Polonovsky (/. P?iarm., xxix. 55).
t S. J. Ferreii-a da Silva, Compi. JUiid,, cxvii. 330, 331.
t FlUckiger's Meactums, 1898,
1 489, 4900
PHYSOSTIGMIKE.
411
soluble ill water, alouholp aod cblorofurm, but not iu etbcr» Chloroform
eitraofea the blue colour froio tbcj wfttery atiimoniacal solutitni orjly par-
tiaUy> The blue &i>lutioim aru rtKldunod at first by IL^S, and diseoloured
aftorwurda, The blue colour is restored by expelling the 11^8 on the
waber-batb. (6) Eserbie utid its i$att^, diiSsolTod in fuming nitric acid,
give a yollow solution which, when warmed on the water-batb, becomes
darker and leavea a green residue. The latter dissolves with a groen
colour in water and alcohol ; in dilute nitric acitl the solution shows
a giTcnish -yellow fluoreacenee by tmnsmltted light, and a blood- red by
reflected light (c) A red Ihiid ia obtained when 0*010 gnu escrinc or
its mlieylate, 0 050 gm. of slacked lime^ and 1 c.c. of water are mixed
together. Warjuod in a water-bath, it turns green ^ and a piece of red
litmns-paper suspended in the te^t tube turu^ blue^ a glasa rod
moistened with HCl gives off the well-known white clouds chaiiuiter-
istic of an ammonia reaction* The green solution does not lose its
colour by evaporation. Biiryta water, ad tied to an eserino solution,
gives a white preci|ntatc that turns red when a trotigly agitated, sensitive
to 0*01 mgrm. (1 : 100000).
§ 489, Pharmaceutical Preparations*— Tfie only preparations officinal
in this country are a spirituotm extract (Exlradurn pht/iiOittigmaiis)^ used
priucipally for extomal application, tbe dose of which is not more than
18*1 mgrins. (*2S grain), and gelatine discs for tlie purpose of the
ophthahnio surgeon, each disc weighing about -^\rth grain, and coutaiiiing
hfVu S*'- ^^ ^^^ alkaloid,
g490. Eflfects on Animals.— A large number of experiments have
been made upon ant mala witli physostignune, most of them with tlic
impure alkali^id, which is a mixture of caiabarine and phygo«tigmine.
Now, the action of calabarine seems to be tlxe opposite to that of physo-
stigmine — that is, it eauisea tetanus. Hence, those experiments are not
of much value, unlcas the different proportions of the alkaloids are
known, llamack and Witkow&ky * made, however, some reaearchei
with pure phys^ostigniine, uf which tlie following are the main results:—
The smallcsst fatal dose for rabbits is 3 mgrms. per kilo, ; cnts about the
same ; while dogs take from 4 to 5 mgrms, per kilo. Frogs, under the
iuflucnce of the alkaloid, lie paralysed without the power of spontaneous
movement, and the seiimbility is dinitin3hei.l ; later, tlie breathing ceases,
and the reflex irritability becomes extinguished. The activity of the
heart is through "5 mgrm. slowed, but at the same time strengthened.
The warm*blooded animals experimented upon show rapid parulysia
of the respiratory centre, but the animals by artificial respiration can be
saved* Fibrillar muscular twitching of all the muscles of the body arc
observed. Death follows in all cases from paralysis of the respiration.
• Arth.f. FcUhifl. u. PhiiTVi., 1876» liiL v.
412 POISONS: THEIR EFFKCTS AND DETECTION. [§491-493.
Experimeats (first by Bexold, theu by Eraser aud Bartholow, aud lastly
by Schroff) have amply shown that atropine is, to a certain extent, an
antidote for physostigmine poisoning. Eraser also maintains an antag-
onism between strychnine and physostigmine, and Bennet that chloral
hydrate is antagonistic to physostigmine.
Eflfects on Man. — The bean has long been used by the superstitious
tribes of the West Coast of Africa as an ordeal, and is so implicitly
believed in that the iunocent, when accused of theft, will swallow it,
in the full conviction that their innocency will protect them, and that
they will vomit up the bean and live. In this way, no doubt, life has
often been sacrificed. Christison experimented upon himself with the
bean, and nearly lost his life. He took 1 2 grains, and was then seized
with giddiness and a general feeling of torpor. Being alarmed at the
symptoms, he took an emetic, which acted. He was giddy, faint, and
seemed to have lost all muscular power; the heart and pulse were
extremely feeble, and beat irregularly. He afterwards fell into a sleep,
and the next day he was quite well.
In August 1864 forty-six children were poisoned at Liverpool by
eating some of the beans, which had been thrown on a rubbish heap,
being part of the cargo of a ship from the West Coast of Africa. A boy^
aged 6, ate six beans, and died. In April of the same year, two
children, aged 6 and 3 years, chewed and ate the broken fragments
of one bean; the usual symptoms of gastric irritation and muscular
weakness followed, but both recovered. Physostigmine contracts the iris
to a point ; the action is quite local, and is confined to the eye to which
it is applied. When administered internally, according to some, it has
no effect on the eyes, but according to others, it has a weak effect in
contracting the pupil. In any case, the difference of opinion shows that
the effect, when internally administered, is not one of a marked character.
§ 491. Physiological Action.— The physiological action of physostig-
mine is strikingly like that of nicotine, which it resembles in being a
respiratory poison, first exciting, afterwards paralysing the vagus. Like
nicotine, also, it produces a great loss of muscular power ; it first excites,
and then paralyses the intra-muscular terminations of the nerves ; and
again, like nicotine, it induces a tetanus of the intestine. A difference
between physostigmine and nicotine exists in the constant convulsive
effects of the former, and in the greater influence on the heart of the
latter.
§ 492. Post-mortem Appearances.— But little is known relative to
the post-mortem appearances likely to be found in human poisoning ;
redness of the stomach and intestines is probably the chief sign.
§ 493. Separation of Physostigmine.— For the extraction of physo-
stigmine from the fluids of the body, Dragendorff recommends benzene :
§494-]
PHYSOSTIGMINE.
413
the nlcoholic filtered extract (first acidified} may be agitated with such
solvents as petroleum and benzeue, in order to remove colouriiig matter ;
then alkalis^ and shaken up with betizeuet atid the latter allowed to
evaporate spontaneously — all the operations being, as before atatedj
carried ou under 40*. If much coloured, it may be purified aeeoniing
to the principles before mentioned. In cases where enough of the
extract (or other medicinal preparation) has been taken to destroy life,
the analyst, with proper care, would probably not have much difficulty
in separating a soiall <|uantity of the active principle. It is rapidly
eliminated by the saliva and oMier secretions. In most cases it will be
necessary to identify phyaostigmine by its phy Biological activity, as well
as by its chemical ch^iracters. For this purpose a small quantity of the
substance should be inserted in the eye of a rabbit; if it contains the
alkaloid in question, in twenty minutes, at the very latest, there will
be a strong contraction of the pupil, and a congested state of the
conjunctival vessels. Further researches may be made w^ith a small
quantity on a bird or frog. The chief symptoms observed will he those
of parsilyais of the respiratory and voluntary nmscles, followed by death.
If a solution is applied to the web of a frog*3 fi>ot, the blood-vessels
become dilated, Physos tig mine appears^ according to Dragendorff and
Pander, to act as an irriUiutj for tliey always observed gastro-enteritis
as a result of the poison, even when injected anl>cutaneously. The
enhanced secretion from all mucous eurfacee, and the enlargement of
the blood-vessels, are also very constant symptoms. But of all these
characteristics, the contraction of the pupil is, for the purposes of
identification, the prlncipah A substance extracted from the tissue or
other organic matters, in the manner mentioned, strongly contracting
the pupil and giving the bromine reaction, would, in the piresent state
of our knowledge, he indicative of physos tigmine, and of tlmt alone,
^ 494. Fatal Dose of Phyftostigmina — One mgrm. (015 grain) as
sulphate, given by Vec to a woman subcntaneously, caused vomiting, etc.i
after half an hour, A disciple of Gubler's took 2 mgrms. without
apparent effect; but another mgrm,, a little time after, caused great
contraction of the pupil and very serious symptoms, which entirely
passed off in four hours. It would thus seem that three times this (»,«,,
6 mgrms,) would l>e Hkely to bo dangerous. Hence man is far more
sensitive to physostigraine than dogs or cats ; and 3 mgrms. per kilo, —
that is, a!>out 205 mgrms. (3 grains) — -would he much beyond the least
faU\l dose.
414 POISONS : THEIR EFFECTS AND DETECTION. [§ 495-497.
IX.— Pilocarpine.
§ 495. From the leaves of the jaborandi, Pilocarpus perinatafolius
(Nat. Ord. Rutacem), four alkaloids have been separated, viz. —
Pilocarpine, CuHj^NgOg; Isopilocarpine, ^-unj^NgOgj Pilocarpidine,
Ci^Hj^NgOg ; Jaborine, Cj^HjgNgOg.
Jaborine (C^iHi^jNgOg) is a strong base, differing from pilocarpine in
its sparing solubility in water, and more ready solubility in ether; its
salts are soluble in water and alcohol, but do not crystallise. P. Ghas-
taing,* by treating pilocarpine with a large quantity of nitric acid,
obtained nitrate of jaborine, and operating in the same way with hydro-
chloric acid, obtained the hydrochlorate of jaborine ; Jowett thinks that
this substance is a mixture of Isopilocarpine, Pilocarpidine, and a little
Pilocarpine.
§ 496. Pilocarpine (C^^HjgNgOj) is a soft gelatinous mass, but it
forms with the mineral acids crystallisable salts. The solutions are
dextrorotatory, a^^ + 100 S**.
If the free base is distilled in vacuo, a large portion of the pilo-
carpine is converted into isopilocarpine. By oxidation with potassium
permanganate, — ammonia, methylaraine, propionic acid, pilopic acid,
CgHj^O^, and homopilopic acid, C8H^2^4» result. Jowett considers that
Pilocarpine is a stereoisomer of isopilocarpine, and that both may be
represented by the following formula
CgHfi— CH— CH— CHg— C— N— CH3.
I I II ^>CH
CO CH2 CH— N====^'
\/
O
The nitrate and hydrochloride are at present much used in pharmacy.
Pilocarpine gives a precipitate with phosphomolybdic acid, potassio-
mercuric iodide, and most general alkaloidal reagents, but none that are
very distinctive. When a solution of gold chloride is added to one of
pilocarpine, a salt falls, having the composition CiiH^gNgOgiHCl + AuClg.
It is not very soluble in water (about 1 in 4600), and has been utilised
for the estimation of pilocarpine. Pilocarpine dissolves without the
production of colour in sulphuric acid ; but, with bichromate of potash
and sulphuric acid, a green colour is produced. It may be extracted
from an aqueous solution made alkaline by ammonia, by shaking up
with chloroform or benzene.
§ 497. Tests. — When a little of the alkaloid is mixed with ten times
its weight of calomel, and rubbed, and moistened by the breath, the
• Cwntipi. £end., vol. xciv. p. 223.
§ 49S0
PILOCAEPINE.
415
caloTnel m blftekcned ; cocaine b\bo acts similarly ; but hhe two could
not be mistaken for each other. If a solution of mercur-potaasiuai
iodide is added to 11 solution of the hydrochloride, the amorphous pre-
cipitate becomeB, in the course of a day or two, oily drops. "A solution
of iodine in potassium iodide gives in pilocarpine solutions a brown
precipitate that often crystallises to feathery brown crystals (micro-
scopically), and of serrated form, something like the blade of a scroll*
saw, when the crystallisation is incomplete." — F/Uckujer'A Uf^aetiom,
When boiled with sodium persulphate it gives an ammoniacal
Buiell, the vapours blacken mt>rcurous nitrate, and turn tnrmeriu piper
blue. Warmed with K^SO^, it gives first a yellow colour, then brownish-
red, blood red, and fnially a hrownish-red. Mandeline's reagent giTes,
on warming, first a goldenyullow colour, thou a clear green, and tinally
a blue,*
§ 498, Effects. — Pilocarpine, given subcutaneoualy in doses of about
32 ragrma. (A grain), causes within tive minutes a profuse perspiration
and salivation, the face hocomos flushed, and the whole boily sweats i
at the same time, the buccal secretion is so much increased that in a
few hours over a pint may be Becretcd. The tears, the bronchial
secretion, ami the intestinal secretions are also augmented ; there are
generally hciidacho aud a fr©picnt desire to pass water ; the pulse is
much quiokeued, and the temperature falls from 14" to 4" : the
symptoms last from two to five hours. Langley has shown that the
over-action of the submastillary gland is not affected by section cither
of the G^torda Itjmpani or of the sympathetic supplying the gland.
Although pilocarpine quickens tiie pulse of man, it alowa^ according to
Langley, t the heiirt of the warm-blooded animals, and that of the frog.
With regard to the frog, Dr, S. Eingor's researches are confirmatory.
With hirgc dosea the heart stops in diastole. If to the heart thus
slowed, or even when recently stopped, a minute quantity of atropine
be applied^ it begins to beat again. There is also a most complete
antagonism between atropine and pilocarpine in other respects, atropine
stopping the excefjsive perspiration, nnd relieving the headache and
pain about the pubes, etc. Pilocarpine, given internally, does not alter
the size of the pupil, but the sight may, with large doses, l>e affected.
This may ho doe to the | presence of pikicarpidine* If a solution ia
applied direct to the eye, then the pupil contracts. No fatal cane of
its administration lias occurred in man. The probable dangerous dose
would be about 130 mgrms. (2 grains) administ-ered subetiWmeonsly,
Pilocarpine must be classed among the heart poisons.
• E. BRTTal, Jouru. Phnrm. Chnn., xix., 1904.
t *'Tln^ Act4<ui of Jftbcfrmidi nti th© Hairt," by J* N4 Tjangloy, B.A.» Joum*
4i6 poisons: their effects and detection. [§ 499-501.
Isopilocarpine,* Ci^H^gNgOg, is an oily liquid, boiling at 261° at a
pressure of 10 mm. (a)D= +42*8'*. The following are the melting-
points of some of the salts of pilocarpine and isopilocarpine :—
Pilocarpine. Isopilocarpine.
Nitrate, 178' 169'
Hydrochloride, 204'-205° 127*
Hydrobromide, 185* 147"
Methiodide, an oil 114**
Pilocarpidine. — C^qHi^NjOj, a crystalline alkaline mass, soluble in
alcohol and chloroform, and a little soluble in water. The nitrate,
CiQHi^NgOgHNOg, gives prismatic crystals, melting at 137*, and
(a)D= +73-2% The aurochloride melts at 124*-125". The picrate is
an oil. Pilocarpidine causes dilation of the pupil.
X.— Taxine.
§ 499. Properties of Taxine.— The leaves and berries, and probably
other portions of the yew tree (Taxus baccaia)y are poisonous. The
poison is alkaloidal, and was first separated by Marm6.
Taxine (Cj^HgjOjQN). — Taxine has hitherto been obtained as a snow-
white amorphous j)Owder, scarcely soluble in water, but dissolving in
alcohol, in ether, and in chloroform; insoluble in benzene. It melts
at 82', gives an intense purple-red, with sulphuric acid, and colours
Frohde's reagent reddish-violet.
A slightly acid aqueous solution of the alkaloid gives precipitates
with all the group reagents and with picric acid.
The salts are soluble in water ; the hydrochloride may be obtained
by passing gaseous HCl into a solution of the alkaloid in anhydrous
ether. The platinochloride forms a yellow micro-crystalline powder,
(C87Er62^ioN)2H2P<^C^6- ^hc salts are generally difficult to crystallise.!
§ 500. Poisoning by Yew. — Falck has been able to collect no less
than 32 cases of poisoning by different parts of the yew — 9 were from
the berries, and the rest from the leaves. They were all accidental ;
20 persons died, or 62*5 per cent.
§ 501. Effects on Animals— Physiological Actioa — From the re-
searches of Marm^Borchers, it appears that taxine acts upon the
nervous centres — the nervous trunks themselves and the muscles re-
maining with their excitability unimpaired, even some time after
death. Taxine kills through paralysis of the respiration, the heart
beating after the breathing has stopped. The leaves contain much
* Jowett, Joum, Chem. Soc., Ixxvii. 478.
t A. Hilgerand F. Brande, Ber,^ xxiii. 464-468,
§ 502. S05J
TAXlKlt
417
fom»ic acjd, and their irritant action on the intestine is referred to this
caune.
§ 802. Effects on Man. — Seveml deaths from yew have resulted in
lunatic asyliima from thu paticuts eL<}wii^g the leaves. For example,
some years ago, at the CheBhire County Asjhim, a female, aged 41, was
audderdy taken ill, apparently faitjtmg, her face pale, her eyea shut, and
pulse alEDOst imperceptible. Upon the administration of stimulants,
she somewhat revived, but in a little while l>ecame quite unconscious.
The pupils were contracted, and there were epileptiform convulsions,
succeedeil by stertorous breathing. These convulBioag returned from
tune to time, the action of the heart became weaker, and there waa a
remarkable slowing of the respiratiojis, with long intervals between the
breathing. The woman died within an hour from the time when h<^r
illness was first observed, and within two horn's of eating the leaves.
Yew leaves were found in her stomach. Fti ant jt her case that occurred
at the Parkside Asylum,'^ the patient died suddenly in a sort of epileptic
6tv Yew leaves were again found in the stomach. In a case quoted by
Taylor, in which a decoction of the leaves was drunk by a girl, aged 1 5,
for the purpose of exciting menstruation, she took the decoction on four
successive mornings. Severe vomiting followed, and she died eight
hours after taking the last dose. In another case tliere were also no
symptoms except vomiting, followed by mpid death, Mr. Hurt, of
Mansfield, hiis recorded a case of poisoning by the berries. The child
died in convulsions before it was fl«en by any medical man,
P'rom these and other i^corded Gases, the symptoms seem generally
to be a quick pulse, faintiug or collapse, nausea, vomiting, couvulsiotm,
slow respiration, and death, as a rule sudden and unex|>ected* We may
suppose that the sudden death is really due to a rapid paralysis of the
respiration, and suffowition,
g 503, Post mortem Appearances,— In the c^se of the girl wlio
drank the decoction, nothing unusual was observed in the stomach or
orgaiis of the body ; but when the l^^Hves have been eaten, usually more
or less congestion of the mucous membrane of the stomacli as well as of
the bowels is apparent. In the case of the child who ate the berries
(Hurt's case), the stomach was filled with mucous and half-digested pulp
of the berries imd seeds. The mucous membrane was red in patches and
softened, and the small intestines w«re alao inflamed.
* Phftrta. Jmrn, (3), No. 29-1,
T]
41 8 POISONS: THEIR EFFECTS AND DETECTION. [§ 504.
XL— Curare alkaloids.
§ 504. Commercial curare is a black, shining, resinoid mass, about
83 per cent, of which is soluble in water, and 79 in weak spirit. It is a
complicated mixture of vegetable extracts, from various plants. Tube-
curare, which, according to Pictet, is the commercial variety, has been
shown by Boehm to contain two alkaloids^ tuhocurarine^ Ci^HgiNO^, a
reddish powder with a bitter taste, and curine, C^gHigNOg, which crystal-
lises in colourless prisms and melts at 212*.
Calabash-curare, from Strychnos toQci/era, is said to contain a substance,
eurarine, CigHggNOg, which is amorphous and very bitter. It must be
remembered that the name eurarine has also been applied to the mixed
alkaloids from commercial curare.
P(d-curare,from Strychnos castelnacuy conisAn^protocurine, CjoH^sNOg,
a slightly toxic crystalline substance, melting at 306°; protocttridine,
Ci^HjiNOj, a non- toxic crystalline substance, melting at 274°-276*' ; and
Proiocuranne, CijHggNOg, a toxic substance. These substances have not
been fully investigated.
Curare is an arrow poison* prepared by different tribes of Indians
in South America, between the Amazon and the Orinoco; therefore,
samples are found to vary much in their poisoning properties, although
it is noticeable that qualitatively they are the same, and produce closely
analogous symptoms. It is now known that some of the curare is
derived from different species of strychnos, and like the South American
strychnines paralyse, and do not tetanise. It is not unlikely that the
active principles of curare (or woorari) may be methyl compounds similar
to those which have been artificially prepared, such as methyl strychnine
* A constituent of the Borneo arrow poison is ** derrid/* a toxic principle obtained
from a leguminous plant, the Derris elHptica ; it is a resinous substance, which has
not yet been obtained in the pure state. It is said not to be a glucoside, nor to contain
any nitrogen (Greshoff, Ber., xxiii. 8537-8550).
The Ck)malis on the east coast of Africa prepare an arrow poison from the aqueous
extract of the root of Oubaion, a tree closely related to Carissa Schimperii.
Oubain is prepared by treating the aqueous extract with lead acetate, getting
rid of excess of lead by SHg, and concentrating in a vacuum. The syrup is boiled
with six times its volume of alcohol of 85**, and allowed to cool in shallow vessels :
crystals are obtained which are recrystallised, first from alcohol, and afterwards
from water.
Oubain, C9oH4eOi2, forms thin white nacreous lamellse. It is tasteless, odourless,
and neutral, almost insoluble in cold water, and soluble in boiling water ; it dissolves
readily in moderately concentrated alcohol, is almost insoluble in absolute alcohol,
and insoluble in ether and chloroform. Its melting-point is 200**. The solution of
oubain in water is Uevorotatory [a]D"-840. It is a glucoside, yielding on boiling
with dilute acids a sugar. It is very poisonous ; 2 mgrms. will kill a dog of 12 kilos,
weight in a few minutes, if subcutaneously injected ; but, taken by the stomach, it
produces no effect. —Amaud, C(tmpt, Rend,, cvi. 1011-1014.
§ S05-]
CUR ARK ALKALOina
419
ami niothyl Urueiiie, both of wliich have a ciiiure-lilte action. And
methoxjL groups have been found in tubo-curariiie and curine.
The mixed alkaloids of ourare were first separateit by Preyer in a
crystalline form in 1865. He extracted eurare with boiliti|^ alcohol, to
which a few drops of soda solntioii had been added^ evaj)orated off the
alcoholj took up the extract with water, and, alter filtration, precipitated
by phosphomolybdic acid, whioh had been acidified with nitric ackL The
precipitate was dried up with baryta water^ exhausted with boiliug
alcohol^ and the alkaloids precipitated from the alcoholic solution by
anhydrous ether. It may also be obtained by precipitating with
mercuric chloride solution, and throwiog out the mercury afterwards
by means of hydric sulphide, etc.
The alkaloids so isolated form colon rless^ four-aided^ very hygroacopic
prisms of bitter taste, and weakly alkaline reaction; soluble iu water
and alcohol in all proportions, but with difficulty aohible in amy! alcohol
and chloroform, and not at all in anb^drons ether, bisulphide of carbon,
or benaeue. The tmses form crystallisable siilts with hydrochloric,
nitric, and acetic acids. The alkaloids strike a purple colour with strong
nitric acid. Concentrated solutions mixed with dilute glycerin give au
ainorphous precipitate with potassic bichromate, and the precipitate
treated with sulphuric acid strikes a beautiful blue colour, Thechromate
m distinguished from strychnine chromate by its amorphouB character,
and by its comparatively easy solubility. If the chromates of strychnine
and curare alkaloids be mixed, and the mixed chromtites be treated
with ammonia, i^trycbnino will be precipitated and eurare alkaloids pass
into solution, thus forming a ready method of separating them,
§505. Physiological Effects, —-According to Voisin and Liouville^s
experiments, subcutaneous mjectiona of curare on man cauae, in small
doses, strong irritation at the place of application* swelling, and pain.
The temiierature of the body is raised from l"" to 2\ and the number of
respirations increased from 4 to 8 per minute. The pulse Ijecomes
somewhat stronger and more powerful. The urine is increased, and
contains sugar. Large doses administered to warm-blooded animals
cause, after a abort time, complete paralysis of voluntary motion and of
reflex excitability, and the animal dies in asphyxia, the heart continuing
to beat.
This state is beat produced, for the purpose of experiment, on frogs,
and, indeed, is the best test for the poison. A very minute dose
injected beneath the skin of a frog aoon paralyses both the voluntary
and respiratory muscles ; the animal continu*^ to breathe by the skin ;
the heart lieats normally, or, perhaps, a little weakly, and tlie frog may
remain in this motionless condition for days and yet recover. Only
curare and its congeners liave this effect. By tying the femoral artery
420
POISOKS: THKIR EFFKCTS AND Dfi^rfiCTION.
[§506.
of one of the frog's legs before administering the poison, an insight into
the true action of the drug is obtained. It h then found that the
refles eKcitabihtj and power of motion in the leg are retained, although
all the rest of the body is jiaraljaed. The only explanation of this is
that CO rare does not act centrally, but paralyseB the intramugcukr enda
of the motor nerves. The expei'imeuts of Overend Hof man {*' Stud ien
liber den Tetanus/* Pfhi'jer'n Archiifj Bd. xciii.), also show that curare
has a special action on the muscular fibre itself, decreasing in a marked
degree its power. Curare is eliminated partly through the liyer and
partly through the kidneys. DragendorfF found it in the faeces, while
a strikin^^ proof that it ia e^c crated by the kidneys is given by the
experiment of Bidder,* in which the urine of a frog poisoned by curare
was made to |X»ison a secondi and the urine of the neeond, a third. The
easy excretion of curare through the kidneys furnishes an ex[}lanation
of the relatively large dose of curare which eau be taken by the stomach
without injury. A dose which, given by subcutaneous injection, would
produce violent symptoms, perhaps death, may yet be swallowed^ and no
ill etfecta follow. It is hence presumed tKat, in the first case, the poison
is, comparatively speaking, slowly absorbed, and almost as fast separated,
and put, as it were^ outside the body by going into the mine ; while, in
the other case, the whole dose is thrown suddenly into the circulation.
g n06. Separation of Cui-ariae.— It is hardly probable that the
toil col oglst will have to look for ourarine, unless it hm entered the
body by means of a wound or by subcutaueous injection j so that in nil
cases the absorbed poison alone nmst be sought for. The seat of entry^
the liver, the kidneyfi, and the urine are the only parts likely to be of
&n^ use, Dragendortf recommends the extraction of the tissues with
water feebly acidulated with a mineral acid, to precipitate albuminous
matters^ etc., by strong alcohol, and the se|mration, by means of benzene,
of fatty matters. The liquid is tlmti made alkaline, and shaken up with
petroleum ether, which removes certain alkaloidal matters. It ia now
evaporated to drynesrs^ mixed with finely -powdered glass, and extracted
with absolute alcohol. The alcohol is evaporated to dryness, and any
curarine extracted from this residue with water. By very careful
drying up of this last extract, and taking it up in alcohol, the alkaloid
is said to he obtained so pure as to respond to chemical teats The
identification may be by the colour reaction of sulphuric acid described
ftnte, in all cuaes supplemented by its physiological action on frogs. t
• Aii'h.f. AnaL u. Fhyshl , 1S79, p. 698.
t It ia kinjwji thfii cunire may caiiao alight syaiptonis of excitation l*afore the
pamlyBis uonieii on. M. Cooty h&s uuctiuddeti iu isolating the»e symptotna hy
eLiiplriyiiig feehlp extracts of Strythnns irij^mervia, or amall dtmeB of csitalii native
prejjaratioas. By thtsii lutsans, in dogB, a new phitse of intoxication may Im> present
for ten or oven twenty miuuiea. In the tinit uiHtiinco the auimal is agiuted, jump-
§ so/, SoS-l
COLCHICINE,
431
Xn. Colchicine,
§ 507. The whole of the Colekinum autumnale^ or common meadow-
aartron, is [joisotiouBj owing to the presetice of an alkaloid (discovered hy
Pel let i e r and Cave n ton ) cal 1 ed CnUh itiijifi.
According to Joliauusou'ij exjieriiiionts, the dried eolohicuni Beeds
contain 1*15 per cent of colchicine; the leaves, r459 per cent,; the
bulbs, from 1"4 to r58 percent ; and the roots ^ 0*634 per cent. The
frci^uent poisoriinj^ of cattle in the autnnin by colclncum, its vise in
quack pills for rheumatism, and its supjioaed occafiioual prepuce hi
beer, give it tin aiudytical imixtrtaiice,
§ 508. Colcliicme (C^^,H,^NOfl) may be extracted from the seeds, etc.,
in the nmouer recommeuded by Hlibler : — The seeds are treated, without
crushing, by hot 90 per cent, alcohol, and the alcoholic solution evapo-
mted to a ayrup, which is diluted with twenty times ita bulk of water
and tiltered ; the liquid is next trcuted with acetate of lead, again filtered,
and the lead thrown out by phosphate of soda, Colchiciuo is now pre-
eipit^ited as a t^vnnate.'*^ The precipiLitiou is best fractional, the first
and last jrortious being rejected as containing impurities. The tim-
nate in decomposed in the utiiial way with litharge and extracted by
alcohoL
A simpler method is, however, extraction by chloroform from an
aqueous solution, feebly acidiBed, as recommended by DrageudorO*.
Ingt Kcmtching, biirking, as if in a state of g«n«ml hy|>0m'Bthe«i». Then it iireHenis
Uulf cliorv^ic t^hiick^ or ti'cmuni ; tliQ pupils dilate, and ara altemntely dllj^ted anil
04)11 tinu^tocl. The lie^rt s o^^tlon i^ incrcaiied or diminiithed in freipiency ; somottunea
there Ih voniitiiijuf, niictviritiou, or dcfec4tb>n ; uiid there is always BslivatioiL Finally,
the ceuiTa! And jseripbertil temperatures are raised, and the excitability of the muscle
And narvea bi^coniea higlily iucrea^d. With the native prefiaration of curare, it is
itiiposiiible to proloni; this stage, and symptoms of psralyeb aoou become asiiocistad
with those of excitement The choreic ahocka were found to be arreated bj i^eetioii
of tbe seistic uerve. Other experimeata proved that the sposme originated from the
Hpinal curd ^ and were inl^lueueed by its preceding runctioual condition. If the cord
was tied in tlie mkl-dorsa] region, and the curare injected^ the s[)asm£ were .Htill jiro-
duced hi th« liind legs ; but if, after tbe ojs^mtion, the eatcitabillty of the poaterior
segment bet:aiue lowered^ the apaam waa mo longer produced in the bind ]eg». This
deiMMidcnce i>n a fierfect functional activity in a potnt of dilference of these iiipasma
from those produced by strychnine, and by asphyxia. The action of snmll dosea of
curare ia not, however^ limited to the apitial cord, The diminti^hed frequentty of the
heart continues after section of the pneumogaa tries, and will eren occur if tlte
pneumogastilea have been p re vionaiy divided. From the%iu facts }kl, Couty coDsidcrs
that €urare nuist not lie regarded sa entirely destitute of a **eouvn(aftUt" aetiou,
nor of an action on the central nervous aystoni,
* The purest tannic acid muat be used. The commercial tannin may be purified
by evajjoratiDg to dryn^aa with lithai^, exhausting the tannate of lead repeatedly
with boihng alcohol and water, and, lastly, suspending ia wat^r^ and separating tba
lead by SH^
422 POISONS: THKR EFFECTS AND DETECTION. [§ 509, 51O.
The parts of the plant are digested in very dilute acid water, and the
resulting solution concentrated and shaken up with chloroform, which is
best done in a separating tube.
Colchicine contains four methoxyl groups, and its constitutional
formula is considered to be C,5H^[NH(CH3CO)](COOCH3)(OCH3)3.
Its melting-point is 143°-147'. It is usually a white, gummy mass.
It is easily soluble in cold water, in alcohol, and in chloroform. The
solutions are laevorotatory. It is hardly soluble in ether. Boiling with
dilute acids or alkalies in closed tubes yields colchiceine, CgiHgsNO^j.
Colchiceiue contains three methoxyl groups. It crystallises with one
molecule of water and melts at 140' ; when anhydrous it melts at 172'.
It dissolves but little in cold, copiously in boiling water. Colchiceine is
a monobasic acid, forming salts with the alkalies, and colchicine is its
methyl ester.
Zeisel* has formed acetotrimethylcolchicinamide(NHAcCi5Hg(OMe)3
CONH3) by boating colchicine with alcoholic ammonia in closed tubes
for four hours at 100'. The amide is crystallised from hot alcohol ; it is
readily soluble in dilute HCl, almost insoluble in water ; when a strong
hydrochloric acid solution of the amide is treated with a small amount of
potassium nitrite a splendid violet colour is produced.
§ 509. Tests. — Ferric chloride, if added to an alcoholic solution of
the alkaloid, strikes a garnet-red ; if to an aqueous solution a greeu or
brownish-green ; nitric acid added to the solid substance gives a violet
colour. Erdmann's reagent (nitrosulphuric acid) gives in succession
green, dark blue, and violet colours, ultimately turning y<3llow, changed,
on addition of an alkali, to raspberry-red. Maudelin*s reagent (1 grm.
of ammonium vanadate in 200 grms. of sulphuric acid) gives a green
colour.
§ 510. Pharmaceutical Preparations. — Colchicine itself is officinal in
Austria — the wine in the British, French, and Dutch, and the seeds
themselves in all the pharmacopoeias. The wine of colchicum, ofhcinal
in nearly all the pharmacopoeias, is made with very ditferent proportions
of seeds or bulbs.
The tincture of colchicum is officinal in our own and in all the
Continental pharmacopoeias ; in the British, one part of seeds is exhausted
by eight parts of proof spirit.
A tincture of colchicum seeds, examined by Johannson, contained
•18 per cent, of colchicine, and a tincture prepared from the bulbs '14
per cent.
Colchicum vinegar is not otiicinal in Britain, but one containing 5*4
per cent, of acetic acid is so in the Netherlands, Germany, and France ;
the strength appears to be about '095 per cent, of colchicine.
* MonaUh,, ix. 1-30.
§ SM,ST2]
COLCHICINE.
423
An extract of colchicum is cflflcitial in Britain and France ; and an
acetic extract in Britain. The latter is the most active of all the
pharmaceutical preparations of colchicum*
Lastly, an oxymel of colchicum is in use in Germany, France, and
the Netherlauds,
Quack and Patent Medicines. — In all specifics for gout the analyst
will niituraUy searcb for colcliienm. Moat gout pills contain the extracts ;
and liquids, such as '^Reynolds* gout specific," the wine or the tincture,
variously flavoured and disguised.
The strength of the different pharmaceutical preparations may be
ascertained by dissolving in chloroform, evapomting off the chloroform,
dissolving in water (which is finally acidified by from 7 to 10 per cenL
of sulphuric acid), and titrating with Mayer's reagent (see p, 264). If
the solution is diluted so that there Is about I part of colchicine tn
600 of the solution, then each c.c. of Mayer's reagent equals 31*7 mgrmSp
colchicine,
^ 5IL Fatal Dosa. — la Taylor's Prhtciplm 0/ Medical Juri^rudmce
la mentioned an instance in which 3^ drachma of colchicum wine, taken
in divided doses^ caused death on the fourth day« The quantity of
the active principle in the colclucum wine* as found by Johannson
{Dratjemlorff)^ being 0^18 per cent, it follows that 24*4 mgrras. (*378
grain) were fatal, though not given as one dose^ so that this quantity may
be considered as the least fatal one, Casper puts the lethal dose of
colchicine at from 25 to 30 mgrms. ('385 to 463 grain). It is, howevetj
incontestable that there are cases of recovery from as much as 70 mgrms,
(r08 grain). The lethal dose of the pharmaceutical preparations of
colchicum may, on these grounds^ be predicted from their alkaloidal con*
tenia, and, since the latter is not constant, in any medico- legal inquiry,
it may he necessary, where facility is given, to ascertain the strength of
the preparation administered.
§512, Effects of Colchicine ou AninmlB. — The researches of
KoBsbach show that the carnivorce are more sensitive to Qolchicine
than any other order of mammals* Frogs show a transitory excite-
ment of the nervous syatein, then there is loss of sensattoUf paralysis
of mution, and of the respiratory apparatus; the heart beata after
the respirfition^ has ceased. Death follows from paralysis of the
respiration. The mucous membrane of the intestine is much congested
and swollen.
The senior author has seen cattle die from the effects of eating the
meadow -safiVon ; the animals rapidly lose condition, suffer great abdominal
pain, and are generally purged. The farmers, in certain part^ of the
country, have had rx tensive losses from want of care and knowledge
with regard to colchicum |x»isoning.
424
poisons: THEIK EFKKCTS AND DKTBCTION.
[§ 513-
§ 513. Effects of Colchicine on Man.— Colchtchie poisoning in man^
ia not verj common: 2 deatliB (acoiJenUd) are recorded in England and
Wales during the ten ye&rs ending 1892, iind a single death ia also
recorded in the Registrar-Gen oral's returns for 1896, ¥\ A, Falck was
able to collect from niedienl Utemturej prior to 1880, 55 cases, and be
gives tho following analysis of the cases :^In 2, colchicnni was taken
for suicidal purposes ; of the uninieiitional poisonings, 5 were from too
Urge a medicinal dose of eolchicum wine, syrup, or extract, given in
cases of rheumatism ; iu 13 cases^ culchieuni waij used as a purg^itive;
42 cases were owing Uj mistaking different prepiirations for drinks, or
cordials — ^the tincture in 5, and the wirje in 14, being taken instead of
orange tincture, quinine wine, schnapps or Madeira; iu 1 case the corms
were added to mulled wine, in another, the leaves consumed with salad ;
in 16 cases (all children), tlie seeds of colchicura were eaten. Forty-six
of the 55 died — that is, 83-7 per cent.
Tn the remarkable trial at tho Central Criminal Court, in 1862, of
Margaret Wilson (Reg. y. Marg, Wilmn)^ who was convicted of the
murder of a Mrs. Soraers, the evidence given rendered it fairly probable
that tlie prisoner had destroyed four people at diflfereut dates by culchi*
cum. The symptoms in all four cases were — burning pain in the throat
and stomach, intense thirst, violent vomiting and purging, coldness and
clamminess of the skin, excessive depression, and great weakness. One
victim died on the second day, another on the fifth, a third on the eighth,
and the fourth on the fourteenth day. Schrofl' witneaseil a case in which
a man took 2 grms. (nearly 31 graius) of tho corms; iu one and a half
hours he experienced general maiaim ; on the next day there were flying
muscular pains, which at length were concentrated in the diaphragm,
and the breathing became oppressed; there was who pain iu the neigh-
bourhood of the duodenum, the abdouien was inflated with g^is; there
was a sickly feeling and faintnesa. Then came on a sleepy conditign,
lasting several hours, followed by fever, with excessive pain in the head,
noises in the ears, and delirium ; there was complete recovery, but the
abdomen continued imhjfnl until the fifth day.
In another instance, a gentleman, aged 50, t had taken twenty eiglit
of Blair*E gout-pilla in four and a half days for the relief of a rheumatic
atfection He suffered from nausea, g^ip^tig pains in tlxe belly, consider-
able diarrhoea, vomiting, and hiccough ; towards the end there was
stupor, convulsive twitchings of the musclea, paralysis, and death. The
fatal illness lasted fourteen days ; he was seen by three medical men at
different dates — the first aeems to have considered the ease one of
* For the curiotie epldi^mic of dinrrhoea which broke out in the Rhone Gorge in
17S5, and wag referred to colchicine, see " Foods," p. 248, 5th edition*
t 8oe Ltined, 1881, vol, i p. 368.
§ 5"4 5*51
coLceicraK,
425
diarrhoea, the aecond oue of suppre&aed goiifc; but JJjv G* Dudd was
atruck with tho Bitiiilarity of tho symptoms to tlioae from uu acrid
poiaon, and discovered the fact that tlie pillu had been taken. These
pills wen? examined by the senior antht^r ; they were ex^esnively hard,
and practimilty cmi»i8tod of nothing else that) the fitjcly -ground uolchicum
comis ; six pi Ik yielded 8 mgmis. of colchicine, so that the whole twenty-
eight would contain 39 mgrnis. {* grain). Dr. Budd considertKi that the
whok of the pills, which were of a Htony hardDesa, remained in the
bowels for «onie time undigested^ so that the ultimate result was the
same as if the whole had been taken in oue dose.
g 514. Tho general eyjuptoniB prod need by colchicnm are^ — raxire or
leas buruiug pain in the whole intestinal tract, vomiting, diarrhoBa, with
not un frequently bloody atooly; but sometimes diarrhosa is absent. In
single eai^es tenesmus, dysuria, and, in oue case, hieinaturia have been
noted. The respimtitm in usually troubled, the heart's action slowed,
the pulse small and weak, and the temperature sinks. In a few cases
there have been ])aiuH in the limbs ; cerebral disturbance Is rare ; but in
two cjises {one dej^cribed ante) there was stujjor. Muscular weakness
has been observed generally. In a few cases there have been cramps in
tiie calves and in tho foot, with early collapse and death.
Post-mortem Appearances. — 8chrofi' found in rabbits fjoisoued with
from O'l to I'D grm* of colchicine, tolerably constantly outeritis and
gastritis, and always a thick, pitch-like blood in the heart and veins,
Casper ha^ carefully reconled the post-morlom appearances in four
labourers, ages ranging from tifteeu to forty years, who, finding a bottle
of colchi cum -wine, and supposing it to be some kind of brandy, each
drank a wine glassful. They all died from \tM efFectft. In all four there
was great hypera^mia of the brain membranes and uf tho kidneys. The
large veins were tilled with thick, dark, cherry-red blood, very similar to
that seen in sulphuric acid poisoning. There wjib an acid reaction of
the contents of the stomach. The lungs were moderately congested.
The mucona mtmbrane of the stomach of the one who died lirst was
swollen and scarlet with congestion ; with the second there was some
filling of the vessels at the small curvature* while the stomachs of the
third and fourth were quite normal. In 5 cases described by Koux
there was also hyperBemia of the brain and kidneys, but no gastritis or
enteritis. It is, therefore, evident tliat tfiere are in man no constant
pathological ciianges from cnlfbicine poisoning,
§515, Separation of Colchicine from Ot^anic Matters.— W.
Obolonaki * bus recoimiienUed the following process : — -The finely divided
viscera are triturated with powdered glass and digeste<l for twelve
houra with alcohol. The liquid is squeezed unt and the dry residue
426 POISONS: THBIR EFFECTS AND DETECTION. [§ 5 1 6.
washed with alcohol. The extract is concentrated at a temperature not
exceeding 80*, and the cooled residue made up to the original volume
with alcohol. The filtered liq^uid is evaporated as before, and this opera-
tion repeated until no more clots separate on addition of water. The
residue is then dissolved in water, the solution purified by shaking with
light petroleum, and the colchicine finallj extracted with chloroform.
In cases of poisoning by colchicum at Berlin, Wittstock used the
following process : — The contents of the stomach were mixed with a
large amount of alcohol, a few drops of HCl added, and the whole
well shaken ; the fluid was then filtered, and the filtrate evaporated to
a syrupy consistence at 37*". The resulting residue was dissolved in
distilled water, the fat, etc., filtered ofi*, and the liquid carefully evapo-
rated. From the extract foreign matter was again separated by treatment
with alcohol and filtration, and the last filtrate was evaporated to a syrupy
consistence. The syrupy fluid was taken up by distilled water, filtered,
evaporated to 30 grms., and 2 grms. of calcined magnesia with 90 grms.
of ether were added. After a time, the ether was removed, and allowed
to evaporate spontaneously. The residue was once more taken up with
water, filtered from fat, eta, and evaporated. This final residue gave
all the reactions of colchicine. In medico-legal researches, it must be
remembered that colchicine is absorbed but slowly, a not insignificant
portion remaining in the bowels, with the f&eces.
XIII.— Muscarine and the Active Principles of Certain Fung-i.
§ 516. The Amanita Muscaria, or fly-blown agaric, is a very con-
spicuous fungus, common in fir-plantations, about the size and shape of
the common mushroom ; but the external surface of the pileus is of a
bright red, or sometimes of a yellowish cast, and studded over with
warts. The common name of the fungus denotes that it was used in
former times as a popular insecticide ; the fungus was bruised, steeped
in milk, and the milk exposed, in the same way as we now expose
arsenical fly-papers.
Some peculiar properties of the agaric have long been known to the
natives of Kamschatka, and of the north-eastern part of Asia generally.
They collect the fungi in the hottest months, and hang them up to dry.
The fungus is then rolled up in a kind of bolus, and swallowed without
chewing. One large, or two small, fungi will produce a kind of intoxi-
cation, which lasts a whole day. It comes on in about two hours' time,
and is very similar to that of alcohol. There is a giddy feeling, the
spirits are exalted, the countenance becomes flushed, involuntary actions
§517.518,]
MUSCABINfi.
427
and words foltow, and sometimes loss of eouscioitstiess* Tt renders some
persons remarkablj active, ami pn^res highly stimulant to muscular exer-
tion ; by too large a dose violent spasmodic effects are produced, ''So
very exciting to the nervous syateni in many Individiials is tliis fungus,
that the effects are often very ludicrous* If a penion under its influence
wishes to step over a straw or small stick, he twkea a stride or a jump
sufficient to clear the trunk of a tree. A talkative person cannot keep
silence or secretfl, and one fond of music is perpetually singing. The
most singular effect of the amanita is the tniiuenee which it has over the
urine. It is s did that froni time immemorial the inhabitants have known
that the fungus imparls an intoxicating quality U) that ^ecrction^ which
continues for a considerable time after taking it. For instance, a man
moderately intoxicated to-day will, by the next morning, have slept
himself sober, but (as is the custom) by taking a taacup of his urine
he will be more powerfully intoxicated than he was the preceding dny.
It is, therefore, not uncommon for contirmed drunkanls to preserve their
urine as a precious liquor against a scarcity of the fungus. The intoxi-
cating property of the urine is capable of being propagated ; for every
one who ptir takes of it has his urine mmilarly a fleeted* Thus, with a
very few amanitas, a party of drnnkurds may keep up tfieir debaucli for
a week* Dr. Langsdorf nientioua that by means of the second person
baking tfie urine of the first, the third of the second, and so on, the
intoxication may be propagated through five individuuls*"*
^517* A few cases of j>oisoning by the fly- blown agaric from time to
time Imvc occurred in Europe* where it has been eaten in mistake for the
cKlible fungi, or taken by ciiildren allured by the bright attractive colours.
In these crises the [lois^ouou:^ ^ymptomH noticed have been tliose of gastro-
intestiual irritation, as shown by vomiting and diarrha^z^ dilated f pupils,
delirium, tetanic convulsions, alow puke, stertorous hrea thing, collapse,
and death. In a few vii&ea epileptic attacks and tri^mu^ have been
observed. The course is usually a rapid one, the death occurring within
twelve hours. In caaea of recovery, convalescence has been prolonged.
The post-mortem characterifitics are not distinctive, a fluid con-
dition of the bkK>d, hyperemia of the brain, liver, and kidneys have been
noticed,
S 518, Mttscame, —These effects are piirtly due to an undiscovered,
toxic Bul^tiincc — which seems to be destroyed at the temperature of
boiling water, and is probably of rather easy destruetibility — and of a
very detinite poisonous alkaloid {mttsearine) flrst separated by a complex
• Lindley's Vt^t^U Kingdmn,
t This is the more cunous, for muacarine strongly oontiucts the [m|fil. It* how-
eveFp fcendR to j^rove what is stated in the lejct— vbc,« tlist therts ia more Uuia oae
poiBonotUi auljuianoe in AmanUm,
428 POISONS: THEIR EFFECTS AND DETECTION. [§ 519.
process by Schmiedeberg and Koppe in 1869.* It is a trimethyl-
ammonium base. Fischer has prepared a base very similar, but not
identical, with muscarine ; the base on oxidation yielded betaino.
Schmiedeberg and Haniack,t by oxidation of choline with nitric
acid, obtained a base also very similar, but not identical, with natural
muscarine : —
/CH2 - ClU - OH /CH2 - CH(OH),
(CH3)3^N< " +0^(CH3)3^N<
Choliue. Muscarine (t).
The true constitution of muscarine has not yet been determined.
Muscarine is a colourless, strongly alkaline, syrupy fluid, which, if
allowed to stand over sulphuric acid, becomes gradually crystalline, but
liquefies again on exposure to the atmosphere. It dissolves in water in
every proportion, and also in alcohol, but is very little soluble in chloro-
form, and insoluble in ether. It is not precipitated by tannin : it forms
salts with acids, and gives precipitates with auric chloride, phospho-
tungstic, and phosphomolybdic acids, and also with potassio- mercuric
iodide. The last precipitate is at first amorphous, but it gradually
becomes crystalline. This was the compound used by the discoverers
to separate the base. With many other general alkaloidal reagents
muscarine forms no compound that is insoluble, and therefore gives no
precipitate, such, e,g., as iodine with potassic iodide, picric acid, and
platinic chloride. Muscarine is a stronger base than ammonia, and
preci[)itates copper and iron oxides from solutions of their salts. Mus-
carine is very poisonous ; 2 to 4 mgrms. are sufficient in subcutaneous
injection to kill cats in from two to twelve hours — larger doses in a
few minutes ; but with rabbits the action is less intense. Cats become
salivated, their pupils contract, they vomit, and are purged, the breathing
becomes frequent, and there is marked dyspnoea. At a later stage the
respirations are slower, and there are convulsions, and death.
The alkaloid has also been tried on man. Doses of from 3 to 5
mgrms., injected subcutaneously, cause, after a few minutes' profuse
salivation, increased frequency of the pulse, nausea, giddiness, confusion
of thought and myosis, but no vomiting, and no diarrhoDa. Small
quantities applied to the eye cause, after a few minutes, a derangement
of the accommodation, but no change in the size, of the pupil ; larger
quantities cause also myosis, which depends upon an excitement of the
sphincter iridis, or of the oculomotorius.
§ 519. The actions of muscarine and atropine are to a great extent
antagonistic. This is especially and beautifully demonstrated by the
* Das Miiscarin, das giftige Alkaloid den FlUgenpilzes, Leipzig, 1869.
t Ai-ch. f, exper. Path,t Bd. iv. u. v.
§ 5^o. 52 1 ]
MUaCARINK.
429
efTects of the two substances on the fn»g*s heart. The action of muscarhie
upon the heart is to excite the inhibitorj nerve apparatus, while the
action of atropine is to paralyse the same sjHtem. One mgrm- of mus-
carine, iiijectetl subcuta neon sly into a frog, arrests tlic heart in tfiaxtoie^
but if a suitalile dose of atropine ia applied to the heart thus arrested,
it begins to beat again ; or, if atropine is first given, and then muscarine,
the heart does not stop. The muscarine heart, when it has ceased to
beat^ ma J be success full j' sti mulcted by galvanism. Muscarine at first
excites the respiratory centre, and then pantlysea it.
I 520. Detection of Mnscarine in the Body,— Muscarine itself is
not likely to be taken as a poison or administered ; but if it is sought
for in the fly-blown agaric, or m the tissues or organs of persons who
have been poisoned by the fungus, the process of Brieger appears the
best. The process depends upon the fact that muscarine pives a soluble
mercuric chloride compound, and is not precipitated by chloride of
piatinnm, whilst most other substances aeoompinying it give more or
less insoluble ju^ecipitates. The aubstanoes are treated with water
aeidulated with hydrochloric acid, and the acidulated extract concentrated
(best in a vacuum) to a syrup* The syrupy residue is now treated with
water, and the aolntion precipitated by means of mercuric chloride
solution and any precipitate filtered off; the filtrate is freed from
mercury by SH.jj and evaporated to a syrup ; the syrup is repciitedly
extracted with alcohol, and the alcoholic solution precipitfited with
platinum chloride and any precipitate filtered off. Tlie filtrate is freed
from idcoliol, and all the platinum thn>wn oat of solution by SH^ ; the
aqueous filtrate is now concentrated to a small volume, and again
platinum chlonde iidded, any precipitate which forms is filtered off, and
the final filtrate allowed to crystallise. If muscarine be present, a
crystalline couipound of muscarine platinum chloride will form.
The crysttds are usually Octahedral in form, and have the composition
(C^Hj^NO.Clj^PtCl^ ; the perceutiige of pLitiiuun is 30-41.
It would probably he necessary to identify farther, by the action of
the poison on a frog,
g 52L The Agaricus phaUoides, a common autumn fungus, has been
several times mistaken for m^lshroomfi, and has proved fatal ; of some
53 cases collected by Falck, no less than 40, or 75 per cent, were
fatal ; the real mortality is much lower than this, for it is only such
oases that are pronoanci»d and severe which are likely to be recorded*
The fungus contains a toxalbumin which has been named "phallin/*
The action of this toxalbumin is to dissolve the blood corpuscles; ac-
cording to Kobe rt, even one 250,000tb dilution produces ** polycholie "
with all its consequences^ such as the escape of haemoglobin and its
deeompositton produotn in the blood and urine, multiple blood eoagula-
430 poisons: their effects and detection. [§ 522, 523.
tioD through the fibrin ferment becoming free, and serious cerebral
disturbance. If into a dog, cat, or rabbit, only 0*5 mgrm. of phallin be
injected intravenously, within from twenty to thirty minutes blood
from a vein shows that the serum has a red colour.
The symptoms in man first appear in from three to forty-eight hours ;
there is mostly diarrhcea, violent vomiting, with cramp in the legs,
cyanosis, and collapse. There are also nervous phenomena, convulsions,
trismus, and, in a few cases, tetanic spasms. The pulse, in seven cases
described by Maschka, was very small, thready, and quick, but in others,
again, small and slow. The pupils have in some cases been dilated, in
others unchanged. Death is generally rapid. In two of Maschka's
cases from sixty to sixty-eight hours after the investigation, but in the
rest from twelve to eighteen hours. Life may, however, be prolonged
for several days. In a case recorded by Plowright,* in which a boy
had eaten a piece of the pileus, death occurred on the fourth day.
§ 522. The post-mortem appearances observed in Maschka's seven
cases were — absence of cadaveric rigidity, dilatation of the pupil, a dark
red fluid condition of the blood, numerous ecchymoses in the pleura, in
the substance of the lungs, the pericardium, the substance of the heart,
the liver, kidneys, and spleen. The mucous membrane of the digestive
canal presented nothing characteristic. In two cases there were a few
ecchymoses, and in one the mucous membrane of the stomach was
softened, red, and easily detached. In one case only were any remnants
of the fungus found", by which the nature of the substance eaten could
be determined. The bladder in each case was full. In three cases a
fatty degeneration of the liver had commenced. The same appearance
was met with in some of the older cases related by Orfila.
§ 523. The Agaricus pantherinus is said to be poisonous, although
Hertwig found it to have no action when given to dogs.
The Agaricus ruber, a bright-hued futigus, growing profusely on
the Hampshire coast, of a purple-red colour — the colouring-matter
not only covering the pileus, but also extending down the stipe — is
poisonous, and has been chemically investigated by Phipson,t who has
identified a colouring-matter ruber ine^ and an alkaloid agarythrine,
Agarythrine is separated by macerating the fungus (from which the
skin containing the colouring-matter has been removed) as completely as
possible in water acidulated with 8 per cent, of hydrochloric acid. The
filtered solution is neutralised by sodic carbonate, and the alkaloid
shaken np with ether. On evaporation the ether leaves a white, some-
what greasy-looking substance, having a bitter burning taste, and easily
fusible into yellow globules, giving forth an odour like quinoleine; it
is soluble in alcohol and ether. From Phipson's observations it would
♦ Lancet, 1879. t Chem. News, p. 199, 1882.
I S24-526.]
DIGITALIS GROUP.
43 »
appear probable that the red oolouring-matter ib derived from a decom-
poaitioo of this alkaloidal subatance. A rose^red colour is produced bj
the aetioD of nitric acid^ and chlorinated lime first reddens and then
bleaches it. Buchwald* has rccordefl threo cuhcs of poisoning by this
fungus; the patients were hiibourers, who, after eating the fungus,
HufiPered from vomiting, thirst, a *' drunken " condition, cramp, albu-
min urlHj and disturbance of the seuaory functions. The fungus causes
in cats mjoais, but is said not to affect rabbits.
§ 524. The Boletus satanas, or luridus (Lena), \& poisonous; very
amall quantities of the imcotik*^! fuugus caused in Lens, who experi-
tuented upon its properties violent vomiting* In cases in which this
fungus has been eaten accidentally, the symptoms have been very similar
to cholera.
g 525. The Common Morelle seems under certain conditions to be
poisonous. From six to ten hours after ingestion there have appe4ired
depression, nausea, jaundice, dilated pupils, and in ti^e worst cascis at the
end of the Brst day, delirium, somnolence, and muscular cramps, followed
by collapse and death. In a cme observed by Krorahoh, the post-
mortem appearances were jaundice, a dark Huid state of the blood, and
hypersemia of the brain and liver. Boatrom fed a dog with 100 grms.
of the fresh young morel le; the animal died on the third day, and the
canaliculi of the kidney were found tilled with the haemoglobin, partly
amorphous, and partly crystalline, t
DIVISION II.— GLUCOSIDES.
L— Digitalis Group.
§ 526. The Digitalis purpurea, or foxglove, is a pUmt extremely
common in most parts of England, and poisouing may occur from the
accidental use of the nxjt, leaves, or seeds. The seeds are very small
and pitted; they weigh ll2t> to a grain (Gu^)f are of a light brtiwn
colour, and in form somewhat egg-shaped. The leaves are large, ovate,
creuate, narrowed at the Imso, rugous, veined, and downy, especially on
the under surface* Their eulour iw a dull green, and they have a faint
odour and a bitter, nauseous taste. The leaf is 1>est examined in section.
* IndtiMr. BL, I87S.
t Sea Uasper'a Viftieij.^ \%A\\ Kober, Prttt^* V^rtii^meif^,^ 1340 ^ BttStrum,
BtT. d. Phffs, Metl, S^., KrlAiJgeir, 18S0; Sch*iiett*tei», 'Htiftige StrLwiiniiue " in
MuBcUka^B Hajuihttehi etc.
432 POISONS: THEIR EFFECTS AND DETECTION. [§ 5?7-S30.
Its epidermis, when fresh, is seen to consist of transparent, hexagonal,
colourless cells, beneath which, either singly or in groups, there are
round cells of a magenta tint, and beneath these again a layer of
columnar cells, and near the lower surface a loose parenchyma. The
hairs are simple, appearing scantily on the upper, but profusely on the
lower, surface ; each is composed of from four to five joints or cells, and
has at its base a magenta-coloured cell. The small leaves just below the
seed-case, and the latter itself, are studded with glandular hairs. The
root consists of numerous long slender fibres.
§ 527. Chemical Composition. — It is now genemlly accepted that
there exist in the foxglove, at least, four distinct principles — digitoLin^
digitoniriy digit axin, and digitalein. Besides these there are several
others of more or less definite composition, which are are all closely
related, and may be derived from a complex glucoside by successive
removals of hydrogen in the form of water.
§ 528. Digitalein is a colourless, amorphous body, probably a mixture easily
soluble iu water and in cold absolute alcohol. It may be. precipitated from an
alcoholic solution by the addition of much ether. It is with difficulty soluble in
chloroform, and insoluble in ether. It is precipitated from a watery solution by
tannin, or by basic lead acetate ; saponification by dilute acids splits it up into
glucose and digitaleretin. It has a sharp, acrid taste, and the watery solution froths
on shaking.
§ 529. Digitonin may be obtained in crystals by treating German digitalin with
water, adding alcohol to the solution, and then shaking with ether ; after a time
crystals separate, 0.28^47^14 + ^a^ i ^he crystals are easily soluble in hot water or
alcohol ; fdth. warm concentrated HCl it forms a yellow solution which quickly
becomes green ; it is precipitated by tannic acid, lead acetate, and ammonia, but not
by magnesic nor ammonium sulphate. Schmiedeberg*s amorphous and Kiliani*s
crsytalline digitonin are, according to Cloetta,* different substances; on the other
hand, Kiliani {Arch. Phann,, 1905, ccxliii.) thinks Cloetta*s compound is a mixture,
and that it cannot be represented by such a simple formula as C.j)H470j4.
Digitogenin is insoluble in water and aqueous alkalies ; it is somewhat
soluble in alcohol, chloroform, and glacial acetic acid ; it forms a crystal-
line compound with alcoholic potash, which is strongly alkaline, and not
very soluble in alcohol.
§ 530. Digitalin, CggH^^Oj^, when perfectly pure, forms fine, white,
glittering, hygroscopic needles, or groups of crystalline tufts; it is
without smell, but possesses a bitter taste, which is at once of slow
development and of long endurance. On warming, it becomes soft
xuidor 100*, and, above that temperature, is readily decomposed with
evolution of white vajwurs. It is insoluble in water, in dilute soda
solution, in ether, and in benzene. It is soluble in chloroform, especially
'n chloroform and alcohol, and dissolves easily in warm acetic acid;
?e l)arts of cold and six of lx)iling alcohol of 90 per cent, dissolve
• Cloetta, Max, Arch, ft, exp, Pharm,, 1901.
§ S3I-S52A]
DIGITALIS GHOUP.
433
nne of digitalin. Oil hydroljmis it yields digitalose* C^Hj^O^^* Con-
centrated aalphuric acid dksKjlvea it with the production of a greoii
c<>lour, wbicJi by bromine passes into violet-red, hut on the addition
of water becomes green again. Hydrochloric acid diis^lves it with the
production of a greyiah-yellow colour, passing gradually into emerald
green ; water precipitates from this solution a reiinoua maaa.
§ 531. Di^taletiii. ^A substenee obtained by Walz on treating bis di^tiliii by
dilute aeidn. It is crysttalLitiftr and ita wiiiery solution tu.ttoii bitten It niPlU at
175', and decomjw>seSj e vol ring an acid vapour at aboat 206'^ It di8*dv(»a in 84 S
[larts of cold, and 222 of boiling, water ; in 3 '5 parts of c«ld^ and In trom 2 to 4 of
bftiling, alfKihol. It m with diflicultj aolublo in ether* It dinsolvea in donoeutmted
sntphuric acid, develop! ug a rad-browti e^ilour, wbioli, on the ndditton of wat^fi
changes to ohTa-green. On boiling with d^ute acidsj it spHts up into sugar and
digitaltiretin.
§ 532. Digitoxm, CjjiH^Oio (according to R Killani, C^E^O^^),
in considered the most aetive poisonous constituent of digitalis leavcH ;
although the extjoriraents of Hans Zie^eitlKsiri {Arch. FharnL, 1902), on
the heart of a fitig, with extracts from dried leaven in which the eon-
tent f»f digit*j3£in was aaeertained, show that siich extracts are far more
toxic than could be predicatwi from the amount of tligitoxiu found*
Similar facta may be shown as to muaearine and other extraets containing
alkaloids ; tuiiBocliited glueosidea or, poeaiblj, unknown toxinea heightening
the to lie effect.
jf 532a. Separation of Digitoxin from Organic Matters. — Digiboxin
may be estimated hy Keller's t method, which m as follow8: — Twenty grmn.
of the powdered leaves are exhausted by percolatiun vvitli 300 c.e* of 70 per
oent. aleohol, and the alcohol got rirl of by cvapomting down in a porcelain
dish on the water- kith to about 25 grnis. ; the reaidue in taken up with
water tuitil the weight is brought up to 222 ^ms. To the turbid
solution 25 grms, of lead acetate are added, whictk produce a copious
precipitate. The thick liquid is translerretl to a filter 10 cm. diameter,
and 132 grmn, filtert*tl tbn>ugh. To the c!e*ir filti^ate, 5 grma. of sodium
hyposulphite dissolved in 7 grms. of water are added to precipitate the
excess of IcHfb The lead precipitate ia ijepvrated by filtration, 2 c.c. of
10 per cent, ammonia sulutiou added^ and the liquid transferred to a
«cptmting funnel and shaken out four or five tiniew with chloroform. The
ebloroforruic extract is filtered through a double filter pnwionsly soaked
by ehlonifoFui, and obtained in this way clear. On distilling the ehlom-
fonn, the dlgitoxiii m obtziiue^l as a yellow varnish. It is dissolved in
3 grms. of chloroform, and preeipiUite<l in flocks by 7 grms. of ether
and 50 grms. petroleum ether* The precipitate is oolleeted in a small
filter, and waahcrl with petroleum ether. The residue, still moist, is
di^SM>lved in hot absolute alejohol, the alcoholic solution evaporated, the
• H, Kiltatiij Ber. !S»8, kxkI t ZeU, /. Ami. Ch^m,, 1900, 267.
434
FOISOKS: THEIR KKFECTTS AKD DKTEOTlOK* [| 535-536.
re§idiie treated with 5 c,c, of ether and allowed to evaporate in the
wator-lmth ; ifc now becomes partly crystallint? and may be completely
dded and then weighed.
Dioacoride Vitali {Che7}K Ceiitr.^ 1900) isolates digitoxiu frora the
tissues by extracting with dilute alcohol, evapomtmg the alcoholic
extract to a small bulk ; the residual liquid is treated with lead acetatt;,
and then with sodic Bulphate to get rid of the excess of lead ; after
filtration the tiJtrate is alkalised as in the previous [iroceas with ammonia,
and shaken with chloroform ; the ehloroform extract may Ike treated as
in Keller*a process.
On hydrolising with alcoholic soda digitoxin breaks up into digi*
toxegenin, C^K^fifi, and dlgitoiose, CgHi^O^, thus:^
g 583. Digitaleretiti, n, decumpositios |irodiict of digitalin^ is a yellowi^li-irhtie
amorfhhouft powder, |iossesgiiig no hitter to^te, melting at 60^, soluble in etlicr or iu
alcoltol, but insoluble in water*
Famdigitaletln la very almilar to the above^ but it melts at lOO**, ^qd ii inaolublfi
in ether.
§ 534. Several other deriTativea have been obtained aod deicrihed,
such aa the inert digitin, digUalamn^ digitalEm^ and othera, but their
properties are, as yet, insufticiently atudied.
g 535, EeactioDS of the DigitalinB. — 0^01 grm, of digitoiuu dissolved
in 5 c.c. of HCl (sp. gr, 1'19) and heated on the water4mth gives a
liquid, at first yellow, then deep red and finally dark blue, Thia re-
action thus serves to distinguish digitonin from the three other con-
stituents, aa well as from sapooiu ; but digital in gives somewhat similar
reactions.
Sidphuric and gallic acids colour the glucosidea of digitalin, digitalein,
and digitonin, red, but not digitoxin, which can be identified in this
way-
Sulplmric acid and bromine give with digitalin a red, and with digi-
talein a violet eoloration, which, on the addition of water, change re-
spectively into emerald and light green. Thb, the most important
chemical test w^e possesii, is sometimes called Gnmdfau^i t^si ; it is not
of great delicacy, the limit being about O'l mgrm.
§ 536, Phaxmaceutical Preparations of Digitalin. — Digitalin itself
Is officinal in the French, Belgium, Portuguese, Russian^ Spanish, and
Austrian pharmacopoeias. It is prepared in our own hy making a strong
tincture of the leaves at 1 20' F, ; the spirit is then evaporated off, and
the extract heated with acetic acid, decolorised by animal charcoal,
and filtered. After uentmlisatiou with ammonia^ the digitalin is pre-
cipitated with tannin, and the tiumatc of digitalin resolved into Uuuate
of lead and free digitalin, by rubbing it with oxide of lead and spirit.
§ 537-1
DIGITALIS aaoup.
43 S
Digitalis leaf la officinal in mtst of the pharma^opn^ias.
Tincture of digitaliH is officmal in our o^u and all the Continental
phamiacopo^iaa, and an ethereal tincture is used in Fmnce and
Cermanj.
An Aretum digUaliA m ofl&einal in the Netherlands and Germany j
an extract and infusion are fdao u&ed to some extent.
With regard bo the nature of the actiye principle in these different
preparatifvnsi, according to Dragendori!^ digitoniu and digitalein aro
most plentiful in the acetic and aqueous propamtions; whikt in the
jdcoholic, digitalin, di^toiin, and digitalein are present
According to Schmiedeberg, commercial digitalin contains, in
addition to digi toxin ; digitonin, digitalin, and digitalein ; of theno,
digitonin is ^^reatest in amount*
S 537. Fatal Dose^^Thc circumstance of eomraercial digitalin con-
sisting of varying mixtures of digitoxin, digitalin, and digitalein, renders
it di then It to im dogmatic al>out the dose likely to destroy life, liesides,
with all heart-poisims, surprises take place; and very minute qiwintitiea
have a fatal result when administered to persons with disease of the
heartf or to such iws, owing to some constitutional peculiarity, have a
heart easily affected hy toxic agents. Digitoxin, aemrdiug to Kopp'sf
oxperiniunts, is from six to ten tirae^j stronger than digiL'ilin or digitalein.
Two ingrm& cause<l iutcnst^ poisonous symptoms. Digitoxin is con-
teiiucd in larger proportions in N'ativelle'a digi till in than in Homolle^ or
in the German digitalin. The digitalin of Homulle is prescribed in
I mgrm. (0*015 grain) doses, and it is thought dangerous to exceed 6
mgrma.
Lemaistro hits, indeedj seen (Lingerous symptoms arise from 2 mgrms.
(0*03 grain), when administered to a lioy fifteen yeani old. It may he
predieat^d from recorded cawes and from experiment, that digiU>iin
\vynl<l iirobuhly l»e fattd to an adult man in doses of 4 mgrms. d'^ gniin),
and digitidin, or digitsileiu, in doaea of 20 mgrms. {0"3 grain). With
reganl to com mere nil digitalin, as much as from 10 to 12 mgrms, (0"I5
to 0'13 grain) have liecn taken witltout a fatal result; on the other
hanii, 2 mgrins, gave rise to |K>isonous symptoms in a woman (Battaille).
Such discrepancies are to he explained on the grounds already men-
tioned. It is, howevr^r, probable that 4 mgrms. (or ^*^ gnun)of ordinary
eomnit?nual digitjilin would be very dangerous to an aduttp
It must also, in considerhig the dose of digitalin, be ever remembered
that it is a cmnulative poison, and that the samedt.tse, liarmless, if tjiken
once, yet frciiuently repeated, becomes deadly : this peculiarity is
shared by all poisons affecting the heart. Wlien it is desired to settle
* H. KHiivii^ Ber., xiiii.
436
POISONS: THEIR RFFKCTS AND DKTKCTION. [§ 538, 539.
the maximum safe dose for the various tinctures, extracts, and infusions
of digitalis used in pharmacy, there is still greater difficulty — a difficulty
not arising merely from the varying strength of the preparations, but
also from the fact of the vomiting almost invariably excited by large
doses. Individuals swallow quantities without death resulting, simply
because the poison is rapidly expelled ; whereas, if the oesophagus was
ligatured (as in the experiments on the lower animals formerly favoured
by the French school of toxicologists), death must rapidly ensue. The
following table is a guide to the maximum single dose, and also the
amount safe to administer in the twenty-four hours in divided doses.
As a general rule, it may be laid down that double the maximum dose is
likely to be dangerous :—
TABLE SHOWING THE MAXIMUM SINGLE DOSE, AND MAXIMUM
QUANTITY OF THE DIFFERENT PREPARATIONS OF DIGITALIS.
WHICH CAN BE ADMINISTERED IN A DAY.
; Single Dose.
Per Day.
i
Grains or
1 Minims.
1
1
Grammes
or c.c's.
Grains or
Minims.
1.V4 grns.
1440 ni.
135 m.
•09 gni.
12-0 „
Grammes
or c.c's.
1-0 grm.
84-9 CO.
9 e.c.
•006 grm.
•8
Powdered Leaves, 4} grns.
Infusion, . . . i 480 m.
Tincture, . . , 45 m.
Digitalin, . . 1 *03 grn.
Extract, . . . S'O „
•3 gnn.
28-3 c.c.
3 c.c.
•002 grm.
•2 „
§ 538. Statistics. — The main knowledge which we possess of the
action of digitalis is derived from experiments on animals, and from
occasional accidents in the taking of medicines ; but in comparison with
certain toxic agents more commonly known, the number of cases of
death from digiUilis is very insignificant. Of 42 cases of digitalis-
poisoning collected by Husemann, 1 was criminal (murder) ; J the
result of misUiking the leaves for those of borage ; 42 were caused in
medicinal use — in 33 of these last too large a dose had been given, in 3
the drug was used as a domestic remedy, iii 2 of the cases the prescrip-
tion was wrongly read, and in 1 digitalis was used as a secret remedy.
Twenty-two per cent, of the 45 were fatal.
8 539. Effects on Man. — It was first distinctly ix)inted out by Tar-
dieu that toxic doses of digitalis, or its active principles, produced not
only symptoms referable to an action on the heart, but also, in no small
degree, gastric and intestinal irritation, similar to that produced by
arsenic. Tardieu also attempted to distinguish the symptoms produced
by the pharmaceutical preparations of digitalis (the tincture, extract.
539-]
DIGITALIS GEOUP.
437
etc.), and the glucosido digitalhi ; hut thei'e docs not appear a sufficient
baais for this diatiuction. The symptoms vurj in a eonsidemble degree
ill differeut peraoiiSj and are more or lesa tardy or rapid in their devclop-
mont, accoi^iing to the dose. Moderate doses continued for some time
(m, for eiampie, In the persistent use of a digitalis tnedioine) may pro-
duce their first toxic effects even at the end of many days ; but when a
single large dose Is taken, the symptoms are rarely delayed more than
threu hours* They may commence, indeed, in half an hour, but have
been known to be retarded far raor® than twenty-four hours, and the
longer periodsi may bo expectetl if digitalis is given in hard, not easily
soluble pills. There m commonly a feeling of general ?nafaise^ and then
violent retching and vomiting. The pnhse at tirsjt may lie accelcn^ted,
but it soon is remarkably slowed — it sinks commonly down to fiOj to
40| and has even been known as low as 25. To these symptoms, refer*
able to the heart and to the digestive tract, arc added nervous troubles ;
there are noises in the ears, and disturbanceii of vision. In a case re-
lated by Taylor, a red-cijal fire seemed to the pitient to l>e of a blue
colour ; in another, related by Lerseh,* there was blindness for eighteen
hours, and for some time a confusion in the discrimination in colours ;
quiet delirium hm also iwen noticed. As the cfise procee^^ls, tlie gastric
sympUmis altso incre^tsc in aevcrity ; the tongue Christison, in one ease,
noticed to be euorniously swollen, and the brc?atb foetid, L>tarrhcea is
commonly present, although also sometimes alisenL The action of the
kidneys is suppressed. Hiccough and convulsions close the scene.
In the uumnlativo form, the symptoms may suddenly burst out, and
the person pass into death in a faiuting-fit without any warning. As a
rare etltTl, hemiplegia may be mentioned.
Tills brief r4sumt' of the sympt^imis may be further illustrated by the
following typical cases :*-A recruit, aged 23, desiring to escape from
military service, went to a so-called ** Freimtic/ier^'* who gave hini 100
pills, of which he was to tfike eight in two doses daily. Eleven flays
after the use of the pills^ he became ill, and wafi received into hospital,
where he suddenly died after three weeks' treatment. His malatly was
at (irat ascribed to gastric catarrh ; for he suffered fnjm Ions of appetite,
nausoii, and const! [mtton. He complained of pain iu the head, and
giddiness, Hia breath smelled badly, and the region of the stomach
was painful on pressure, The pulse was slow (56), the temi>erature of
the body normal. Towards the end, the pulse sank to 52 ; he suffered
from vomiting, noise in the ears, troubles of vision, great weakness , and
later, hiccough and swelling in the neek. Tlie mere act of standing up
in order to show his throat caused him to faint ; on the same day on
which this occur rence took place, ho suddenly died on the way to the
* M€f^ tV^$8K Gorr, SL, 1&, 1^43; HiueiujiuR iti Unmhka.'^ UaHdi^u^L
438 POISONS: THEIR EFFECTS AND DETECTION. [§ 539.
iiight8tool. Thirteen of the pills were found in the patient's clothes,
and from a cliemicjil and microscopical examhiation it was found that
they contained digitalis leaf in fine powder. The quantity which the
unfortunate man took in the four weeks was estimated at 13*7 grms.
( = about 211 grains).
Two of his comrades had also been to the " FrehnacJier,'' and had
suffered from the same symptoms, but they had left off the use of Xhe
medicine before any very serious effect was produced*!
An instructive case of poisoning by digitoxin occurred in the jierson
of Dr. Koppe, hi the course of some experiments on tlic drug. He had
taken 1*5 mgrm. in alcohol without result ; on tlie followhig day (Nfay 14)
he took I mgrm. at 9 a.m., but again without appreciable symptoms.
Four days later he took 2 mgrms. in alcoholic solution, and an hour
afterwards felt faint and ill, with a feeling of giddiness ; the pulse was
irregular, of normal frequency, 80 to 84. About three hours after
taking the digitoxin. Dr. Koppe attempted to take a walk, but the
nausea, accompanied with a feeling of weakness, beciime so intense that
he was obliged to return to the house. Five hours after the dose, his
pulse was 58, intermittent after about every 30 to 50 beats. Vomiting
set in, the matters he threw up were of a dark green colour; after
vomiting he felt better for a quarter of an hour, then he again vomited
much bilious matter ; the pulse sank to 40, and was very intermittent,
stopping after every 2 or 3 beats. Every time there was an intermission,
he felt a feeling of constriction and uneasiness in the chest. Six and a
quarter hours after the dose there was again violent vomiting and
retching, with paleness of the face. The muscular weakness was so
great that he could not go to bed without assistance. He had a disorder
of vision, so that the traits of persons well-known to him were changed,
and objects had a yellow tint. He had a sleepless night, the nausea
and vomiting continuing. During the following day the symptoms
were very similar, and the pulse intermittent, 54 per minute. He
glassed another restless night, his short sleep being disturbed by terrible
dreams. On the third day he was somewhat better, the pulse was 60,
• Kbhnhorn, VierUljhraschr, f. ger. Med., 1876, u. F. xxiv. p. 402.
t There is an interesting case on record, in which a woman died from the ex-
pi-essed juice of digitalis. She was twenty-seven years of age, and took a large
unknown quantity of the freshly expressed juice for the puri>ose of relieving a swell-
ing of the limbs. The symptoms came on almost immediately : slie was very sick,
and was attacked by a menorrhagia. These symptoms continued for several days
with increasing severity, but it was not until the fifth day that she obtained medical
assistance. She was then found semi-comatose, the face pale, pulse slow, epigastrium
painful on pressure, diarrhoea and hiccough were frequent. She died on the twelfth
day. The i)ost-mortem appearances showed nothing referable to digitalis save a few
8|K>ts of inflammation on the stomach.— Causs^, Bull, de ThSrapeutique, vol. Ivi.
p. 100 ; liriL and For. Med, Chir, Hevuw, vol. xxvl, 1860, p. 628.
§ S4oJ
DIGITALIS GROUP.
439
but irregular and fitiil hitcrmittmit ; the imiiaea was also a little abatid.
The night was similar in its diatarbed sleep to the preceding. He did
not regain his full health for seveml days.*
A third case may bo quottHl, which differs very markiidlj from the
preceding, and shows what a protean aspect digitalin poiaoiiiiig may
aaeiime. A woman, twenty- three ycai'S old, took on June 26th, at 7 A.M.,
for the purpf>at3 of suicide, 16 granules ot digitalin. Two hcjura later
there was shivering and giddintisa, so that aho was obliged to go to bed.
In the cQUTfie of tiie day she had lialluei nations. In the evening at
8 PM*i after eating a little food, she had a shivering fit so violeiit that
her teeth chattered ] there waa cold sweat, and difticnlty in breathing ;
she became groditally again warm, but eould not sleep. At 1 a.m. the
difficulty of breathing was so great that she di^agged herself to the
wuidow, and there remained until 3 a.m., when she again went back to
bed, slept until 7 a.m,, and woke tolerably well. Since this attempt of
aeU-destructinu hatl failed, she took 40 gnuiules. After one hour she
became giddy, had hallucinations, chilhness, cold sweats, copious vomit-
ing, and colicky painaj there was great muscular weakness, but no
diarrhoea. Towards evening the vomiting became woree. There was
no action of the bowekj nor was any urine passjed ; she felt as if her
eyes were prominent and large. The sufferings described lasted during
the whole night until five o'clock the following day, when the vomithig
ceased, whilst the halluciuationa, chillineas^ and cold aweat continued ;
and the thirst, sick fceliug^ and weakne^ increased. The next morning,
a physician found her motionless in bed, with jmle face* notable double
exophthalmuB, dilated pupils, and cold skin, eovcred with sweat; the
pulse was atnall and intermittent, sometimes scarcely t-o bo felt (46 to
4tJ per miuute) ; the epigaatrium was piunful on pressure. Bhe passed
this second night without sleep, and in the morning the pulse had riaen
from 56 to 58 heats^ but was not quite so intermittent. There wjis
some action of the bowels, bnt no urine waa passed, nor had any been
voided from the commencement ; the bladder was not distended. The
following (third) day some red-coloured, oflbusive urine Wiis passed; the
skin was warmer^ and the pidso from 60 to 64, still somewhat iuter-
mitteut — from this time she began to improve, and made a good
recovery- 1
§540. Phyaiological Action of the DigitaliuB, — Whatever other
physiological action this group may have, its effeet on the h earths action
is ao prominent and decided, that the digitalina stand as a type of heart
poistms. The grtmp of heiirt poisons has been mnch extended of late
• ArvX/, ejjit, FtUh. a, FhamK, voL iil p. 280, 1875,
t Related hy Daa»jix i tk t*EmpQi»onnemmi par !a DigiiAl* $i la IHg^aiine*
Paris, I8di.
440
POISON Si: THKIK EFFECTS ANLi UETECTION, [§ 541, 542*
jeare, and Urh bcmi found to inclnde the folio wmg : — Autkrin, ati arrow
poisoti ; hellel*orin, i\ gluuoyide contained in tliC heUelxjre fmnily j a
glucoside found in the A2^oeffiiaeetJ^'j Thevaiia fwnifolia^ and themiiti
iceotli ; thu poisonous principle of the Nerium oletmder and N. odorum ;
the glncoside of Tanghinia immnfei-a ; convallamariti, deriverl from the
Bpetiiea of Couvailaria ; Bcillotoxin, from the squill ; superbiUj from the
Indian lily ; strophanti n, from the aoedK of Stropliaidhits hii^pidus ;
euony mo toxin, from Euomjvin^ airo-purpureus ; urecthin and nrechi-
toxiri, from Urefhiiu subef-ecta; and tho alkaloid erythropMeiu from
the EryikropJiliBum judicifiJe {m^ p, 447 et ^eq.). This list is yearly
iucrca&ing.
g 541. Local Action. — The digitalins have an esdting or Btimnlatiug
action if applied to mneous niembraneii — e.^. if kid u^jon the nasal
mucous surface, sneezing is exeited ; if applied to tlie eye, there is red-
ness of the conjunctiva; with smarting ; if to the tongue, there is much
irritation and a bitter taste. The leaves, the extrnet, and the tincture
all have thi« directly irritating action, for they all redden and inflame
m UGons m i^ra brai ics .
§ 542* Action on the Heart, — The earlier exptnimenters on the
influence of digitalis on the heart were Stauniua and Traube. Stannius *
exiJcrimcnttid on cats, and fomitl atrong irregnlnnty, and, lastly, cc^isation
in diastole, in which state it res{>onded no longer to stimuli, Rabhite
and birds — especially those birds which lived on plants — were not so
susoeptible, nor were frogs.
T ran be f made hie researches on dogs, using an extract, and admmis-
tering doses which corresponded to from 0'5 to 4^0 grms. He divided
the symptoms witnessed inU> four stages : —
}d Siage. — The pulse frequently diminishes, while the pressure of
the blood rities.
2nd Stage. — Not seen when large doses are employed; pulse
frequency, as well its blood pressure, abnormally low;
Zrd Stage, — Pressure low, pulse Itetitu aljovc the normal frequency.
The curves in accompanying (igurc illustrate one of Tranbe*s experi-
ments on blood pressure and pulse frequency in a dog treated by
intravenous uijcctions of digitalis infusion, and ilhistmtuw the three
stages just described.
The slowing of the heart J b attributed to the stimulus of the iukibi-
♦ Arch./.Fh^iwi,, 1862,
i Ann* d. Chariii'Kr(tnHnknujK'.% vtfL ii> p. 786.
X Slowing of the pulse wnA menti^jiied fin*t by WitLoring {An AccouiU of the
Fwc^loWt Load*, 17S&), Btjddoes aftorwards observed th&t digitalis iucrBiiaed the
fcirre of the eirculation, the ilowittg of the pulse not being e^lwaya obaerved ; record-
ing to Ackeramtm, if the inliibitwry iii>i>uf jtus is affbcted by at rupiiic, or if the |mtietit
is under dt^ep imrLoaifj the blowing is absent.
^^H 1 542.] DIGITALia GMQim ^^^^ 44I ^H
^^^^1 toty uorreSi but the later oonditiot) of froqiioDcy to their pimly^ta. ^^M
^^^^m MtGT the aeetion of the Tfigi the slow puli^ frtxiuetitly reTiiaiii», and thm ^^M
^^^^^
S 10 rs 20 25 30 35 40 45 50 55 60 mmutes.
^■1
^^^^^H ^^0
1
^
••^^
^V
\
(J/
>
V
^
\
^f
\
J
^
/
V
^
r
/
\
t*/,
>ject
/0/7
^
^
>^
.^
\
f
.--
.-^''
\
T
1
, 1
\
'1
y
qj 1
\
tj
\
Dea
Jt
If
* ifrifsvefiOii^
1
or t
nrvs
m/i
r
^
■
1
^^^^H
i
I'^/n/i
c^d
ft
1
\
t
!
V
i
1
1
i
1
1
V
Pffd
ifiji
C//tf
1
^^^^^H
1 I
y 1
Q 1
s 2
0 2
5 3
0 3
5 4
0 4
5 5
0 5
5 £
0 rr
linM
t£S.
I
^^^^^^^1 ClLrre showing changea in tb« puhc, &ud drterial Umitm produced by ^^|
^^^^^^^^P intmvenous ii^ectioa of to fusion of Digitalie in a dog. ^^H
^^^^1 ia itTplniniurl hy iho inhihitjirv tiptinn rtf ihn /yifdifir* rwnfi-o Thn irH|rt^a^ ^^H
^^^H hi poiut of time, is paralysed earlier than the muscular subetaiioe of the ^^^H
^^H ^^H
^^^^L^^ The iucrua^Hl bU>u<l prt^iirc Tmuljij Httribuk'd to iiicroMSf^ ouergy ^^M
442
POISONS: THEIR EFFECTS AND DETKCTIOH, [| S43-54;
of the heart's coutnictiouj thixmgh tht- iriotor centre beitig stiinulfited
later ; the commencing paralyaiti explains the abiiortnally low pressure.
There is^ however, also an influence on vaso-motor nervos. What
Dr. Johnson \m^ deacriWi tis the *^ stop-cDck " action of thi' small arteries
comes into phiy, the small arteries contract and attempt, as it were, to
limit the supply of poitsoned blood. Ackeromnn,* indeed^ witnessed this
phenomenon in a rabbit's tnesenteryj distinctly seeing the arteries
eontmct, and the hlood press ure rise after section of the spinal cord.
This obsorvatioUt therefore, of Aekermann^a (together with ex peri men t»
of Eohm t and L. Brnntoti |) somewhat modifies Traube*s explanation,
and the views generally accepted respeeting the cftuse of the inoreased
blood pressure may be stated thus : — The pressure is due to prolongation
of the systolic stixike of the cardiac piuup, and to the ** stop-cock ^' action
of the arteries ; in other words, there is an increase of force from behind
{vie a terffo)^ and an increased resistance in front {vis a fro7iie).
g 543. Action of the BIgitalins on the Muco-Intestinal Tract and
other Organs. — In addition to that on the heart, there are other actions
of the digitalina ; for example, by whatever channel the poison is intro-
duced, vomiting has been observed. Even in frogs this, in a rudimentary
manner, occurs. The diuretic action which \mj& been noticed in nian
is wanting in anlmaJs, nor luus a lessoned diminution of urea been
confirmed.
Ackermann foimd the temperature during the period of increased
blood pre^isuro raised superficially^ but lowered internally. According
to Bueck § there is ul^ increase in the decuni[Kisition of the albuminoids.
§ 544. The Action of Bigitalln on the Common BloW'fly.— The Mviiiar author h&a
Btediiul the elfecls ol digitjiUUp m^dc uji into a thhi pa^te with iratL^r, mud appliud bo
the he5M:i i>f tlie common bh>w-fly. Thoro are at iiuct? gt^at Higns of irritation, the
iiuckei- i» i^xtnided to its full lenglh^ and tlie lly wotlts %l^ frre feet, attempting to
bruah or romove the Irritatiiig agent The nuxt Bympt^mi in ct dlfticulty in walking
up a per^ieudicular glass aoiface* This difticulty inereasea^ hut it is distuictlj
observed that weaklier arid (MiralyBis occur in the leg» before they m-e aeeii in the
wing^. Within an hour the wingB become parulysf^d also, and the tly^ if jerked from
its support, falls likfi u, stone. Tbo iustj^^t becomes dull and motionl6Ǥ9, and ulti-
mately dies in from ten to tM^enty foiu" hours. A dose, in itself insufficient to da*tmy
life* does so on rcp«tition at intervals of & couple of hours. The observation ia not
without interest, Itiastiiuch im it shows that the digitalinti are toxic subatanc45S to
the miiscukr 3ub»tance of eveo tho&e life -forms which do not |H:>sse^ a heart,
§ 545. Action of the Digitalins on the Frog's Heart,— The f^encral
action of the digitalins m tieat studied on the heurt of the frog. Drs.
Fagge and Stevenson have shown || that, under the influence of di gitalin,
• JkuUth. Arch./, kiitt, Med., vol lix. p. 125,
t ArtMvf, d. Ges. Pftys., vol. v. p. 153.
t On Di'fUsUis^ "fmiksmfie Obsetvtilums on lAc Urine t Lond.^ 1868,
§ Int^KdaUiaA, p. 404* || Uti^^3 MttttpL Ik^H^rts^ ard i*f,, vol, itii. |*. 37.
§ 54^1
DIOtTAtlS GROUP.
443
there h a peculiar form of inregularitj in the ivenU of the heart of tha
frog; the veiitrick ultimately stupH in tjio white contnictcd state, the
voluntiirj power being ret-ained for fifteen to twenty minutes after-
war ds; in very large dt^sea there is, however, at once pai?AlyBia louder
Brunton * considerti the action on th® heart U) essentially consist in the
prolongation of the syatokp
Atropine or curare have no influence on the heart thus poisoned. If
the anirnsil under thu iufiueuce of digitalin be treated with niuscariue,
it atopK hi diastole instead of systole. On the other band, the heart
|Kiisoiied by uiusc^irine is relieved by digitalin, and a similar inHueuco
appears to Ije exereised by atropine. The eystoUc stiliuKss of the heart
is also removed bj substances which paralyse the heart, as delpiiinin,
sapinun, atid apomorphin.
Large donea of digitabn, thrown suddenly on the cireulation by intra*
vcuouB injection, cause convulsions and sudden death, from quick palsy
of the heart. With frogs under theae eirenuiatauces there arc no con-
Tulsions, but a reflex depression, which, according to Weil t and
Merhuizen, { disiippears on deca^ntation. The central cerebnil symptoms
are without doul.it [rnrtly due to tlie disturbance of the circulation, and
there i^ good gnmnd for attributing theru also to a toxic action on tiie
nervous substance. The arteries are afli'eeled as well as the heart, and
are reduced in calibre ; thtj blood pressure is also iucreased,§ This ia
essentially due to the firm, strong contraction of the heart, and also to
the ** stop-cock " action of the small arteries. |f
g 546. Post-mortem Appearances.— In the ease of the recruit
poisontd hy digiUvlis leaf (p. 437), the blood was found dark and fluid ;
the right ventricle and auricle of tbe heart were filled with bhiod ; the
left empty ; the brain and its inembmuea were antGnnc ; the stomach
and mucous membrane of the intestiues were in parti eechj^mosed, and
tiicre were patches of injection. In the cfise of the widow De Pauw,
poisoned with digitalin by the homceopath (Coiity de la Pommerais),
the only ahnormaUty discovered was a few hyperiomic points in the
* On J5ii7iWw, mlh mtme Obnervaiimt^ ^% th4 V^rinut Lon4, 186S,
t Archivf. Amit. u. Phymaf., 1871, (i. 282.
t Archivf, d. 0«s. i^kff^iGL^ voL vii. p. 20 L
§ The following 18 ft lirief sumuiflry uf ubservntiona ou the blood pressure ; four
sLu^e^ may ho uoticfd— (1) Rise of nomiiil blood prv^aure, not accessarily acconi-
|i«nied with a dinunutiou of pulsp frt^tueucy ; {2} contiuuntiou of heightened blood
pre^iari'^ the {aiW being raised beyond the normal rale ; (S) cootinued high jireasure,
with gre»t iiTP^Urity of the lieart MEid intermittent pulfie ; (1) quick deprewian of
pfessnre, ftuddeu stopping ot the heart, and death,
11 According to Boehm {Arck.f, d. Oes. Phenol. ^ Bd, v, S» 189) And to Wil limns
{Arch,/^ expcr. Paihtft., Bd. xiii S. 2), the rise of prnaure ia due entirely to th«
heart, and not in the coutractlons of Ihc amall arttnw ; but it i^ difficult to aee how
the bUtitU u^rteri^ ciui cgutmct, aud y«t not heighten tbu pa^ssure.
444
POISONS : THBIB EFFECTS AND DETECTION.
[§ 547.
mucous membrane of the stomach and small intestines. It is then
certain that although more or less redness of the lining membrane of
the intestine track may be present, yet, on the other hand, the active
principle of the digitalis may destroy life, and leave no appreciable
sign.
§ 547. Separation of the Digitalins from Animal Tissues, etc.—
It is best to make an alcoholic extract after the method of Vitali, already
detailed, the alcohol being feebly acidulated, if necessary, by acetic acid,
and all operations being carried on at a temperature below 60*. The
alcoholic extract is dissolved in water feebly acidulated by acetic acid,
and shaken up, first with petroleum ether to remove impurities (the
ether will not dissolve any of the digitalins), then with benzene, and,
lastly, with chloroform. The benzene dissolves digitalein, and the
chloroform, digitalin and digitoxiu. On allowing these solvents to
evaporate spontaneously, residues are obtained which will give the
reactions already detailed. Neither the bromine nor any other chemical
test is sufficient to identify the digitalins ; it is absolutely necessary to
have recoiurse to physiological experiment. The method used by Tardieu
in the classical Pommerais case may serve as a model, more especially
the experiments on fr(^:s. Three frogs were properly secured, the hearts
exposed, and the beats comited. The number of beats was found to be
fairly equal. Frog No. I was placed under such conditions that the
heart was constantly moist. Frog No. 2 was poisoned by injecting into
the pleura 6 drops of a solution in which 10 mgrms. of digitalin were
dissolved in 5 c.c. of water. The third fn^ was poisoned by a solution
of the suspected extract. The number of boats per minute were now
counted at defiuite iutervals of time as follows : —
TABLE SHOWING THE ACTION OF DIGITALIN ON THE
FROG S HEART.
FnigNu.1.
VnpolaiMMd.
Nv. ot b««ts per miuule.
After 6 minutes, 42
„ 10 ,. 40
,» 20 ,, 40
„ 28 „ 88
„ 81 „ 8«
PoiBOB««l l^ ft known
qnanUty of digitolin.
No. of be«t» per minute.
20
16 irregular.
15
0
0
Frog No. 3.
Poiaoned by the tospecied
extract.
No. of beats per minvte.
26
24 irregular.
20 „
12 very uregular.
0
In operating in this way — which is strictly comparative, and, with
care, has few sources of error — if the heart of the frog poisoned with
i 548-550.]
POISONOUS GLUCOBIT>KS.
415
the uukuown extract behaves in the number and irregularity of it»
contractions similarly to that of the digitalin-poisoned heart, it la a fair
infen&nce that, at all eveutSj a "heart- poison " has been separated ; but
it 1% of course, open to question whether this ia a digitalin or one of the
nvimerouis groups of glucosides acting in the same way. If sufficient
r|uantity litia been separated, chemical reactioDSj especially the bromine
test (Grandeau's test)i may decide ; but with the larger nuinT>er (yearly
inereiiaing) of substances acting similarly on tlie hearty great caution in
givmg an opinion will be necessary.
lU— Other Poisonous Glucosides Acting on the Heart.
§ 548, Several members of these glucosides have been studied by
Schmiedelierg,* and his con veu lent divisions will be followed here; —
1, CRYSTALLISABLE GLUCOSIDES.
Astiarin (C^H^jOjQ-f 4H^0). — ADtiarin ia an tLrrow poison obtained from thd
milky juice of thft Antiariii tmrtcaria (uji^ trcp) growing iu JaVEi. Antiariij ia oU-
t&tntMl in crysUilit, by liritt trealiiig the iimpisfi&UNi milky juice with pi'tioleiim etli^r
to roinoYo latty at id other matters, und thou fljstsolvjn^ the active principle out with
abi^hite ah^ohol. The akobcUc extract is tiiken up witb water^ prt^cijiitatM with Ifstkd
acetate, filtert'd, and from the llltniie antiariu obtAined by rrt^ciug the stjlutLun from
lead, and tlien evaporating. De Vry and Ludwig obtaine'l almut 4 j^r cent, frum
the juice. Autiarlu b ciyytalllnis tb? cryaluln cuutaining 4 atoni.H of waU^r. It4
melting-point is givpn as 220 0 ; the crystals arc soluble in watcfr (264 jiarU coldj 27 "4
Itntta boiling), they are not fioluhle in bcnK^ener and with diffitiully in etlier ; 1 }mTi
of anti»rin r^uirlng 2702 jMirta of ether.
The wat*ry aolution h not precipitated by metallic salts. On hydrolysing with
dilute aioobolic hy^lrochloric acid it sjilits up into antiang^nin and antjarot^. Autiari'
gen 1 n , C^ H ^O^^, is a ciy's Ui\ 1 i lie sii Xm tan ce , m, \h. above 1 DO', An tiaro^^e is isomeric with
rhamnose, It is o3cidis*?d witb bromine and water to antiaronic acid^ QjHjiO^COOH
^Heinrtcb Kiliani, ArdK Pharm,^ \%M), (.^ticftitnitt^*! sulphuric acid gives with
antiarin a yi^now-browu solution, hydrochloric aud nitric acids etrike no dhttinctive
colours.
I 549. Eff acta.— Antiarin n estsentjally a muscular and a heart powm. When
given in a sufficient do»e H kills a frog hi from half ati hour tfj an hour. It» nuM
marked cITect is on the cardiac tutt^clej the heart fieats more and more sluwly, and at
last fttojia, the veutrielt! l>ping lii mly contmctt^. As with digitnliji^ there is a very
marked proloogatioii of Xhv asystole, and as with digitalin^ afti^r the beaUi have ceased^
a foiiiible dilatation of the venti'icle will rtsatore tbcin (Sclimiedciberg), It ti^ doubtful
whether by physiological t"X]>erinient atitiariii could !»« ditfcretitiated from digitalin.
I G50. Separation of Antiarin. — In any case of jjoiEomng by antiarin^ it would Iw
best to extract with alcohol ^ evaporate^ dissolve the alcoholic eie tract in water, \iv^-
cipitate with l^ acetate, filter^ free the filtrate from leaii, and thou, after alkaliNing
with nmniotiiaj shake the filtrate Ruccesslvelj with (letroleuni ether, ben^ene^ and a
small quaatity of ether iti the manner roeommeuded at |^gc 255 €t «^. ■ Tho liquid^
446
poisons: their ICFFKCTS ANTl DHrTKCTION. [§ 55 I, 552.
now (reed from all fivtty, reslDoiLs, aiid alkolaidal bodies, in neutmlined and evaporated
to drynoi§fi it) n vac u unit f^ii*^ the dry rosidne taken uji with abaoluto filcciho], Hltcredi
the alcohol ovapurutod at a very low temp^ratui'e, and liually the extiact dissolved in
a Hiujill quantity of water, and submitted to physiological teatfi,
§551. The Active PrincipleB of the Hellebores. ^ — The Christmas
rose (Hellebofus itiger)^ rb well as //. virt'dh^ H, fmtidus, and, iu short,
&11 the Bpecies of hellebore, are poisonous, and if the root is treated with
Hlcohol, from the alcoholic extract may he separated two glucosidcs,
fieliehunn and heUehorein.
Hellehorm is in the form of white, glittering needles, insoluble in
water, but soluble in ether, whiclij if placed on the tongue, are almost
tasteless, btit if dissolved iu alcohol, and then tiisted, give a burning,
numbing nensation. By boiling with zinc chloride, hollebonn splits up
into sugar and a re^m^MlelJoreiiin. Concetitruted sulphuric acid
dissolves the cryatala with the production of a beautiful red colour ;
oil standing, the solution after a while becomes colourless, and a white
powder separates. K. Thaeter {Arch. Pharm.^ 1897) separates it from
an ethereal extraut of the plant, by heating the extract first with light
petroleuui to remove fat, next with acetone to remove tarry and colour-
ing matters, and crystal Uses the reaidual impure helleborin froni a
mixture of alcohol and ether.
Helleborein forms colourless crystals mostly consisting of Hne
needles ; they have a hitter taste, excite sneezing, and are very
hygroscopic. The crysUils easily dissolve in water and dilute alcohol,
but are with difficulty soluble iu abHolnte alcohol ^ and not soluble in
ether* They dissolve in fatty oils, Helleborcin splits by the action of
mineral acids into sugar and amorphous hellehoreiin.
Helleboretin is in tbe muti^t condition of a beautiful violet-blue
colour, becoming, when dried at 100°, dirty green. Conceutmted
sulphuric acid dissolves it with the production of a brown>yellow colour,
which on standing passes into violet and then iulo brown.
Marmo separated from //. fmtiilm, in addition, a white, intensely
odorous substance, but too small iu quantity to thoroughly investigate
its properties.
g 552, There is little doubt that hellebore owes its properties to the
glucosides just described* There are several instances of poisoning hy
hellebore ro<it,* and by the pharmaceutical preparjitions, but none of
poisoning by tlie pure active principles- Morgagui mentions a case in
which 2 grms* (nearly 31 grains) of the watery extract of H. nifjer
caused death within eiglit hours ; and Ferrari saw, after the use of the
• Then) Usisd to ho a tiiiclure officinal in our i>hiiriimc:o|iiiia : the root nf H.
viridu ia officinal in the Germnii pharnuveopteiji, TiiaxiiiujTn Hitigie dosf, '5 grin* ;
maximum total quantity in twenty- four houiii, 1 '2 grin. Th^^ tiTicturiJ h also
ofiieLnal on the Continent.
I 553-555 ]
POISONOUS GLTJCOSlDfiS,
447
wine in whiijU the root had beeu botled, two persons poisoned with a
like result. A more recent case was recorded bj Felletar, in 1875, tn
which a person died from an infuaioii of hellebore; there was, however,
old standing heart diseascj so that there may be a doubt as to the real
cause of death in this instance. Schauenstein mentions a case in which
the roots of hellebore were accidentally used in Boup^ but the bitter
taste preveuted any quantity being eateo. The physiological action,
especially of helleborein, is that of an intense heart poison, and the
sympfcomM produced by the hellebore are so strikingly like those of
the digitalios that it might be ditHcult to distinguish clinically between
them. In any case of poisoning, the active principle must be separated
in the form of an alcohol ic extract, and identified a^ a heart poison by
physiological esperimeut
§ 553. EuoDymiQ U found lu & I'eftin ohtAincil frum tho Euuntfimis almptir'
pttrem ; it U er)'titiiUiii«j cryflttiUisSu^ tti colon rless^ caaliflowpf-hke miifiaes I'oiisL'itiiig
of gFoujRi of tttelUte needles^, which ar& soluble in wator, but with i]ilJieulty in
alcohoU It is a gluco^ide, &Dd tsk pawerfui hea^i i>o\squ, 1 mgrm. ctiusitig i\u* [ankti
uf &, fn>|^ to cuABt in diastole/
i 5&I. Thevetln (CjyH4^0^X— A glucoside which has been separated from the-
Theiviiu nerii/oUft^ and iwrliAps altki from the Crrhrra Odallnm. It U soluble iu
124 parts uf water at li", and is csaKily solqhle in spinti but uot in ether. It is
calonit;d by imlphuric a«id j-ed browu^ piasing into cberry-red, and then, in a t^w
huurs, into violet. On boiling with dilute^^l addn^ it »plit<! nji into tiugar and
thoveresin. Both thtjvetin and theveresiu are (Miweifnl heart poiwona^t
2. SUBSTANCES PARTLY CRY8TALLI SABLE BUT WHICH ARK
HOT GLUCOSIDES,
§ S55. Stropbantia (Q^H^^OJ {^)u- -^^^ i^ ^ ^^^y poiaonous suhstauce wbicli
belongs [iby^inlfiffically tu this groups but dofi** uot acein to bo a ghictiside. It is
soluble in water and in alcohol, leaa so in etht^r and chloralorm. It la found tn
tbe k&mf^i^, nmngaiyjaf iiie^f or oimje, a West African poi^m d<-*riv!»d from the
SirophatUhtfs hisinduji of the faaiily of JfH^iptif^^tr. Th© poison has Ut^m inv^^ti-
gat^d by several ol>serviiirs,t
Dr, Fmscr couBidf^rs^ from his BXperiments, (I) That Htrophantin acts) primarily
on tbe beart, prcHlucirig, a» an ond result, heart jjaralyaiB, with iH'Fniaiit?rii-e uf the
ventricular systok', ('2) He fonud tbt? (lulmonaiy rubspiration to itmtinue in cold-
bloodfHi animuls many nuuutCH ufter the heart was paralyst^d. (S) Tbti .str)|}«d
musclea ftf thfi biidy aiv alfecteil, and twit'Cbet* tx^citr in them ; thvir tonieity is
exaggemb^J, and finally thi'ir fttuctiotial activity is di'stnjyod. Tbb chatige is
referrtKl t" an a(?tion on the muscular HtructiiT'e itself, indepndt'nt i>f that u(»on th*'
heart, and aXaa iridijjstindent of tbe cer^lmi sjiinal nervous aysteni. (4) Tbe rt^lhi
»<itinn nf tbcs spinal curd is suspended afti^r the heart U piimlysed^ but the mot«r
ixinductivity of tlie apinal i^ord and of tbe nt*rve trunk* continue alter tin* striped
miisclfs of the body ar^ ^lamly&L-fL (fi) The lympbdit^rt^ of thi? fixtg continue to
contract for umuy minuk^ after the bhxMldieart lios been |iar!i)y^cL
• Sohtniedebei^t op, til*, from unpuhli«hed j-escarebesi of Professor H* Meyer,
Dorpat,
t Huaemann, Archwf, e^jter. Ptith. if. FharmttM., Hd. v , S. 228, 1^7^-
Z Digiiotmn (see ante, p. 43S) belongB to this group.
448
POISONS: TiiEm kffkcts and detection. [| 556-559.
3, NON-CRYSTALLISABLE GLUCOSIDES ALMOST INSOLUBLE
IF WATER.
§ 556. Scillain, or SoillitlDi & glncoaide which has heeu separated from the
Imlbs of thfl eoiiimoii squilL It 18 insoluble or ocarly so in water^ but easily dis-
solves in aloohol. It is little Baluble in ether. It aets upon the b^art^ atid is
pOlAOHOllS.
§ {»57. Adonidia, a very similar Bubstance, has been sepArated froin tbe mot df
the Adonis verneUiiti'^a.t. Ord, J^inuncida^cir), to which th^nnmo ofadomdmbatibeen
given,* It isananicirphouHj colourlt'^ substaneo, without odour ; solublu in jvlcohol,
but with difficulty s<i1ub]e in other and water. It i^ jirecipitated by tannin, and fin
safKiDification by uiiiicial acids, splits up into sngar and a suhatance solnble in eth<?r.
Tlie etfpcts rm animal b are identical with those of digital in. The root has be^n UBcd
recently In nn>«li^ine» and found to alow the heart and incToa^ tba urinary ^^rotion ;
in tbb also it in like digitaJIs,
§ 558. Oleandrin.— Oleander leaves contain two chemically •difTerent, nitTOg«ii'
free substances. The one ia probably id^nticiil with digitalein j but as tliis in not
cei'tain, Schinlecleborg proposes to eall it provisionally mHiti, The other active
substance is essentially the same as the oleandrin of Lukomsk«t and Betelli.t
Oleandnn has basic projiertiea, and Is aejiarated in th« form of an amorphous mass,
aolubk in aleohol^ etheri and chloroform, and aligbtly soluble in water* Schmii?de.
berg obt^iined a third product from AfrinaTx leaves^ wliich ho calls ncrianthin, Tliis,
on treatment with snlpburic acid and bromine, gives a beautifal colour |>ecu1iar to
ole«ncler le4ives» It is very similar in physiological and cbEmicul profierties tii
digitftljn, and in probably derived by decomposition from oni^ of the princtplisa nl ready
di'sciilMxl. Tbei^ is also a pToduct similar ttj digital iresin*
Tlic active principleR of the oleander nn^ Be^iamted bjr digestion of tbe leaves with
alcuhffl of 50 \MiTGiitiU, and precipitating tbe aloobolic extract with lead acetate and
ammonia. The lii^t precipitate h yellow^ and ia probably CJitnposed of a tannin-like
mi balance ; the next preeipitafc© is white, consisting of the Jead com|»o^nd of neriin.
The precipitate^ are filtered oft, and the filtrate concentroted ; neriaothin, after a
while J sepamtea in light floeks, and the filtrate from tlini contains some of the other
products,
§ Sf»9, Neriin or Oleander Digitalin.^Keriin is, iu the presence of miieb free
mineral acid, precijtituted by potass- bismuth iodide, a reaction tirst pointtyi out by
Mariu^%§ as uncfnl in the isolation of the hellchorins ; or it may be precipitated by
tannin, and then the precipitate decomposed by dias^idving in alcohol, and eva|ioraUn/|
it to dry ne^s with ^iiic oxide on the water-ltath. It is next extracted by absolute
alooho!, and precipitated by the addition of much ether. The further purification
consisbi of re-8olutLon in alcohol^ and fractional precipitation liy ether. If, however,
the potass* bismuth iodide pi-oeeas is usi^i, the lii|uid munt be acidified RtTtn\i*]y with
sulphurtc acid, and the precipJtJ^te waaherl with diluted sulphuric acifl. The pi*e^
cipitate inay be decomjtosed by baryta, filtered, and the filtmte freed from baiyta by
carbon dioxide ■ tlie filtrate from this contiiins neiiin with baric ifdidc ; it is tliere-
fore treat*\1 T^qth silver sulphat^ej tlnin again with baiyta, next with carbon dioxide,
and also with SHg lo get nd of tlte lai*t trac« of si hen
Tbe filtmte will also contaiti Bomo oleandrin whicht by evai^orating slowly tn
a vurnum, sejiaratcs gi^adually in the foim of a clear, resinonj maHS. It can be flltei'ed
' Cervello, Archiv fUr ATp. Pfrlh. Ph^rm,, 1882, p* 338.
t ReprrL iJU ChimU dU JFuHz d Bttrrrsivil, %. in. p* 77, 1861.
+ BtilL M&lL diBvlogna, L xix. p. 321, 18G5.
§ Ztiiacftr.f. rat. Mtd, (3 R.), Bd, xxvi. S, 1, 1866,
§ S60-S62.]
POISONOUS GLUCOSIDKS.
449
©flf, Aiid the neriin then may be precipitated pure by fructiorwU prireipitfttioju Ita
phjdologjoal action i^ tlie same aa thivt of digiialem.
g 600, The Nerium okander has &eTenil timfta canaed grave ijmptoma of pobon-
ing, and they have usually fairly agreed with those produced by foxglove. For
example, Maschka* relates the case of a boy, 2 years old, who ate two handfuls
of the NiiriuTn oltamler. The etfeeta commenced \m ten niii]tite9, the cMld waa
uneasy, and vomited. In six hours a sleepy condition came on ; the faoe was pale,
th0 akin cold, the pupils contracted, and the pulse sjlow and irregular, AfUr the
aickneaa the boy woke up, but again Ul\ asleep, and Hn^ o<^iirre<i frequently ;
cofTae wis given, whieh appeared to do good. The [lulse was iiitem;ittent. On
the following day t^ie chiM wa« atill ill, with an intermittent pulse* frequent
vomiting, feebleness, aleeplesanesi, and dilatation of the pupil ; there was no
dian-litBa^ on the contrary, the bowels were coofinerl* Oo the thitd day recovery
followed.
In an Indian case,t the symptoms were altogether peculiar, and belonged
rather to tht; convtilaive or<!er. A woodcutter, oginl 35, n^ar Kbolafkore^
toak, for the pnrj>ose of suicide, a little over an otince of the eacjiresatMl juice
of the oleander. The symptom^i bc^an ao rapidly tliat ht had not time to walk
five yards before he fell insensible ; ho was brought to Iho hospital in tbi« state ;
the face on his arrival was noticed to be flush i>d, tbe breathing atert*:)rous, there
were riolsot a^iasimodio eoutractions of tbe whole body, more marked on tbt*
left than on the right side. The effect of this was roniurkable* During tbi*
intenrals of tbe sfjasm, the patient lay evenly on bis back, and wlien the con^
vulsions commenced tlie superior contraction of the left side threw bhu on to
the right, in which po«titit>n he remained during the jiaroxysm, afti!r tbu Kubsidence
of which be fell back iubi hia old position. The evacuatinns were iiivoluntary
ftnd watery ; the man was inaentsible, with frequent convulwions of the kind
described^ for two days, hut on the third day became conscious, and made a goiKl
recovery.
In any c^iw of (toisoning, the methods by which uertin and oleandriii are separated
fixtm the plaut catk he applied to oepvatc them from the tissues with more or lesA
.Huccesa, Here, as in ilII tlie other digitalln-like glucotddes, physiological tests are
alone of value iit the tinal identiftcHtiou.
lh%\* The Hadagaacar Ordeal Folaon.— To this group may aljto bekng the
poison of the Tanfjhhiia tvjitcHt/rm, a tree iij the Island of Afadagosoar, tll0 fruit of
which ia naed as an ordea! poi^n. It may be obtained in crys^tala ; it is insoluble
in water, and vstry jjoifionoua. Tim ujmw of fiingajKire is also said to contain with
strychnine a glucoeide timilar to antiann*
I. 9UBSTAXCES WHICH BEHAVE LIKE THE DIGITALIHa
§ fi62. Ap€>cynin, which with apotr/ymn (a gltteoside) occurs In jipoq^itm
tannahmum vnuimmf an 'Knat Indian arrow poisun ; t^hvjin, a north-west African
arrow [wison ; Hr&^t,hi?i aud HreehtUtj-iHr from Urvtkitis mbertUa \ koiHtilnmariUf
a glucoside from May'liowers ; loroniiliUf a glucoside from CoronUla mitpimdtt ;
thiiranihin^ ft glucoside from CfmranUtus chtiri ; are all sulatancea which have a
aimilar action to digital; a on the hearw Efythrophlein is an alkaloid, not a gluco-
side, and h obtaiued frum the bark of the Mfffihtitphiaum tiuinetnse (W^t Afriea),
It acts on the he^t (ike digitalis, and has also effects similar ta picmtnxiTu
• FierUlJfihrMehnftf. ffet-khL MrtL, Bd, ii, N*i» 17, 18(J0»
Chir. lUvieWf vol xxvi. p. 5*£3, ISflO.
t Tramm^ <f M^d^ and Phtf». Siic, &/ Btymbatfj 1854
BrU, nnd F&r, Mrd.
29
4SO POISONS : THEIR EFFECTS AND DETECTION. [§ 563, 564.
III.— Saponin— Saponin Substances.
§ 563. The term *^ saponin " of late years has been applied to a class
of glucosides which possess the common property of being poisonous,
and, when dissolved in water, forming solutions which froth on shaking
like soapsuds.
The substances which have these properties are not all of the same
series chemically, but those of the general formula, CnHja-sOjo, are
most numerous, and the following is a list : —
Name. Fonnula.
Saponin, senegin,
Quillaja-sapotoxin,
Sapindus-sapotozin, ^ - ^f^ss^io*
Oypsophila-sapotozin,
Agrostemma-sapotoxin,
Sai)onin II., digitonin, saporubrin, assamin, ^is^as^io*
Saponin III., quillajic acid, polygalic acid, 1 n u f\
Hemian-saponm, \
Cydamin, sarsaparilla-saponin, ^H3aOio.
Sarsa-saponin, ^^^flafiio*
Parillin, Ca8H440io.
Melanthin, Cs^HsoOjo.
Possibly also dulcamarin, C22H34OJQ, and syringin, Ci^Hj^Oiq, may
belong to this series.
There are some 150 distinct plants which thus yield saponins ; a
few of these plants are as follows:— 5apcmart a officinaliSj G^ypsophila
strufhtum, Agrostemma githago (com cockle), Polygala senega, Monimia
polystachia, the bark of Quillaja saponaria, and Chrysophyllum gly-
cyphieum.
The saponin separated from Saponaria and from the com cockle
will be here described.
§ 564. Properties. — Saponin is a white amorphous powder, very
soluble in water, to which it gives the curious property of frothing just
like soap solution. To obtain this effect there must be at least 1 mgrm.
in 1 c.c. of liquid. Saponin is neutral in reaction, it has no odour, but
causes sneezing if applied to the mucous membrane of the nose ; the -
taste is at first sweet, and then sharp and acrid. It is almost entirely
insoluble in absolute alcohol, but dissolves in hot alcohol of 83* to
separate again nearly completely on cooling. It is precipitated by basic
lead acetate, and also by baryta water, but in each case it is advisable
to operate on concentrated solutions. Picric acid, mercuric chloride,
and alkaloidal ''group reagents '' give no precipitate. When a little of
the solid substance is treated with "Nessler" reagent, there is a
§ 56;.]
SAPONIN,
45 '
greenish or yellow colour produced, A drop of strong sulphuric acid,
miied with a minute quantity of saponin, strikes slowly a bright red
colour, which, on heating, deepens to maroon-brown. Nordhaueen
sulphuric acid shows this better and more mpidly. If saponin is boiled
with dilute acid it breaks up into sapogeniu and sugar, and therefore
the liquid after neiitrahsation reduces ** Fehling/'
Sapogenin may be aeparated by evaporating the neutraliHed liquid to
dryness, treating the dry residue with ether, which dissolves out the
sapogenin, and tinally recovering the substance from the ethereal
solution, and crystalliaing it from hot akohol. Crystals are readily
obtained if the alcoholic solution is allowed to evaporate spontaneously,
A solution of eaponin exposed to the air gets turbid, and devobpe
carbon dioxide ^ not unfrequentlj the solution becomes mouldy*
W. von Schuk* has shown that aiiponibin, the active principle of
SapfMamt nihea^ when treated vvith dilute sulphuric acidj gives glucose
and various itajfotjetun^ according to the temperature and having the
ft^rmulse Cj^H^ji^O^, C^gH^yO,^, CigHg^O^, Cj^H^gt^^t ^^'^ 1**^^ melting at
2 4 8*- 250** The sugar formed has (ti),^ - + 23"67 and is not fermentable
by yeasty the oaazone melts at IS^^-WO',
g 565v EfFecta.^Pelikant has studied the effects of various saponins
on frogs* One to two drops of a saturated watery solution of saponin
applied subcutaneously to the leg, cauBcd, in from five U) six minutes,
great weakness, accompanied by a loss of sensibility ; but strong
mechanical, chemical, or electrical stimuli applied to the foot excited
reflex action, for tiie ischiatic nerve still retained its functions* Never-
theless, from the commencement, tike excitability of the poisone<l muscles
was much weakeoed, and just before death quite disappeared. Section
of the ischiatic nerve delayed the phenomena* Cnrarine did not seem
to have any efTect on the poisonous action* A concentrated solution
applied to the heart of a frog soon arrests its l>eata, but weaker doaes
first excite, and then reUird, I
The senior author has studied the general action of saponin on kittens,
inaects, and infusoria* Small do&ses, such as from 13 to 32 mgrms. (J to
^ grain )j were injected beneath the loose akin of the back of the neck of
a kitten, when there w*ere immediate symptoms of local pain. In from
*ive to ten minutes tlio respiration notably quickened, and the animal
fell into a lethargic statOj with signs of general muscular weakness ; just
before death the hrea thing became very rapid, and there were all the signs
of asphyxia. The pathological apjjt^arances after death were fulucsa in
the right side of the hearty and intense congestion of the iutestiual canal,
the stomach generally being perfectly normal in appearance, and the
• Vhem. C*ntr., 18&7, 302, t BerL klin. Wo^h^iv., 36, 186,
t J, Hop|je, Nett'etttHrkim^ tier M^ilmiUel^ H* 4, 37,
452
miSONS : THBIR RFFECTS ANH BRfECTION. [| S^i 5^7*
kidneys and other organs healthy. Tlie least fata! doee for a kitten
seems to be 13 ragrms.* or '04 grm, to a kilogramme.*
^566, Action on Man. — The efTecta of saponin on man have been but
little studied ; it has been adniinistered bj the mouth in doses of from
'1 to '2 grm., and in those doses seems to have digtinet physiological
effects. There is increased mucous secretion, and a feeling of nausea;
but neither diaphoresis nor diuresis has been obseryed. From the fore-
going study it may be predicated that 2*6 grms. (40 grains), if adminia-
tered subcutaneously to ati adult, would endanger life. The symptoms
would be great muscular prostration, weakness of the hearths action^ aud
probably diarrhoea. In fatal cases^ some signs of an irritant or in Bam-
matory action on the mucous niembranes of the stomach and intestines
would be probable,
S 567. Separatioii of Sapoaiji,— Sapouiu is separated from bread,
flour, and similar Bubstatjces by the process given at p. 153, ** Foods.*'
The process essentially consists in eitracting with hot spirit, allowing the
saponin to sepamte as the spirit coolS| collecting the precipitate on a
filter^ drying, dissolving in cold water, and precipitating with absolute
alcohol. In operating on animal tissues, a more elaborate process is
necessaiy. The senior author has successfully proceeded as follows ;— The
finely divided organ is digested in alcohol of SO to 90 per cent, strength,
and boiled for a quarter of an hour; the alcohol i» filtered hot and
allowed to cool, when a deposit forma, consisting of fatty matters, and
containing any saponin present. The deposit is filtered off, dried, and
treated with ether to remove fat The insoluble saponin remaining
is dissolved in the least possible quantity of water, and precipitated with
absolute alcohol. It is also open to the analyst to purify it by precipi-
tating with baryta water, the baryta compound being subsequently
decomposed by carbon dioiide, Basic lead acetate may also be used as
& precipitant, the lead compound bein^, as usual, decomposed by hydric
sulphide ; lastly, a watery solution may be shaken up with chloroform,
which will extract saponin. By some one of these methods, selected
according to the exigencies of the case, there will be no diflficulty in
separating the glucoside in a fairly pure state. The organ best to ex-
amine for saponin is the kidney. In one of the experiments, in a cat
poisoned with a subcutaneous dose of sapouiri (2 grm.), evidence of the
glucoside was obtained from the kidney alone. The time after dejith at
which it is probable that saponin could be detected is unknown ; it is a
* Tlie action of sa^wtiin when Applied in concent rat<*d Bcilutiou to Oioa is that of
an intflaae imt&nt Tliere is protnision of tlic sucker^ aud progrfisHi v^e puralysja.
The common infusf^ris live fur soum iiiue in diluto Bolmtioaa of saponin — this is h\$g
true of some of the higher formg ; for example, « Cfifekpi fUadtiGormii seemed ia no
m^y ftlToctad bj li 2 i>er cent, solution.
S 568-570.] SAHTOHIN. 453
Bubstanc€ easily decomposed, and, therefore, success in separntiwg it from
highly putrid matters is not probable.
g 668. Identification of Saponin. — An amorpiious white powder,
very soluble iu water, itisoluble in cold alcohol or ether, having gluoo-
sidal reactions, striking a red colour with sulphuric acid, imparting a
soap-like condition to water, and poisonous to animals^ is most probably
a saponin.
DIVI810K III,— VARIOUS VEGETABLE POISONOUS PRIN-
CIPLES NOT READILY A I >M ITT I KG OP CLASSIFICA-
TION IN THE PREVIOUS DIVISION,
L— Santonin,
S 569, Santonin (CjqHijj^Ojj) is a lactone extracted from the
uuexpanded beads of various species of Afttmtma(j^^t. Ord* Conijumike).
The seeds contain, according to DragendorfTi 2^03 to 2' 13 percent, of
ifantouin, and about 2*25 [>er cent, of volatile oil, with 3 per cent, of fat
and resin. Santonin fortiis brilliant, white, four-sided, flat prisms, in
tafite feebly bitter, m.p. 170*. Santonin in a concentration of 2 per
cent, in 80 per cent, alcohol turns the plane of polarised light to the
left, [a]^„ at 15'* = -176 -5* ; in cbloroform, **17L5\ Santonin dissolves
in alkalies, changing into santonic acid, Cj^H^oO^ ; this may be retrans-
formed into santonin and water by beating at 120'.
Santonin contains a ketone group and its phtjnyl-hydrazone melts
at 220*. It is believed to be a derivative of b exa- hydro-dim ethyl -
naphthalin. The crystals become yellow through age and exposure
to light ; they are sciireely soluble in cold water, but dissolve in 250
parts of boiling water^ freely in alkaline water, in 3 parts of boiling
aleobol, and in 42 parts of boiling ether. Sodlo eantonate (Cj^^H^^NaO^
+ 3JH^0) is olHcinal on the Continent; it fornis colourless rhombic
crystals, Bolnble in 3 piirts of cold w^ater.
^ 570. Poifioning by Santonin. ^ — Eighteen cases of poisoning, either
by santonin or santonin-holding suhstanceSj whicli F, A. Falck has been
able to collect, were nearly all occasioned by its use as a remedy for
worms. A few were poisonings of children who had swallowed it by
accidentL With one eicception those poisoned were children of from
2 to 12 years of age; in five the flower heads, and in thirteen
santonin itself was taken. Of the eighteen eases, two only died (about
1 1 per cent.)*
454
5tS0H9: THKIE EFFECTS AND DETECTION. [§ 571^573.
§57L Fatal Dose.— So Bmall a number of children have died
froDi santoum^ that data arc not present for fixing the niiuimitm
fatal dose. "12 grni. of santonin killed a boj of 5 J years of age
in fifteen hours; a girl, 10 jetiTE old, died from a quantity of
flower heads equal to *2 grm. of santonin. The tuaximum do&e for
chUdren is from 65 to ID4 mgrms, (1 to 3 grains), and twice the
quantity for adults*
§572. Effects on Animals. — Experiinenta on animals with santonin
have been numerous. It has first an eiciting action on the centres of
nerves from the second to the seventh pairs, and then follows deer ease
of exci Ability. The medulla is later affected. There are tetanic con-
vulsions, and death follows through asphjxia. Artificial respiration
lessens the number and activity of the couvtikiona, and chloroform,
chloral hydrate, or ether also either prevent or shorten the
attacks.
g 573, Effects on Man, — One of the most constant effects of
santonin is a peculiar aberration of the colon r-sensej first observed by
Hufeland in ISO 6. AH things seem yellow, and this may la»t for
twenty 'four hours, seldom longer. According to Hose, this apparent
yellowness is often preceded l)y a violet hue over all objects. If the
lids are closed while the *' yellow sight " is present, the whole field is
momentarily violet. De Martiny,* iu a few cases, found the **y el low-
sight " intermit and pass into other coloure, e.y.^ nfter '3 grm. there was
first the yellow perception, then giving the Biime individual *6 gTm.» all
objects seemed coloured red, aftei' half an hour oraugej aud then again
yellow. In another patient the effect of the drug was to give *' green
vision/' aud in a third hlue,
Hufner and Helraholtz explain this curious effect as a direct action
on the nervous elements of the retina, causing them to give the per-
ception of violet ; they are first excited, then exhausted, and tlie eye h
"violet blind." On the other hand, it has been suggested that
santonin either colours the media of the eye yellow, or that ttiere
is an increase in the pigment of the macula lutea. The two last
theories do not, however, account for the intermittency and the play
of colours observed in a few cases. To the affections of vision are
also often added haUucinations of taste aud smell ; there is headache
and giddiness, and in fourteen out of thirty of Rose's observations
vomiting occurred. The urinary secretion is increased. In large and
fatal doses there are shivering of the body, clonic, and often tetanic
convulsions ; the consciousness is lost, the skin is cool, but covered with
sweat, the pupils dilated, the breathing becomes stertorous, the heart's
action w^oak and slow, and death occurs in collapse — in the case observed
§ S74. S7SJ
SANTONIN.
455
by Griram in fifteen hours, in one observed by Linatow in forty-
eigbt bours^ In those patients who have recovered, there have
Bho been noticed convukions and loss of consciousness. Sieveking^
has recorded the case of a child who took *12 grm, (1*7 grain)
santonin; an eruption of nettle rash showed itself, but disappeared
withiu an hour,
.§ 574, FoBt-mortem Appearances. ^Tbe post-mortem appearances
are not ch a ract eristic.
§ 575, Separation of Santonin from the Contents of the Stonmcbj
etc.— It is speciaily important to atialyae the fafces, for it has been
observed that some portion goes unchanged into ihe intestinal canal.
The urine, also, of persons who have taken santonin, posse^es some
important peculiarities. It be cornea of a peculiar yellow-green, the
colour appearing soon after the ingestion of the drug, and lasting even
sixty hours. The colour may be imitatedi and therefore confused with
that which is produced by the bile acids ; a similar colour ia also seen
after persons have been taking rhubarb. Alkalies added to urine
coloured by santonin or rhubHrb strike a red colour. If the urine thus
reddened is digested on aina dust, santonin nriue fades, rhubarb urine
remains red. Further, if the reddened urine is precipitated by eiLcess
of milk of lime or baryta water and filtered, the filtrate from the urine
reddeneii by rbubiirh is colourless, in that reddened by santonin the
colour remains. Santonin ntay be isolated by treating substances con-
taining it with warm alkaline water The water may now be acidified
and shaken up with chloroform, whieh will dissolve out any santonin.
On driving off the chloroform, the residue should be again alkaHsed,
dissolved in water, nud acidified with hydrochloric acid, and shaken up
with chloroform, in this way, by operating several times, it may be
obtained very pure. Santonin may be identified by its dissolving in
alcoholic potash to a transitory earmine-red, hut the best reaction is to
dissolve it in concentrated sulphuric acid, to which a very little water
has been added, to warm on the water-bath, and then to add a few dro|)ti
of ferric chloride solution to the warm acid ; a ring of a beautifvd rod
colour passing into purple surrounds each drop, and after a little time,
OP contiiiuiug the heat, the purple piisses into brown* A distinctive
reaction m also the production of '^ iso-santonin " ; this substance is
produced by warming santonin on the water- bath with sulphuric acid
for a few hours, and then diluting with water ; iso-santonin is pre*
cipitated, and may be crystallised from boiling alcohol. Iso-suntonin
melts at 13B*j it has the same composition as santonin. It b dis-
tinguished from santonin by giving no red colour when treated with
aulpburic or phosphoric acids.
' BriL Mid. Jmm., 1871.
456
POISONS: THIIR EFFECTS AND DETECTION. [§ 5/6-578.
IL— Mezereon-
i 67ti. The Daphne Mezereum (L,).— Mexereon^ an indigoiions Bbmb belnngjug
to the Thyniel^^i'ci^, is rutlier mre tti the wild fitate^ but verj fi'cquent in gardeM&
Thf^ flowers are purplt^ and Ihe berne^i red. Buckhtjim isolated by iiioiTis of ctlier hu
wond iTesin, which was c^in verted by aiijHvuifymg agents into mezc^ci^t neid ; the aerid
resin is the anhydride of the acid, Tht; resin ii j>rBeuiiiL'<l to be tlie active jfoisonoua
ooDstituont of the platit^ Imt th6 subject awaits ftivther investigation* There are a
few eases of poieKniing on reconl, and th«y havt^ beDH m^fstlj from the iK^rriea. Tbu»,
Linm'^ has reetirded an instane*^ in which a littlff girl died after oatlng tw*?lvp bomes.
The sjmj^toms observod in the rf?corded cases liavu been burning in the mouth,
gastroenteritis, vomitingt gi'^flJn^ss, narcoi*is, and convtilsimifi, ending in death.
The lethal doise for a horHC Li about 30 grm^. of powdered bark ; for a dog, the
«^ophagua being tied, 12 gnii?». ; but smaller doses of the fresh leaves may be deadly.
III.— Ergot of Bye,
§ 577. Ergot is a peculiar f nugiis attacking the rye and other grami-
naoeous plants;* it has received various names, Olaviceps pui*2mrea
(Tulasne), S^er»ia3*i*a damm (Fries), ScieroHum datms (D.C), etc. The
peculiar train of symptoms arising from the eating of ergotised grain
(culminHting occasionally in gangrene of the lower limbs), its powerful
action on the pregnant uteruB, and its styptic eflbcta, are well known.
The very general use of the drug by accoucheurs has, eo to speak,
popularised a knowledge of its action among all classes of societyj and
its criminal employment as an abortive is not infrequcntt
The healthy grain of rye^ if examined microscopically in thin sections,
is seen to be composed of the geed-coating, made up of two layers,
beneath which are the gluten*cellsj whilst the great bulk of the seed
is composed of cells containing starch. In the ergotised grain, dark
(almost black) cells replace the seed^oat and tho gluten-cells, whilst
the large starch-con tainlng cells are filled with the small cells of the
fungus and inimerous drops of oil.
g 578. The chemical confitituents of ergot are a fixed oil^ trimetbyl-
am hie, certain active principles, and colouring- matters.
The fixed oil is of a brownish^yellow colour, of aromatic tlavonr and
acrid taste ; its apedfic gravity U 0*924, and it consists chiefly of
palmitin and olein ; it haj5 no phyaiological action.
TnmethylamiQe is always present ready formed in ergot j it can also
be produced by the action of potash on ergots
With regard to the active principles of ergot considerable confusion
still exists, and no one baa hitherto isolated any single substance in such
* Some of the Cifp^racete are also attacked.
t The Euasian fieaaantiy use the drug for the same purpose. FicU Mackcode
Walkce*s '*Rui*aij4/M, p, 117.
§ S78.1
ERGOT OF RYH;
4S7
a state of purity m to inspire coufidetice m to its formula or other
chemical charftcters. They may, however, be briefly describod.
C. Tauret * hm separated an alkaloid, which appears identical with
Wenzeru ergot mine. To obtain this the ergot ia extracteii by alcohol of
86'' t the spirit removed by distillation, and the residue cooled ; a resin
(which ia depOv^ited) and a fatty layer (which floats on the surface) are
separated from tlie extractive liquor and wasiied with ether ; the ethereal
solution 13 HItered and Ejhaken with dilute tjulphuric acid, which takca
up the alkaloid ^ the aqueous solution of the stibstance is then Altered,
rendered alkaline by KHO, and agitated with chloroform. The
ei'gotiniue ia now obtained by evaporating the chlorofonn solution, cure
being taken to protect it from contact with the air. It gives precipitatca
with chloride of gold, potassium iodohydrargyrata, phosphomolybdic
acid, tanuin, broniitie waterj and the chlorides of gold and platinum.
With moderately concentrated SO^H^, it gives a yellowish-red coloration,
changing to an intense violet, a reaction which does not occur if the
alkaloid has been exposed to the air. The composition of the base is
represented by the formula CyyH^^N^Ojjjj and a crystalliue sulphate and
lactate have been obtained, t
Wen^el's Ecboline is prepared by precipitating the cold watery
extmct of ergot with sugar of lead, throwing out tfie lead in the usual
way by hydrie sulphide, concentrating the liquid, and adding mercuric
chloride, which precipitates the ecboline only. The mercury salt is now
decomposed with hydrie sulphide, and after the mercury precipitate
hm been filtered off, the filtrate is trcateil with freshly precipitated
phosphate of silver, and refiltered ; lastly, the liquid is shaken up with
milk of lime, again filtered, nnd the lime thrown out by CO^. The last
hltrate cont^iins ecboline only^ and is obtained by evaporation at a gentle
heat. It is an amorphous, feebly bitter substance, with an alkaline
reaction, forming only amorphous salts,
A research by Dragendorff on ergot tends to show that Wenzel's
alkaloids, ergotinine and ecboline, are inactive, Dragendorif describea
also (a) Sderomucinj a slimy substance which goes into solution upon
extraction of the ergot with water, and which is again precipitated by
40 to 45 per cent, alcohol. It is colloidal and soluble with diflienlty
in water. It contains nitrogen, bnt gives no albuminoid reaction, nor
any reaction of an alkaloidal or glucosidal body ; it yields to analysis—
8^26 per cent. Water.
268 „ Ash.
39 0 „ Carbon.
6*14 „ Hydrogen,
641 „ Nitrogen.
* Cofiipf. Mmtdm, vol, %x%L y. 866. t Ibid.t April 1878.
4S8
POISONS: THEIR EFFECTS AND DETECTION.
t§ 578.
(h) Sclerotic acid, — A feeblj-acid siibataiicej easily soluble iti water
mid dilute atid mcMJeratelj conceiitmte^l alcohol. It passes^ in ftasocia-
lion with other co»atitueiiU of the ergot extract, into the difTusate, when
the extract is stibmitted to dialysiB ; but after its separation in a pure
state it is, like scleromuoin, colloidal. It is precipitated by 85 to 90 per
eent alcohol, together with lime, potash, soda, silica, and manganese ;
but after maceration with hydrochloric acid, the greuter part of the ash
ooaBtituents can be separated by a fresh precipitation witii absolute
alcohol The sample gave 40^0 per cent, of carbon, 5*2 per cent, hydro-
gen, 4 '2 per cent, nitrogen, 50"G per cent, oxygen, with 3-1 per cent, of
ash. Sclerotic acid forms with lime a coiupotind that ia not decomposed
by carbonic acid, and which upon combustion leaves from 1 9 to 20 per
cent, of calcium carbonate. Both these substances are active, although
evidently impure. Sclerotic acid Is sold in commerce, and has been
employed snbcutaneously in midwifery practice in Eueaa and Germany
for some time.
The active principle of ergot has been recently called Sphacelo- toxin,
but has not been separated iu tx pure form* According to Jacohi {Pharm.
Cmih\, H. xixviii, 58, and AtcIk expt, PatfL Phann.t xxxix, 85-143)
there are three substances, all pOBSesaing similar therapeutic }K}wers,
which may be obtaiued from ergot, viz., spbacelo- toxin, as yet only
obtained as a tarry substance containing no nitrogen ; secal in- toxin, a
compound of sphacelo-toxin with the inactive secatiu ; and chry so- toxin,
a compound of spbacelo-toxin with the inactive ergo-chrysin, C^jH^sO^.
Of these, by far the moat definite is Ghrt/»Q-t(Mi\ which has the same
ejfecbi as ergot ; chryso-loxin can be precipitated from the ethereal
extract of ergot by light petroleum — by re dissolving this product in
ether and Eigain precipitating and repeating the process many times ; it
may nltimately be obtained as a yellow, tasteless, odourless powder;
crystallising from an ethereal saturated solution in needles. It is
soluble in most orgimic solvents^ but insoluble in light petroleum and
dilute acids. It is slightly soluble in alkalies and ammonia^ and from
such solutions is precipitated by carbon dioxide.
Secalia-toxm, C^^Hj^N^O,^, is apparently a nitrogenous substance;
posBibly, as Jacobi suggests^ a compound ; in any case it seems to be
identical with the so-called alkaloid, **Cornutia/* It is obtained from
the ethereal extract by shaking it with acetic acid^ and precipitating the
acid extract with sodium carbonate. It is very easily soluble in alcoliol,
et hylic acetate, benzene, and chloroform- It is not very soluble in ether,
very slightly soluble in water, and insoluble in petroleum ether. The
oxalate may be prepared by precipitating its ethereal solution with
an alcoholic solution of oxalic acid.
The comutin of Kobert is obtained by thoroughly exhausting ergot
§ 5780
KRQOT OF-FTK
459
hj petroleum ether, drying the ergofc thtus freed from fat, and
exhausting with ether ; the ethereal solution is shaken up several times
with dihite hydrochloric acid (0^5 per eent); the at;id solution is now
satunited with iimmotiiti, ami the cornutin extracted by shaking the
ammotiiacal liqtiid up ^vlth ether.
The ethereal sohUion on ^vapomtion leaves the alkaloid, which j
when it becomes crystalline, is with difhcidty soluble in ether, but
dissolves easily in chloroform and alaohol. It ie insoluble in petroleum
ether, and may be precipitated from an ethereal solution by that reagent
in white Jlocks* The alcoholic solution shows a blue-viulet fluorescence ;
from the alcoholic solution the alkaloid can be precipitated by the
addition of water. The SiUts are obtAinod best by adding to the
cbh*roform solution au ethereal solution of an acid, in the dark, for the
salts are scufjttive to light ; in this way the hydroehloride, tartrate, and
citrate can be obtained^ the gaits separating out.
The alkaloid gives precipitates imniediately, or after a little time, with
picric acid, iodine in iodide of potassium solution, bromine water,
ferr id cyanide of potassiura, Mayer^s reagent, and tannic acid ; a few
mgrms. of the acid dissolved in 1 c.c, of strong snlphorie aeid becomeB in
a few hours of a beautiful violet*bhie colour^ which only after several
days bleaches out. If to the solntion in sulphuric acid a small drop of
ferric chloride solution is added, the mixture beconaes first of an orange-
red colour, passing into a deep red colour ^ this reaction succeeds beet
with from 2-3 mgrms. j larger quantities do not give the reaction so
neiitly (Keller, ZeiL/. anal, Chetme, 1895).
Tlie inert principles of ergot are — (1) A red colouring-matter,
Sdereri/thrinf insoluble in water, but sobibl*.' in dilute and strong
alcohol, ether, chloroform, dilute solutions of potash, ammonia, etc. It
can be obtained by dissolving in an alkali, nentralishig with an acid,
and shaking up with ether. Alcoholic solution of sclererythriu gives
with aluminium sulphate^ and with zinc chloride, a splendid red
mixture ; with salts of calcium, barium, and many of the heavy metals
it gives a blue precipitate; the yield is only *1 to '05 in a thousand
parts,
(2) Another colon ring-mat ter, dissolving in concentrated sulphuric
acid with the production of a fine blue- violet colour, the discoverer has
oamed Sderoidin. This h not soluble in aleoiiol, ether, chloroform, or
water, but dissolves in alkaline solutions, potash producing a splendid
violet colour ; yield about 1 per lOOO*
(3^ 4) Two cryatalhne substances, which maybe obtahied from ergot
powder, first treated with au aqueous solution of tartaric acid, and the
-colouring- matters extracted by ether. One Dragendorff names Sderty
ystaUin (C|^H|qO^) ; it is in colourless needles^ insoluble in alcohol and
460
POISONS 1 THEIR KFFECTS AND DETECTION, [§ 579"58t.
water^ with difficulty soluble in ether, but dissolving in ammonia and
potash 8ohitiou». The other orjBtailitie aubstatice i^ thought to bu
merely a hydrated compound of BClerocryatalliQ. Both are without
physiological action,
§579. Detection of Ergot m Flour (see " Foods,'' 5th edition,
p, 155), — The best procesa is to exhaust the flour with boiling alcobol.
The alcoholic solution is acidified with dilute sulphuric acid, and the
coloured liquid oianiined by the spectroscope in thicker or thinner
layors, according to the depth of colour. A similar alcoholic solution of
ergot should bo made, and the spectrum compared. If the flour ia
ergotised, the solution will be more or lem red, and show two absorp-
tion bands, one in tiie gruen^ and a broader and stronger one in the
blue. On mixing the original solution with twice its volume of water,
and shaking Buccessive portions of this liquid with ether, amyl alcohol,
benzene, and chloroform, the red colour, if derived from ergot, wiU
impart its colour to each and all of these solvents* Ludwig Medicus
and Koljcr [Zeit. Nahr. Getutssm.^ 1902] detect ergot in Hour by treating
10 grms. with 20 c.c, of ether and 10 drops of sulphuric acid [1 : 5],
The ethereal extract on shaking up with 10 drops of sodium hydrogen
carlKinate gives a violet coloration if ergot is present.
§ 580, Pharmaceutical Preparations. — Ergot itself is oflicinal in al!
the pbarmacopa'iati, and occurs in grains from J to 1 inch in length, and
about the same breadth, triangular, curved, obtuse at the ends, of a
purple colour, covered with u bloom, and brittle, cxhjl>itiug a pinkish
interior, and the microscopical appearancca already detailed. Ergot may
also occur ss a brown powder, possessing the unmistakable odour of the
drug. A liquid eitraet of the B.P, is prepared by digesting lit parts
of ergot in 80 parts of water for twelve hours, the infusion ia deciinted or
tiltered off, and the digestion repeated with 40 parts of water ; this is
also Hltered off, and the residue pressed, and the whole filtrate imited
and evaporated down to 11 parts; when cold, 6 parts of recti tied spirit
are added, and, after standing, the liquid is filtered and made up to
moasnre 16. A tincture and an infusion are also ofiicioaJ ; the latter is
very frequently used, but seldom sold, for it is preferable to [>reparc it
on the spot. The tincture experience has shown to be far inferior in
power to the extract, and it is not much used. Ergotin k a purified
extract of uncertain strength j it m used for hypodermic injection i it
should be about five times more active than the liquid extract.
§531. Dose. — The main diificiilties in the statement of the medicinal
dose, and of the minimum quantity which will destroy life, are the
extreme variability of diflferent samples of ergot, and its readiness to
decompose. A fnll medicinal doso of ergot itself, as given to a woman
in labour, is 4 grmg^ (6 17 grains), repeated every half-hour. In this
I
J
§ 582. 5830
way enormous doses may be given iu some oaaes without lauch effect.
On the other hand, aiugle doses of from 1 to 4 grros. hare caused fieri ous
poisonoua ajmptoms. The extract and the tincture are seldom given in
larger doiea than that of a drachm as a fii^t dose, to eicite uterine cod-
traction. In fact, the medical practitioner has in many cases to experi-
ment on his patient with the drug, in order to discover, not only the
hadividaal stisceptibility, but the activity of the particular preparation
used. From the experiments of Nikitin, it is probahle that the least
fatal dose of sclerotic acid for an adult man is 20 iiigrms. per kilogrm.
g 582. Ergotism, — ^Ergotised oe reals have played a great part in
various epidemics^ probably from very early times, but the only accurate
records respecting them date from the sixteenth century* According to
DrTiasotp* the tirst recorded epidemic was in 1596, when a strange,
spasmodic, convulsive disease broke out in Hessia aud the neighbouring
regions. It was probably due to spurred rye. Tn VoigtlHudor, the same
disease appeared in 1648, 1649. and 1675 ; in 1T(*2 the whole of Freiberg
was attacked In Germany and in Fmnce suocesaive epidemicB are
described throughout the eighteenth century. In France, iu 1710, Ch,
Noel, physician at the Hold Dieu, had no le^s than fifty cases under
treatment at the same time.
It is generally said that in 1630, Thuillier, in describing an ergat
epidemic which bruke out in Colog-ne, first referred the cause of tlie
disease to spurred rye.
It ismteresting to inquire into the mortality from this disease. In
1770, in an epidemic described by Taube^ iu which 600 were affected,
16 per cent died. In a nineteenth-century epidemic (1855), iu which
according to Husemaun, 30 were ill, 23*3 per cent died. In other
epidemics, according to Heusinger, out of 102, 12 per cent, died *
according to Griepenkerl, out of 155, 25, or IG per cent, died ; and
according to Meyer, of 283 casea^ 6 per cent. died.
There arc two forms of chronic poiaouiug by ergot — one a spasmodic
form» the other tlie gangrenous form.
§ 5B3. The convulsive form of ergotism mostly begins with some
cerebral disturbance. There are sparks before the eyes, giddiness, noises
in the ear«, and a creeping feeling about the body. There is also very
commonly atifesthesia of the fingers and toes, and later of the eitremities.
of the back, and even ol the tongue. Diarrhcea^ vomiting, colic and
other signs of intestinal irritation seldom fail to be present ; there are
also tetauic spasms of the muscles, rising in some ciisea to well-marked
tetanus ; epilepsy, faiutings, aberrations of vision, amaurosis, and ainbly*
opia ivre frequent ; the akin becomes of a yellow or earthy colour, and is
• Dr. Tissot in PhiL Trans., vol h\ p. lOe, 17GT>. This ia a Utiti letter hy Dr.
Bak«r, liud givea n good hlatory of the vaiious ejtid«auea ^^1 ergotiHtu,
4^2
poisons: THKIE EFFECTS AND DETECTION.
L§ 584.
covered with a cold sweat ; boila and other eruptiona luay break out ;
blebs^ like those caused bj burns or scalds^ have in a few caaes been
noticed. Death raaj oi^cur hi from four to twelve we eke after the eating
of the spurred grain from exhaustion. In those individuals who recover,
there remain for some time weakness, cotitractions of groups of muscles,
anfpmia, or affections of vision*
§ 5B4. fhe Gangrenous Form of Ergotism, —In this form there is
general 1 J acute pa tn in the limb or limbs which are about to mortify ; and
tiiere may be prodromata, similar to those already described. The limb
swells, is covered with an erymp^elatous blush^ but at the same time feels
icy cold ; the gangrene is generally dry, occasionally moist ; the mummi-
fied parts separate from the healthy by a moist, ulcerative process;
and in this w^ay the toes, fingers, legs, and even the nose, may be lost.
During the process of separation there is some feverj and pypBmia may
occur with a fatal result.
Foutenelle described a ease in which a rustic lost all the toes of one
foot, then those of the others after that the remnant of the first foot,
and lastly the leg. But probably the most extraordinary case of gim^rene
oauaed by the use of ergot is that which occurred at Wattisham, SuSblk,
in the family of a labouring man named John Downing. He had a wife
and six children of various ages, fronj 15 years to 4 montlus* On
Monday, January 10, 1762, the eldest girl complained of a pain in the
calf of her left log; in the evening her sister, aged 10, also experienced
the same symptoms. On the following Monday, the mother and another
child, and on Tnesdny, all tho rest of the family except the father, Irecame
affected. The pain was very violent* The baby at the breast lived a few
weeks, and died of mortification of the extremities. The limbs of the
family now began to slough off, and the following are the notes on their
condition made by an observer. Dr. C. Wollaston, F.RsS., on April
13 I—
''The mother, aged 40. Right foot off at the ankle, the left leg
mortified ; a mere bone left, but not off.
** Elimbetli, aged 1 3. Both legs off below the knees.
" Sarah, aged 10. One foot off at the ankle,
"Bobert, aged 8. Both legs off below the knees.
*' Richard, aged 4, Both feet off at the ankle.
" Infant, 4 months old, dead;'*
The father was also attacked a fortnight after the rest of the family,
and in a slighter degree^ the pain being confined to the fingers of his
right hand, which turned a blackish colour, and were withered for some
time, but ultimately got better*
As a remarkable fact, it is specially noted that the family were in
ther respects well. They ate heartily, and slept soundly when the pain
8 S85. S86l]
EBGOT OP BTE.
463
begao to abate* The mother looked emaciated, "The poor boy in
particular looked ae healthy and florid as possible, and was sitting on
the bed quite jollji drumming with his stumps/* They lived as the
country people at the tirae usuallj lived, on dried peas, pickled pork,
bread and cheesej railkj and small beer. Dr. Wollastou strictly ex-
amirjed the com with which they made the bread, and he found it
**very bad ; it was wheat that had been cut in a rainy season, and had
lain iu the ground till many of the grains were black and totally
decayed/^ *
§ 5S5. Symptoms of Acute Poisoning by Ergot. — In a fatal case
of poisoning by ergot of rye, recorded by Dr Da v id son, t in which a
hospital nurse, aged 28, took ergot, the symptoms were mainly vomiting
of blood, the paNsiug of bloody urine, intense jaundice, aud atupor. But
in other cases, jaundice and vomiting of bloai have not been recorded,
and the general course of acute poisoning shows, on the one hand, symp-
toms of intense gastro-inteatiual irritation^ as vomiting, colicky pains
and diarrhoea; and, on the other, of a secondary affection of the nervous
system, weakness of the limbs, aberrations of vision, delirium, retention
ol urine, coma, and denth,
g 5S6. Fhysiological Action as shown by Experiments on Animals.
— In spite of numerous experinrienta on animals and man, the action of
the ergot principles remains obscure. It has l>een found in medicine to
exert a specific action on the uterus,]: causing powerful contractions of
that organ, especially in labour. It is also a li^mostatic, and is used to
check bleeding from the lungs and other internal organs of the body.
This hemostatic action, as well as the eittraordinary property possessed
by ergot, of producing an arrest or disturbance of the circulation
inducing gangrene, has naturally led to the belief that ei^t causes
a narrowing in the calibre of the small arteries, but this has not
received the necessary experimental sanction. HolmesJ Eberty,
* In the PhU, TVans. for 1732 there am two atrictly cenoordaut accounts ot this
case; »nd in th« {uimU church of WAttiah&m, tliere ia said to he a nif^morial
tablet^ which runa iw follows : — '^ This inscription serves to authenticate tha tnitlj
of a singular calumity which ftufld^nlj ha[>j>einxl to a poor family in thb jiartBli,
of which iix {}eDion^ lost their fi^^t by a mottiltcation not to be sccoimted fofi A
full narratlre of their case is recorded in the Parish Register and Philim/fthital
Tranjiaeti&ns for 1762."
t Laiuxt, Sept 30, 18S3.
t In a ca^ in which the senior author was engaged* a dabhle? in druga, liaving
sfiductid a young woman, adin in in tercel to h(?r a doie of eigut which prisduced a
miscarriage, and for this offence he wa» convicted. The defence raised was* that ergot
i^ a conimoT) medieine uaed by physic iann in the treatment of anienorrhcea, and
other utoriiie aHectiong. Althongk in itself ttii» statement was perfectly true^ aa &
^feni:^ it waa invalidated by the large doae given, the fact of the aeductiou, and the
rlher eircumatancefi of the case,
§ Arohiv €L FkifmL JWrm. »* PrUMLj lii p* 3S4.
464
POISONS: THBIR EFFECTS AND DKTBCTION.
[§ 586.
Kohler,* and Wemick t all obfter^ed a contraction in the part to which
the ergot was applied, both in frogs and in warm-blooded animals;
but L. Hermann,! although he made many experiments, and used
various prepamfcions, never succeeded in observing a contraction, tt
would also seem reasonable to expect that with a narrowing of the
vessels, which means a peripheral obsstruetion, the blood -pressure would
rise, but on ihe contrjirj the preasure siuka, a fact on which there is no
division of opinion.
Nikitin has made some researches with pure sclerotic acid^ which
certainly ^loasesses the most provninent therapeutic effects of ergot ; but
Bince it is not the only toxi€ substance, it may not represent the
collective action of the drug, just in the same way that morphine is not
equivalent in action to opium. Cold blooded animals are very sensitive
to sclerotic acid ; of the warm-blooded the carnivora are more sensitive
than the herbivora. The toxic action is specially directed to the
central nervous system — with frogs, the reflex excitability is diminished
to full paralysis ; with WEirm-blooded animals reflex excitability is only
diminished, and continues to exist even to death.
The temperature falls, the breathing is slowed, and the respiration
stops before the heart ceases tn beat ; the peristaltic action of the intes-
tines is quickened, and the uterus (even of non-pregnant animals) is
thrown into contraction. The termiuations of the sensory nerv^ are
paralysed by the direct action of sclerotic acid, but they remain intact
with general poisoning. The heart of frogs is slowed by sclerotic acid.
Kberty observed that this slowing of the heart (he used ergotin) was
produced even after destruction of the spinal cord ; he therefore con-
sidered it as acting on the inhibitory nerve apparatus of the heart itself.
Eossbtich, using Wenzeln's ocbollDf has also studied its action on the
heart of the frog, and observed that the slowing affected the ventricles
rather than the auricles, so that for one ventricle^ystole there were two
contractions of the auricles ; besides which, the contractions themselves
were peculiar and abnormal in character. The cause of death from
Bcl erotic acid seems to be paralysis of the respiration. It is said not to
affect animal fmtal life. With regard to the effects produced by feeding
animals with ergotised grain, experiments made during the last century
have proved that it producer a gangrene uh disease — e.g.^ 0. Salerne mixed
one part of spurred rye with two of good barley^ and fed pigs with the
mixture ; a few days afterwards the pigs pfiHshed with dilated, hard,
and black bellies, and otteusively ulcerated logs ; another pig, fed entirely
on the rye, lost its four feet and both ears.
* Ut'ber die IFirkungm dex Ssetde ComuiMm, DiD^rL Halle, 1871
t Ardi./. paihuL AtitU.^ Ivi p. 505.
t lekrbmh der tjeper. ToximlogU, Berlin, 1874, p. S86,
§ 587. sm
nCROTOXlN.
465
Kobert* has investigated the effocta produced on auiraals by **spUa-
ceUc acid,*' and by " comutin/' Sphacelic add appears to cause gangrene-
like ergot, and Kobert belieyes that in ^^ sphacelic acid *' is to be fouiid
the gangrene- prod iici tig substance- In cases of death putrefaction is
rapid, the mucous membrane of the intestine is swollen, and the bpleen
enlarged* If the mucous membrane of the intestine is examined micro-
seopieally, a large quantity of micro-organisms are fotmd in the vessels^
in the villi, between the muscular bundles, and in the deeper layers of
the intestinal walls ; this is evidence that the protective epithelial cells
have been destroyed. The mesentery of cats, pigs, and fowls contains
numerous Rmall extravasations of blood. The organs generally, and
espeeiiiUy the subcutaneous cellular tissue, are tinged with the colouring
matters of the bile ; this Kobert considers a& evidence of weakened vitality
of the red blood corpuscles. The walls of the blood-vessels show hyaline
degeneratloiij and give with iodine a quasi-amyloid reaction. The vessels
are often partly filled with a hyaline mass, in which, at a later date, a fine
black pigineut appears^ These pigmented hyaline masses probably
fxjclude the i^essels, and hence cause gangrene.
Cornutin, accnnling to Kobert, first excites the vagus ; consequently
there is alow puke and heightened blood -press are ; then it paralyses the
vaao-iiiott:kr centre, and the pulse is accelerated. Severe convulsions,
preceded by formicatlonj follow. Paralysis of the extensor miiecles, with
permanent deformity, may result, Connitin stimulates the uterus to
contraction, but it does not act so well in this respect alone as when
given with sphacelrc acid. In animala poisoned with connitiii, no special
piathoKigical cbatiges of a distinctive nature have been described,
!^ 587. Separation of the Active Principles of Ergot from Axmnal
Tissuefl. — There iias lieen no experience in the tie partition of the constitu-
ents of ergot from the organs of the body ; an attempt might be made
on the principles detsiiled on page 25 i, but success is doubtful.
H I 588, The berries of the Menwpermum cacculus! comprise at least
H til ree defi n i te cry sta 1 1 i n e p ri n c i [ * lea : mefiiaperm m^, t pa ni m ermpermine
H ttmt\
m exti
I exti
I Ut«
Il.-Picrotoxin, the Active Principle of the Cocculus
indicus (Indian Berry, Levant Nut),
* Lehrhif^:h tkr Intoricittimitm, by Dr. Rudfiljih Kobert, StuttgArt, 1S93»
t Sfenisjfrrtiiijt^' {Cif^H.^^ ^0^1), iiiimtveiiid in 1S34 by Pelletkr iiikJ CouHms, U
B«aociifct«d whli a j*ec(»iid iiamecl panTnicni^prrmiNe, The i^iowdered beniea are
extmct^sd by akoKol of UG" ; the pit^mtoxiii ns moved by hot watisr tVisiu the alcoholic
extinct ; the mouis|t«ninnv uiid jiaran»einsj>enTiiije dissotved tint togcthei- by acidu-
Ut^ water, %nci from this solution ]n^|nUte<i by atiimr}ni&. The browii precipitoto
so
466
POISONS: THKIR EFFECTS AND DETECTION.
[§ 589.
{nitrogen containing b^iaes)^ and picrotoxiUi which possesses some of the
characters of an acid,
§ 589. Picrotoxin was discovered in 1820 by Boullay, It is usually
prepared by ejttracting the berries with boiling alcohol, distilling the
alcohol off, boiling the alcoholic residue with a large quantity of water,
purifying the watery extract with sugar of lead, concentrating the
colourless filtrate by evaporation^ and crystalHsing the picrotoxin out of
water. Picrotoxin, so prepared, is probably a mixture of two bodies —
picrotoiinin, Oj^Hj^O^^, and picrotin, Cj^H^gOp although some authors
consider it to be a definite compound of these two bodies.
The mixture crystallises out of water, and also out of alcohol, in
colourless, flexible, four sided prisms, often arborescent, and possessing a
silky lustre. They are unalterable in the air, soluble in 150 parte of
coldj and 25 parts of boiling water, dissolving easily in acidified water, in
spirit^ in ether, in amyl alcohol, and chloroform. They are without smellj
but have an extremely bitter taste. Caustic ammonia is also a solvent.
The crystals are neutral in reaction. They melt at 199*'-20t)° C. to
a yellow mass ; at higher temperatures giving off an acid vapour, with
a carameMike odour, and lastly carbonising. Picrotoxin rn cold concen-
trated sulphuric acid dissolves with the production of a beautiful gold-
yellow to saffron-yellow colourj which becomes, on the addition of a trace
of potassic bichromate, violet passing into browu. An alcoholic solution
turns a ray of polarised light to the left Wn = -28'l^
Concentrated aqueous solutions of alkalies and ammonia decompose
picrotoxin fully on warming. It reduces alkaline copper solution, and
colours bichromate of potash a beautiful green. The best test for its
presence is, however, as follows :- — The supposed picrotoxin is carefully
dried, and mixed with thrice its bulk of saltpetre, the mixture moistened
with sulphuric acid, and then decomposed with soda-lye in exeess, when
there is produced a transitory brick-red colour. For the reaction to
succeed, the picrotoxin should be tolerably pure.
is dissolved bj acetic wM^ filtered, and again precipitate by ammonia. This
precipitate is dried, treated with cold alcohal to separate a jelli^w resinous tub*
stance^ Bad lastly with ether, which dissolves out the? mein5|)«niiiue, but leaves the
paramenii^p^nuiiic,
Menisperniine forms white s^mi -transparent, four-sided^ truncate prisms, melt-
ing at 120°, decomposed at a bigher UnifHsmture, insoluble in water, but diaijolvmg
in warm alcohol and ether. Combined with 8 atoms of water it crj'staJljBea iu needle*
and jirism^ The crystals are without any taste ; in combination with acids^ salts
may he formed.
Paramenhpcrmini forms four>sided prisms, or radiating crystalline maaadB,
melting at 26D% and ffuhliming undecom posed. The crystals are soluble in absolute
ether, inaolable in water, and scarcely soluble in ether,
Paramenisfiermim dissolves in acids, but apft^rently without forming definite
§ S90, 59J ]
PTCROTOXIN.
467
Solutions of picrotoxin are not precipitated by the chlorides of
platinum, mercury, and gold, iodide of potaasium, ferro- and ferri-cyanides
of potassium, nor by picric nor tanuLo acids,
Picrofcoxinin (Ci^Hj^Og) is beat obtained by brominating picrotoxin
in hot solution with a alight excess of bromine water, and removing the
excess of bromine from the crystalline raonobroraopicrotoxinin, which is
separated by means of zinc dust and acetic acid. It crystallises from
hot water in colourless anhydrous crystab, and from cold water
In rhombic plates. It melts at 200*-201"; with H^^SO^ it gives an
intense orange- red colour. Bromopicrotoxinin (Ci^,Hj,^BrO^) meltn at
259''-2G0'.
Plcrotiii (C^^^H^gO*.) separates out on cooling the filtrate from the
bromopicrotoxinin ; it may be purified by washing with small quantities
of hot chloroform and recrystalliaing from water. It forms small
needles or rhombic prisms melting at 248*-250'' ; it is soluble in almoin te
alcohol or acetic acid, and only slightly in ether, chloroform, and benzene.
It reduces Febling*s solution and has (a)i, = -64^70"*; it forms a numl>er
of derivatives, such as benzoylpicrotin (C^pH|^Oh^Bk), crystallising from
absolute alcohol in colourless crystak-^m.p. 236' ; acetyl pier ot in
(Cip,H^«0^ Ac), m,p* 244°— 245° ; anliyd rod i acetyl picrot in (C^^Hj^OflACj) ;
and diacetylpicrotin (CisH^^^O^Ac^), an oil.*
g 590. Fatal Dose. — Vossler killed a cat in two hours with a dose of
*i2 grm. (rS grain); and another cat, with the same dose, died in 45
minutes. Falck destroyed a young hound with OG grm. ('92 grain)
in 24 to 26 minutes. Given by »ubcutaueoos or intravenous injection,
it is, as miglit be expectetl, still more lethal and rapid in its effects. In
an experiment of Falck's, *03 grm* (*46 grain), injected into a vein,
destroyed a strong hound within 20 minutes; 016 grm. ('24 grain),
injected nnder the skin, killed a guinea-pig in 22 minutes; and *012
grra, ("18 grain) a hare in 40 minutes. Hence it may be inferred that
from 2 to 3 grains (12"9 to 19"4 centigrmsj would, in all probiibility, he
a dangerous dose for an adult person,
^ 59 L Effects on AnimalR. — The toxic action of picrotoxtn on Gah
and frogs has been proposed as a test* The symptoms oiiserved in fish
are mainly as follows :— -The fish^ according to the dose, show uncertain
motions of the body, lose their balance, and finally float to the surface,
lying on one atde^ with frequent opening of the mouth and gilhcovers.
These symptoms are, however, in no way rlistinguishable from those
induced by any poisonovis subst^ince in the water, or by many diseases
to which fish are liable. Nevertheless, it may be conceded that in
certain cases the test may be valuable — if, «?f/,, beer be the matter
of research, none of the methods used for the eitraotion of picrotoxin
' K, J» Meyer ftud P. BcDger, Ber., kesu., 18&8.
468
POIBONS: THEIR KFFKCT8 AND DET&CTIOK, [§ 592-594-
will be likely to extract any other substance bavin g the poisonous action
described on £sh, so tbat^ as a confirinatory test, this may be of use.
Frogs, under the influence of picro toxin, become first uneasy and
restlesa^ and then somewhat somnolent; but after a short time tetanic
oooTaktons set iu, whicb migljt lead the inexperienced to imagine that
the animal was poisoned by stiychnine. There is, however, one marked
distinction between the two — viss., that in picrotoxin poisoning an
extraordinary swelling of the abdomen has been observed, a sympfcom
whichj so far as known, is due to picrotoxin alone. The frog is^ therefore,
in this instance, the most suitable object for physiological testa.
Beer extract oontainiag picrotoxin is fatal to flies ; but no definite
conclusion can be drawn from this, since many bitter prineiplea (notably
quassia) are in a similar manner fatal to insect life.
§ 592, EfiFects on Man, — Only two fatal cases of poisoning by picro-
toxin are on record. In 18 '2 9 several men su fie red from drinking rum
whicb had been impregnated with Cocculit^ indicus; one died, the rest
recovered. In the second case, a boy, aged 12, swallowed some of a
composition w^hich was used for poisoning fish, the active principle of
which was (hccuhnf mdicus: ; in a few minutes the boy experienced a
burtjing taste, be had pains in the gullet and Btomach, with frequent
vomiting, and diarrham* A violent attack of gastro-ententis supervened,
with fever and delirium ; he died on the nineteenth day. The poat-mortem
signs were those usual in peritonitis ; the stomach was discoloured
and its coats thinner and softer than was natnral ; there were also other
changes, but it is obvious that, as the death took place so long after the
event^ any pathological .signs found are scarcely a guide for future cases,
^ 593, Physiological Action. — The convulsions are considered to arise
from an excitation of the medulla oblongata ; the vagus centre is stimu-
lated, mid causes Bpasm of the glottis and slowing of the heirt's action
during the attack, liohrig also saw strong contraction of the uterus
produced by pirroiimn. According to the researches of Crichton Browne,
chhi'al hjilniie acts in antagonism to picrotoxin, and prevents the con-
vulsiotis in animals if the dose of picrotoitin is not too large.
§594. Separation from Organic Matters. — Picrotoxin is extracted
from aqueous acid solutions by either chloroform, amyl alcohol, or etlier ;
the first is the most convenient. Beuzene does not extract it, if employed
in the same manner. On evaporation of the solvent the crude ptcrotoiin
can be crystallised out of water, and its properties examined.
U. PaUu^ has taken advantage of the fact that picrotoxin forms a
stable compound with freshly precipitated lead hydroxide, by applying
this property as follows: — The solution supposed to contain picrotoxin is
eva].K>rated to dryness, and the extract tlien taken up in a very little
* J. liiurtfu (6), xvii. 19-20.
S S94A ]
TUTIN — 4:.0BTAMYBTIK,
469
water, acidified and ahakcu out i^ith ether. The other m evaporated,
tho ethereal extract dissolved iti a little water, the aqneoua stoiuUoii
filtered through auimal charcoal, and precipitated by nieana of lead
acetate, avoid in*:,^ excess. The solution m filtered, and shaken with freshly
prepared lead hydroxide. The lead hydroxide ii* dried and teisted direct
for picrotoiin ; if it does contain picrotoxin, then, on adding to it eon^
centrated H^SO^, a beantiful aafFron-yellow is produced as bright as if tho
»ul;^tance waa pure picrotoxin.
IIL— Tutin— Coriarayrtln.
g 594a, Theru are three apcciea of Goriaria in New Zealand — C. Sar-
ntejUomy 0. arborea^ and G. Tidu ; the latter is commonly known aa the
tree toot. From the New Zealand plants Easter field and Aston* have
separated a crystalline non-nitrogenous glncoside, tutin, very nearly
allied to a glucoside previously separated from the European species by
Eribau, and named by him coriamyrtin.
The chemical differences between these two principles are as
follows : —
Tutln
Ckfiio-myrtin
C„H^Ot
CibH|^Oji
Solubility in 100 parts of
water * ♦ . .
1-8 at 10'
1-44 at 23"
Solubility in 100 parta of
ttlcoliol . , . .
8-2 iit lU'
3*00 at 22'
Eex&ciiori with HI follu^ved
with I»0t44s)l ,
Nil
Mi4^i!^DU coluur
Uouuentrtttijd HySOi »
Blood- red oobur
Dirty yellow
Sublimiug point
About 120'
About ISO"
The Tutu plants are highly toxic to animali who have not become
immune by eating small (|uantities; for the native cattle in the Tntu
distriets apparently consume moderate amounts of the shrnba with
im|mnity, whereas other cattle become Kenously ill. Botli ooriamyrtin
and tutin belong pharmacologically to the picro toxin group of animtances.
Tutin ia somewhat leda toxic than coriamyrtin. There is first dopreision,
followed by aalivation ; the pulse is slowed, the respirations increased in
frequency, and, finally, clonic convulsions occur: 129 mgi-ms* killed a
kitten weighing 1 kilogramme in iO minutes ; 1 mgrna. induced in a cat,
2 kilogrras. in weight, a convuklve seisGure, and the animal did not
recover for 24 hours.
The method of extracting tutin is, briefly, as fallows : — The plant,
finely divided, is boiled with water^ this aqueous extract precipitated by
alcohol, the filtrate freed from alcohol, and the tutin ertraoted by ether.
* Kii9t«itield*uii Astoa, Jeum. L'fbtfa^ Soc^^ lyaia^^ 190L
470
POISONS ; THEIH EFFECTS AND DETICTION. [§ SPS-JQ?.
IV.— The poison of Illioium Eelig-iosum— A Japanese Planti
§ &&5. A new polsou beloDging to th& picrotoxiu cl&sa }m& heeu described bj Dr.
A, LaDgaftrd. In 1880, 5 childrBn in Jajwati wer« poisoned by the aeeda of the
lUicium rdigioKum : 3 of tha cliildreti died. Dr, Laugoard then iiiade varbus ex*
pcrimeuts on animals with an active itx tract prepared by cxhaustioo with spirit, and
ultimate solution of the extract in water. Eykmann hits sdso imperfectly t:xamined
the chemistry of the plant, and haB succeeded in isolating a crystal line body which
ii not a glucoside ■ it is soluble in hot wat4ir, in chlorofoiTn, tthcr, alcohol, and
acetic a<^^d, but it is insoluble in petrolenm ether; it melts at 175^, &nd above that
tenijieratnre gives an oily subliniato. Lflugaard'a conclusions ai-e that all i>arts of
the plant are poisonous* The poison produceB excitatiou of the Of^ntml ap|>aratiis of
the medulla oblongata and cloDic convulsions analogous to those pi-oduced by picro*
toxin, toziresln, and cicutoxin. Before tlie occurrence of oonvubioD^i, tbe rcllex ex-
uitability of frogs is dinutnshed, the respiratory centre is stimulated, hence frequency
of the respimtion, Smiill doses cause slowing uf the {ml»c through sttmnlattoti of tlie
iraguB and of the [peripheral terminations of the vagus; in the heart the functional
lotivity is later diminish&rL Suiall dtjfies kill by iiaralysing the iiesptratory cetitre ;
large, by heart paralysis. The proper treatment seems to he by chloral hydrate, for
when animals are i>oiBoned by small lethal dose8 it appe-arsi to save life, althotlgh
when the dose is large it has no etlect. — Ucb^r dm Oi/twirkiiiig v(m Japanischdm
Sternanis {lilwiwii rcUtjimumt Sieb,), FircK ArMi}^ Eld. Ixxxvi, 1881^ S, 222.
V, Picric Acid and Picrates,
.OH
g 596. Picric Acid, Cj^HgNgO^, or ^q^^ >« trioitropbetiol ; it
forms a number of 8alts, all of which are more or le&a i^oisoniius. Picric
acid is much uaed in the arts, eapecially as a dye. The pure Btibetancc
m in the forra of pale yellow crystalB^ not ^ery soluble in cold waterj
but reailily aoluble in hot water^ and readily solublt^ in bensieue, ether,
and petroleum ether. The eolution is yellow, taster bitter, and dyes
animal Hbres, auoh as wool ; but it can be washed out of plant tibrea
auch as cotton,
§ 507, Effects of Picric Acid. — Picric acid and ite salta huve a ten-
deacy to decompoBe the elements of the blood, and to produce ujethaB-
moglobin ; picric add is also an exciter of the nervous system, producing
tjonvultions. To these two effects rnust be added a tbinl ; !» acid solu-
tion it has a strong afhuity for albumin, so that if it meets with an acid
tissue it combines with the tissue, and in this way local necroses are set
up* The action on albumin is somewhat weakened by the reduction in
the body of part of the picric acid to picraminic acid, CJi2(K02X^K It^^^H,
a substance that does not so readily form compounds with albuminous
matters. Doses of 0*5 to 0 9 grm. (about 8 to 1 4 grains) may be taken
§ 598. 599']
PICRIC ACID CICUTUXIN,
471
several days in yaccession wltljout marked symptoma. Ultimately^ how-
ever, what is known aa "picric jaundice " appears, the conjunctiva and
tte whole skin being atftioed more or less yellow, Tbe urine, at first of a
dark yellow, m later of a red-brown colour. Dyapepsia, with flatulence atsd
an inchnalton to diarrhcea, have been noticed. A single dose of a gramme
(1 5' 4 giuins) caused in a case described by Adler^ pain in the stomach,
headache, weakness, diarrhcea, Yomiting of yellow matters, qmckenirig
and afterwards slowing of tbe pulse ; the skin was of a brown-yellow
colour, and there were nervous symptoms. The urine was ruby-red* In
both fffices and urine picric acid could be recognised. The excretion of
picric acid continued for six days. A niicroseopical examination of the
blood showed a diminution of the red blood corptiBcles, an iuerease in
the white. Charon t has described a case in which the application of
0'45 grm. {6*9 grains) to the vagina produced yellowness of the skin in
an hour, imd the urine was also coloiireii red, Erythema, somnolence,
burning and smarting in the stomach and in the kidneys were also
noticed,
§ 598. Tests* — Picric acid is easily separated from either tissues or
other orgauic matters. These are acidiHed with sulphuric acid and then
treated with 95 per cent* alcohol ; the alcohol is filtered otf, distiUed^
and the residue treated with ether ; this bist ethereal extract will con-
tain any picric acid that may be present.
If the ether extract contains much impurity, it may be necessary to
drive off the ether, and to take up the residue with a little warm water,
then to cooli hlter through a moistened filtcr*paper, and test tbe aqueous
solution. Picric acid, warmed with KCN and K HO, gives a blood-red
colour^ from the production of iso-purpurate of potash. Ammouiacal
copper sulphate forms with picric acid yellow*green crystals which
strongly refract the light. If a solution of picric acid be reduced by the
addition of a hydrochloric acid solution of stannous chloride^ the suV
sequent addition of ferric chloride produces a blue colour, due to the
formation of amidoimidophenol hydrochloride^ C^H,jOH(NH^)(NM}^HCl.
VL— Cicutoxin.
§ 599, The Oieuta virosOj a not very common umbelliferous plant
growing in moist places^ is extremely poisooons. It is from 3 to 4 feet
in height, with white flowers ; tbe umbels are large, the leaves are tri-
partite, the leaflets linear lanceolate acute, serrate decurrent; the calyx
has five leaf-like teeth, the petals are obcoi^ate with an inflex point;
the carpels have five equal broad fattened ridges with solitary strips,
* H^kmrni^. troek, ISSO, 81S. f J* Cli4ron, Joum. d& Th^., Um, 121.
472
P0IB0N8 ; THKIU EFF'BCTS AND DETECTIOK. [| 6oO, 6oi,
Bohtn* Buccetfded, in 1876, in st?par4ituig an a<:tive priuciple from this
plant. The ruot was dried, powdered, and exhaustod with t:ther; on
evaporation of the ethor the extract wag taken np with alcohol^ and after
several days' standing the filtrate was treated with petroleum etlier ; after
removing the petroleum, the solnliou was evaporated to drjnesa in a
vacuum ; it waa found to ho a resiiioiis miisH, to which was given the
name cicutoxifL It waa fully soluble in iiloobol^ ether, or chloroform,
and waa very poisonous, hut what its exact chemicai nature may be is
still uukncvwn.
^600. Effects on AninialB. — SubcutanoouBly injected into froga,
cicutoxin acts something like picrotoxin, and H^jmething like the liariura
compounds. Ten to lifteeu minutes after the injection the animal
assumes a peculiar posture, holding the legs so tbsit the thigh is stretched
out far from the trunk, and tho leg at right angles^ with the thigh ; volun-
tary motion is only induced by the strongest stimuli, and when the
frog springs, he falls down plump with stiffly stretched-out limbfe. The
frequency of breathing is increased, the museles of the abdomen are
thrown hi to contraction^ and, the lungs being full of air, on medianical
irritation there ia a peculiar loud cry, depending upon the air being
forced under the conditions detailed through the narrow glottis.
Tetanic convulsions follow, gradually paresis of the extremities appeal's,
and, lastly, full paralysis and death ; these symptoms are seen after
doflea of from 1 to 2 mgrms. The lethal dose for cals is about 1
centigrm. per kilo. Diarrluea, salivation, and frequent breathing ure
(irst seen, and arc followed by tonic and clonic convulsions ; then there
is an interval, during which there is heightened excitability of rellex
aetiotij so that noises will excite convulsions. Small dtises by exciting
the vagus slow the pulse; larger doses quicken the pnise, and raise the
arterial pressure, Cicutoxin is supposed to net ajieeially on the medulla
oblongata, while the spinal cord and the brain are only secondarily
atTected*
§ GOL Effects on Man.— F. A. Falck was able to collect thirty- one
cases of poisoning by cicuta; of these 14 or 45'2 per cent* died. The
symptoms are not dissimilar to those described in animals. There are
pain and burning in the stomach, nausea, vomiting, headache^ and then
tetanic convulsions. These, iu some cases, are very severe, and resemble
those induced by strychnine; hut in a few cases there ig early coma
without convulsions. There is also difficulty or absolute impossibility
of swallowing. In fatal oases the respiration becomes stertorous, the
pulse small, the pupils dilated^ and the face cyanotic, and death occurs
within some four hours, and iu a few cases later. The fatal dose is
unknown.
* Atrh./. e^p. Patli,, lid. v.. ISrt?.
§ 602--604]
fENANTHK CROCATA,
473
§ 602. Separation of Cicutoxin from the Body.^An attempt might
be niadc to estnict eicii toxin from th*i tissues on the Bama pnticipl^s aa
tho&o by which it hus beeu separated fr-om tho pkiit^ and iilcntified by
phydulogii^'il experiments. Id all recorded e^iaea, ideutificatiou has been
iioither by chemical nor physiological aids^ but by the recognition of
portions of the plant.
VIL— ^thusa Cynapium (Fool's Parsley).
§ 603. This plant has long beeu considered poiaonuaB, and a n timber
of cases are on record in which it is iillege<l that death or illness resulted
from its ubc, l)r, John Harley,* howeverj iti an elaborate paper^ haa
asserteti the innocence of thiB plant, and haa analyaed the cases on
record, He haj^ ex^^erimeuted on himself, on animals, and on menj
with the expressed juice and with the tincture. The res nits were
entirely negative; eome of the pnblialied cases he refers* to coniutrij and
others to aconite. The discuBEion does not seem entirely closed, for
Dr* Davison t relates a cme of serious illness he attended in which he
identified the plant taken by the patient as that of fool'ti parsley.
VlII,— CEnanthe Crocata.
S GO 4. The Water Hemlock.*— This, a poisnnons umbelliferons
plaut| indigenous to Etigland^ and growing in moist places such as
ditclies, etc., is in flower in the month of Augnst. It resembles some-
what celery, and tlie root is something )ike the parauip, for which it
has been eaten. AH parts of the plant are said to be poisonous, biit^
the leaves and stalks only slightly so, while the root is very deadly.
We unfortunately know nothin|^ whatever about the active principJea
of the pknt ; its chemistry has yet to be worked out. M. Toulmouche
{Ow:. M&tf 184C) has rccortied, as the escpert employ Cil in the case,
an attempt to murder by using the omaniii^ as a poison ; a woman
scrafjed the root into her husband's soup with evil intent, but the taiste
was? iui|dejisant, and led to the detection of the crime. The root has
* SL Thmttfti* Hospital EtjM/rts, N.S., 1875,
t BriL Mfid JmiTii,, 1904, vol ij, 124.
t TJie earliest trifJitLse on poiaoaing by the water- hemlock i» by Wcpfer — Cictdee
Aqua/. Hiii<fHa d Noxti\ 1079. For coaes, aee Trojain^Wiiky, Darp. in^f. -%., 1875 ;
Mejer, Med, 2eU$, /, Ptcu^iscn.^ 1842 ; St'hlc&ier in C*sj»er*a IVQt^mm^hrift^ 1343 *
Maly, tEAtit, mtd, Wotftttischr., 1844 ; Btidgeley, Mmdrefd Med, Gaz., 1844 ^ Leader,
V^rklj.f, 0r, Mmi t 1865 ; Gampf, Ci^n, PAwrm, .^tf%,, 1S7& ; and the treatises ot
Tttiylt^r aud uthet^.
474
POIBONS: THKIE EFFECTS AND DETECTION, [§ 6o5i 6o6.
been mistaken several timee for parsnip and otber edible roots, and has
thua led to poisonings. The case of 36 soldiers poisoned in this way, iti
1758, hay been recorded by Orfila ; there was one death. In 1803 three
soldiers were poisoDed at Brest -^1 died. In Woolwich, Bossey witnessed
the poisoning of 21 convicts who ate the roots and leaves of the plants
6 died. In 1858 there were several sailors poisoned in a similar way—
2 died ; while there have been numerous cases in which the plant has
been partaken of by children.
g 605, The effect* of the poison may be gathered from a case of poison-
ing* which occurred in 1882 at Plymouth; a Greek sailor, aged thirty,
found on the coast what he consider^ " wild celery/' and ate part of the
root and some of the stem. Two hours after this he ate a good meal and
felt perfectly well, but fifteen minutes later he suddenly and violently
vomited ; the whole contents of the stomach were completely evacuated.
In five minutes he was completely unconscious, and had muscular twitch-
tngs about the limbs and face. There was a copious flow of a thick
tenacious mucus from the mouth which hung about the lips and clothing
in viscid strings. Twenty-four hours after the poisoning he was admitted
into the South Devon Hospital apparently semi-comatose; his legs dragged,
and he had only feeble control of them; the extremitieB were cold, but
there was general free sweating. He could be roused only with difficulty.
There were no spasms, the pupils were dilated and sluggish, the respira-
tion only 14 per minute. Twelve hours after admission he became warmer,
and perspired freely ; he slept continuously, but could easily be roused.
On the following day he was quite conscious, and made a good recovery.
Two companions who had also eaten a smaller quantity of the hemlock
drop wort, escaped with some numbing sensationSj and imperfect control
over the eitremltieB. In the Woolwich cases the symptoms seem to
have been something similar ; in about twenty minutes, one man, without
any apparent \^ arning, fell down in strong convulsions, which soon ceased,
although he looked wild ; a little while afterwards his face became bloated
and livid, his breathing stertorous and convulsive, and he died in five
minutes after the first symptoms bad eet in, A second died with similar
symptoms in a quarter of an hour ; a third died in about an hour, a fourth
in a little more than an hour ; two other cases also proved fatal, one in
nine days, the other in eleven. Tti the two last cases there were signs of
intestinal irritation. The miijority of the others fell down in a state of
insensibility with convulsions, the after-symptoms being more or less
irritation of the intestinal canal.
§ 606. Post-mortem App&arances.— It was noticed in the Woolwich
cases that thos^e who died quickly had congestion of the cerebral vessels,
and, in one instance^ there was even extravasation of bloody but the man
* iMHcelf Dec, 18, 1882.
S6o7.]
OIL OF BAVIN.
475
who died first of all had no congestion of the cerehral vessels. The
lining membrane of the wind -pipe and air- tubes was intensely injected
with blood, and the lunga were gorged with fluid blood i the blood in
the heart was black and fluid. The stomach and intestines were exter-
nally of a pink oolour^ The mucous meinbraue of the stomach was much
eorrngated^ and the follicles particularly enlarged. In the two pn>tracted
cases the stomach waa not reddened internally, but the vessels of the
brain were congested ,
IX. -Oil of Savin.
§ 607. The leaves of the Sahina commumn {JuiUim-U€ Sabmu)^ or
oommon savin, an evergreen shrub to be foutid iu many gardens, contains
a volatile oil, which has highly irritant ji roper ties. Savin leaves are
occasionally used in medicine, maxianmi dose 1 grm, (15^-1 grains).
There is also a tincture — maximum dose 3 c,c. (about 45 mins.) — and
aD ointment made by mixing eight parts of savin tops with three of
yellow wax and sixteen parts of lard, melting and digesting for tiventy
minutes, and then straining through culico. The oil, a tiucture, and an
ointment, are oflicinal pharmaceutical preparations.
The oil of savin is contained to the eitent of about 2 per cent, in the
leaves and 10 per cent, in the fruit- It has a peculiar odourj its specific
gravity is '89 to "94, and it boils at 155° to 160"*, An infusion of savin
leaves (the leaves being drunk with the liquid) is a popular and very
dangerous abortive.
It is stated by Taylor that oil of savin has no abortive eftect, save
that which is to be attributed to its general effect upon the system ; but
this is erroneous* Hohng found tliat, when administered to rabbi tSj it
had a very evident effect upon the pregnant uterus, throwing it into a
tetanic contraction. The action was evident after deetruction of the
epinal cord Tlie plant causes great irritution and inflammation, whether
apphed to the skin or taken internally. The symptoms are estcmciating
pain, vomitings and diarrhma, and the person dies in a kind of collapse*
In a case in which the senior author was engaged some ye^ra ago^ a
woman, pregnant by a married man, took an unknown quantity of
infusion of savin tops. Bbe was violently sick, suffered great pain,
with diarrhum, and died in about 26 hours. The pharynx was much
reddened, and the gullet even congested ; the stomach was inflamedj and
contained some greenish matter, in which savin tops were detected,
a few drops of a strong savin-like smelling oil were separated by distilla-
tion, The time whioh would elapse lie t ween the swallowing of the
poiaou and the commencement of the pain was an important factor in
476
poisons; THKIK KKFKCTS AND DETECTION. [§ 608-610.
this citse, for the man waa aceused of having supplied her with the
infusion. From the redness of the pharynx, and, geuerally, the rapid
irritation caused b/ ethereal oils^ a few minutes only must hare
passed between the taking of the liquid and the sensation of considcr-
uUe hyniing pain; altbough it is laid down in some works, m, for
eiample, Falck'a ToMologie^ that commonly the syni]>toaia do not
comnieijce for several houFi. Symptoms which have l>een noticed
in maii3* cases are — some cons* id e ruble irritation of the urinary organs,
such as strangury, bloody uriuCj etc, ; in a few cases vomiting of blood,
in others anfieathesia, convukions, and coma. Death rauy occur within
twelve hours, or may be |K)Btponed for two or three days,
g 608. Po&t-inortem Appearances. ^M ore or less inflnmination of
the l)owelSj stomach, and intestinal tract, with considerable congention
of the kidneys, are the sigua usually found,
S 6uy. Separation of the Poison and Identification.— Hitherto
reliance hua been plarwi entirely on the hnding of the a^ivin tops, or
on the odour of the oil. There is no reliable chemical test.
X.— Croton Oih
§ 610. Croton oil is an oil expressed from the seeds of Crofou tttylium^
a plant belonging to the natural order Euphorbiacea^ growing in the
West Indies. The seeds are oval in shape, not unlike caii^tor-oil seeds,
and about thrce'cightha of an inch in length. B^jth the seeds and the
oil are very poisonous*. The chemical composition of croton oil can
scarcely be considered adequately settled. The most recent view, how-
ever, seems to be that it contains a fixed oil (QiTIj^O,,) with certain
glyceridcs.* On safKinifying and decompoiing the soap a series of
volatile fatty acids can be distilled over, the principal of which are
methyl cro tonic acid, with small quantities of formic, acetic, iso-biityric,
valeric, and perhapa propionic, aud other acids, t The peculiar pro-
perties of croton are due rather to the fixed oil than to tlic volatile
principles. The only officinal preparation in tiio British pharmacoptaia
is a "eroton qU liniment ^^^ containing one |mrt of croton oil to seven of
eijual parts of oil of cajuput and recti Bed spirit.
* G. Schmidt, Arch, Ph^ntu [3], xiii. 213-229. Schlipijc, Liehig's Anmlm,
cv, 1, Geuthor and Frtihhcli, Z*^itifehri/i / Chifm.t 1870, 2G *tid 649 ; Jonm. Chem.
Society. Maroh 1879, p. 221.
t Benedlkt h»» fmind 0*55 per cent, of iias&poaifiAhl« matter in croton oiL
Lewkowitacli givci the lodimi value 1017 to 1047» *nd solirlifyiii^ point m 18'6*-
IJ'O". {Chejnl, Annh/!ti<^ of the Oih^ Faf,% and, JFtMC&j, by E. Bemjdikt, tmiiKlatcd
and 6 ti forged by i^* Lewkowitfich, London, 1895.)
§611-613]
CHOTON OIL.
477
jS 61L Dose. — The oilis givea medicinttlly as a powerful purgative
in do&es up to 65 mgrms. (about a gmiii). It is used externally as an
irritant or vesicant to the skin. A very dangerous dose would be from
fifteen to twenty tiniea the medicinal dose,
Effectfl. — Numerous cases of poisoniDg from large doeea of croton
oil are recorded in medical literature, but the sufferers h&ve mostly
recovered. The ayraptoms are pain, and excessive purging and
vomiting.
In the ease of a chemist^ * who took half an on nee of impure croton
oil iijBtead of cod -liver oil, the purging was very violent, and he had
more than a hundred stools in a few hours ; there was a burning pain in
the gullet and stomach, the skin was cyanosed^ the pupils dilated^ and
great faintneas and weakness were felt, yet tlie miin recovered. A child,
aged four, recovered from a teaspoouful of the oil given by mistake
directly after a full meal of bread and milk, lu five minutes there
were vomiting and violent purging, but the child was well in two days.
A death occurred iti PariSf in 1339, in four hours after taking two and
a half drachms of the oil. The fiyinptonis of the sufferer, a man, were
those just detailed, namely, burning pain in the stomach, vomitingi and
purging- Singularly enough, no marked change was noticed in the
mucous membrane of the «tomach when examined after death. An
aged woman died in three days from a teaspoouful of croton-oil embro-
cation ; ill this case there were convulsions.
In the case of Reg. v. Matwei/ miil Fe.n*att(lfi the prisoners were
charged with cfiusing the death of a nmn, by poisoning his food with
jalap and six drops of croton oil. The victim, with others who had
partaken of the food, suffered from vomiting and fuu'ging ; he lieeame
better, but wius subsequently affected with iuflamnmtian and ulceration
of the bowelfl, of which he died. In this caae it was not clear whether
tlie inflammation had anything to do with the jalap and croton oil or
not, and the prisoners were acquitted. In a crinnnal case in the United
States, a man^ addicted to drink, vva.« given, when intoxicated, 2 drachms
of croton oil in a glass of whisky. He vomited, but was not pnrge<l,
and in aljont twelve hours vias found dead. The mucous membrane of
the istomach and liimaU luteslines proved to he much inflamed, and in
some parts eroflcd, nnd croton oil was separated from the stomach.
§ 612. PoBt*mortera Appearances. — hiflamnmtiou of the atomach
and intestines are the Feigns usually foun<l in man and animals,
§ 613. Chemical AnalysiB. — The oil may be separated from the con-
tents of tlie stomach by ether. After evaporation of the ether, the
blistering or irritant properties of the oil should be essayed by placing a
droplet on the inside of the arm.
• Ji^ue de ThirajieuL, May 1881. f Qtfita, t. i. p. lOS.
47S
POISONS: THEIR EFFECTS AND DETECTION. f| 614,615,
XI.--The Toxalbumins of Castor-Oil Seeds and of Abrus.
§ 614. The Toz^bumin of Cafitor-Qll Seeds,^Tu castor-oil seeda,
besides the well-known purgatiye oil, there exists an albumjuous body
intensely poisonous, which has been carefully investigated by Stillmark,*
imder the direction of Robert. t Injected into the circulation it is more
poisonous than gtrycbninc, prussic acid^ or arsenic ; and since the pressed
seeds are without taste or smell, this poison has peculiar dangers of its
own.
It is essentially a blood poison, coagulating the blood.
The blood, if carefully freed from all fibrin, ia yet again brought to
coagulation by a sraall amount of this body»
If castor- oil seeds are eaten, a portion of the poison is destroyed by
the digestive processes ; a part is not thus destroyed, but is absorbed,
and produces in the blocd- vessels its coagulating property. Where this
takes place, ulcers naturally forna, because isolated sraall areas are
deprived of their blood supply. These areas thus becoming dead, may
be digested by the gastric or intestinal fluids, and thus, weeks after,
death may he produced. The symptoms noted are nausea^ vomiting,
colic, diarrhoea, tenesmus, thirst, hot skin, frequent pulse, sweats,
headache, jaundice, and death iti convulsions or from eihaui^tiou.
Animals may be made immune by feeding them carefully with small
dases, gradually increased.
The post-mortem appearances are ulceration in the stomach and
intestines. Tn animals the appearances of hsBmorrhagic gastro-enteritis
with diffuse nephritis, haemorrhages in the mesentery, and so forth have
l>een found.
S 615. Toxalbumin of Abrus, — A toialbumiu is found in the Ah-us
preeatori7i^ (Je(|uirity) which causes quite similar effects and symptoms.
That it ia not identical is proved by the fact that, though animals may
become immune by repeal ted doses of jequirity against "Abrin," the
similar substance from castor-oil seeds only confers immunity against
t!ie toxalbumin of those seeds, and not against abrin ; and similarly
abrin confers no iaimunity against the castor albumin. Either of these
substances applied to the conjunctiva produces coagulation in the
vessels and a secondary inflammation, to which in the case of jeqtiirity
has been given the name of " jequirity-ophthalraia.*' J
The general effect of these substances^ and, above all, the curious fact
that a person may acquire by use a certain immunity from otherwise fatal
• IL SUlltimrk, Dorp. Ark, Bd, iii-, 1889* f Kobert's Lehrhuch, 453~4&6.
X Hatnr. Hell in, B€r tfi/tige Eimtisskorpei'-^brin v, m'nf Wirkuytg ttuf das.
§616,617.]
tCTROGKN.
479
doseSj is so similar to poisonous prcwiiicts evolved in the sjstem of perBona
sufTering from infectious fevers that tbej have excited of late years much
interest, and a study of their methods of action will throw light upon
many diseased processes.
At present there are no chemical means of detecting the presence of
the toxalbumins mentioned. Should they be ever used for criminal
purposes, other evidence will have to be obtain ail.
XIL— IctPOffen,
§ 616. Ictrogen.— Various kipins, e.g. Lupinus luteui^ L. angasti'
foliim^ L, thm^inis^ L. linifoUuB^ L. kirsuim^ contain a substance of which
nothing chemically is known, save that it may be extmcted by weakly
alkaline water, and which has been named ** ictrogen " ; this must not
be confased with the alkaloid of lupins named "lupinine/' a bitter-tast-
ing substance. In large doses a nerve poison, ictrogen has the unusual
property of acting ranch like phosphorus. It causes yellow atrophy of
the liver, and produces the following symptoms ; — Intense jaundice: at
first enlargement of the liver, afterwards contraction ; somnolence, fever,
paralysis. The urine contains albumen and the constituents of the bile.
After death there ia foimd to be parenchymatous degeneration of the
heart, kidneys^ muscles, and liver. If the animal has su^ered for some
time, the liver may be cirrhotic.
Hitherto the cases of poisoning have been conBned to animals.
Many thousands of sheep and a few horses and deer have^ according to
Robert, died in Germany from eating lupin seeds. Further information
upon the active principles of lupins may be obtained by referring to the
folio winy; treatises : — G. Schneidemuhl, Die lupiumi Krankheit der
Sdta/e ; VortrUye /. Thi£rm*zte. Ser. 6, Heft. 4, Leipzig, 1883. C,
Arnold and G. Sehneidemuhl, Vi^er Beitrag zur Klarddlung der
Ursache u. des Wesens der IfUpinme^ Luneburg, 1883 ; Julius Lowenthal,
U^bm- die phf/siol u. ioxkoi, Wirkungen der Lupinenalkafoidfij Inang-
IHu,^ Konigsherg, 1868.
XIIL— Cotton Seeds.
I 617. Cotton seeds, used as an adulterant to linseed cake, etc.,
have caused the death of sheep and calves. Cotton seeds contain
a poison of which nothing is chemically known, save that it is
poisonous. It produces ansmia and cachexia in animals when given in
small repeated doses.
4So
POISONS; THEIR KFFBCT8 AND DETECTION.
[§ ^f^-
After death the ehanges are, UDder these circumstanceSj confined to
thi kidnej ; theae organs ahowirig all the sigoa of nephritis. If, how-
eyer, the aQitnal has eaten a large quatitttj of cotton seeds, then there
is gastro-enteritiSj as well aa tnfiainniation of the kidneys.
XIV,— Lathyrus Sativus.
j§ 618. Variovia species of vetchlinga, such as /a ^ativfis^ L. cirertft
L. dynumum^ are poisonous^ and have cauied an epidemic malady in
parts of Spain, Africa^ Friince, and Italy, among people who have eaten
the seeds. The symptoma are niairilj referable to the nervous system,
causing a trans vcnie myelitis and paraplegia. Id this country it is
chiefly known aa a poisonous food for horses; the last instance of hotHe-
|M>iaoning by lathy ni» was that of horses belonging to the Bristol
Tramways and Carriage Company.* The company bought some Indian
peas ; these peas xvere found afterwards to consist mainly of the seeds
of Lathy ms ^tduniSj for out of 335 peas no fewer than 325 were the
seeds of Laihyrti9. The new peas were snbstituted for the beans the
horses had been having previously on the 2nd November, and the
horaaa ate them up to the 2nd December, Soon after the new food had
been given, the horses began to stumble and fall about^ not only when
at worki hnt also in tbeir stalls ; to these symptoms sncceeded a paralysis
of the larynx ; this paralysis was in some cases accompanied by a curious
weird scream in gj which once having lieen heard coil Id never be forgotten ;
there was also giisping for breath and symptoms of impending suffoca-
tion* A few of the hursca were saved by tracheotomy. Some dietl of
suffocation \ one horae beat its brains out in its struggles for breath j
127 horaea wore affected— 12 died.
The above tniin of symptoms has also been recorded in similar casea ;
added to which paralysia of the lower eitremities is frequent. After
death atrophy of the laryngeal muscles, wasting of the iiervus recurrena,
and atrophy of the ganglion culls of the vagus nucleus as also of the
multipolar ganglion cells in the anterior horns of the spinal cord, have
been found.
The active principle of the seeda has not been satisfactorily isolated.
The symptoma suggest the action of a toxalbumin. Teillcux found a
resin acid ; Louis iVstier a volatile alkaloid^ and he explains the fact that
the seeds, after being heated, are no longer poisonous owing to the
disj^ipation of this alkaloid.
■ Hri»t«>l TrAmtt{i3'H jiiid CiuiiAge CriinjMiiiy t*. Weston k Co. » Timt^, July 17^
1S94.
§ 6ig-622,]
ABUM — MALE FERX,
481
XV.— Apum— Bryony— Loeust Tree- Male Fem.
^619* Arum maculatum. tho common cuckoo-pint, flowering in
April and May, and frequent in the hedges of this couutrjj is
extromelj poiionous. Bright red Buoculent attmctiye berries are
seen on a single Btalk, the rest of the plant hitving rotted away,
and these berries are frequently gathered by children and eaten.
The }>oi$on belongs to the elass of acrid irritants, but its real nature
remains for investigation.
Some of the species of the same natural order growing in the Tropics
are far more intensely potsoncus.
§ 620. The Black Bryony.— Tamrit communu, the black bryony, a
common plant by the wayside, flowering in May and June, possesses
poiaouons berries, which have been known to produce death, with
symptoms of gastro enteritifii In smaller doses the berries are stated to
produce paralysis of the lower extremities,*
g 621. The Locust Tree. — The Robinia paeutlo-acacia, a papilionaceous
tree, contains a poison in the leaves and in the bark^ K. Coltmann f
has recorded a case in China of a woman^ twenty-four years of age,
who, at a time of famine, driven by hunger, ate the leaves of this tree.
She became ill within forty-eight hours, with high fever ; the tongue
swelled and there was much eryaipelatous-like infiltration of the
tissues of the mouth ; later, the whole body became swollen. There
waa constipation, and so much oedema of the eyelids that the eyeballs
were no longer visible. Beooyery took place without special treat-
ment. Power and Cam bi erf have separated from the berk an
albumose, which is intensely poisonousj and is probably the cause
of the Bymptoms detailed.
g 622, Male FenL- Au ethereal extract of A^idium Filix masm
used as a remedy against tape- worm,
Poullsou^ has collected up to the year 1891 sixteen cages of
poisoning by male fern ; from which it would appear that 7 to
10 grms* (103 to 154 grains) of the extract may be fatal to a child,
and 45 grms. {rather more than 1^ oz«) to an adult The active
principle seems to be filieic acid and the ethereal oil, Filicic aeid,
under the influence of saponifying agencies, breaks up into butyric
acid and phlorogluoin.
The symptoms produced are pain, heaviueas of the limbs, faintness,
aomnolcDce, dilatation of the pupil, albumin uria, convulsions, lockjaW|
t Medical m\d Sunjitnl Rfpart^^ Ixi^j 1889.
t Ffmrm. /<mnw, 14590^ 711.
f Arch, ecp. P., Bi xxl^
482 POISONS : THEIR EFFECTS AND DETECTION. [§ 622.
and collapse. In animals there have also been noticed balivation, amau-
rosis, unsteady gait, dragging of the hind legs, dyspnoea, and paralysis
of the breathing centres. The post-mortem appearances which have
been found are as follows: — Redness and swelling with hsBmorrhagic
spots of the mucous membranes of the stomach and intestines;
acute oedema of the brain and spinal cord with petechia in the
meninges; the kidneys inflamed, the liver and spleen congested, and
the lungs oodematous.
There is no characteristic reaction for male fern; the research
most likely to be successful is to attempt to separate from an
ethereal exti*act filicio acid, and to decompose it into butyric acid
and phloroglucin ; the latter tinges red a pine splinter moistened with
hydrochloric acid.
PART VIL—POISONS DERIVED FROM LIVING OR
DEAD ANIMAL SUBSTANCES.
DIVISION L— POISONS SECRETED BY LIVING
ANIMALS.
L— Poisonous Amphibia,
g 623. The Salamander. — The glands of the akin of certain amphibia
possess a aecrelion that is poisonous ; the animal is uunbl^ to empty the
paison glands by any voluntary aetj but the secretion can readily be
obtained by pressure.
In 1899^ Faust * nmde a research on the aalamftoder, using no less
than a thousand of these small amphibia^ and separated two active bases
in the form of crystalline sulphatea.
The animals, killed i*y chlorofurm, were finely minced, and the product
extracted with water acidified by acetic acid, at a boiling temperature.
The extract was precipitated by lead acetate, the excess of lead got rid
of by sulphuric acid : the Imses precipitated by phospho-tungstic acidj and
set free by Vmryta ; the solution thus obtained had to be jnirified from a
snbstauee giving a biuret reaction. After more than one precipitation
with phospho-tungstic acid, the iiual solution is exactly neutralised with
sulphuric acid and evaporated to dryness ; the yellow residue is dissolved
in alcohol, nnd ether added until a ttirbidity results. After a few days,
if the liquid be kept at a low temperature, crystals appear ; the sub-
stance is separated, purified, and finally dissolved iu hot water, and the
solution allowed to cool slowly . In this, fine needle-like crystals were
obtained, to which Faust ascribes the formula (C,_>^Hg(,N20)g + HjSO^, and
giTea the name of samandarin sulphate. The sulphate is optically
active (a^,— - 53 69*)< A few of the crystals treated in a test-tube with
eoneentrated hydrochloric acid and lioilcd for a few minutes gives a
solution at lirst violet, and finally deep blue. The free bnse
* Die Thiiriaehtn Q^U^ Brautischwetg, 1^06,
4fia
484
poisoHS 1 f Hi;rR effects and detection, f § 624-626.
** SamandariQ " is an oil af a pale yellow colour, A second alkaloid
(Cj^Hg^N0)3+ HgSO^ was obtained by Faust, the sulphate of whicb is
lees soluble than that of eamandarin ; to this he gives the name of
SamaQdarldin sulphate. It is optically inactive^ The crystals are in
the form of rhombio plates or tables. There is more aamandaridin to
be obtained from the salamander than samandariUj the proportion being
about 2 to 1, On dry distillation with zinc dust an alkali ue distillate
is obtained, from which Faust isolated isochinoUn; the Bame author
states that the more volatile constituents of the decomposition give the
reactions of pyrrol. With regard to the chemical relationship between
the two alkaloids, Faust suggests that samandarin possesaes one more
niethyl'pyridin group, C^jH,^(CHg)Nj than samandaridin.
§ 624. Poisoning by the samandarins produce symptoms strikingly
similar to those of rabies, in all its thr^e stages — viz., the excitable stage,
With exaltation of the refleies, restleasoess, acceleration of the respira-
tion, dilatation of the pupil, and increased secretion of the nasal and
buccal secretion ; next, the convulsive stage, with catching respiration,
dyspuoja, and convulsions* and, lastly, the paralytic stage ending in
death, the cause of death usujilJy being paraly^sts of the respiratory
centre.
Like rabies also, when once the characteristic symptoms develop, no
case of recovery {in animals) is known^death sooner or later iiupervenes.
The fatal dose is surprisiugly small— subcutaneous injections of 0*7
mgrm. to 0*9 mgrm. samandarin per kilo, of body weight is fatal,
acGordhig to Fauat, to dogs ; but with regard to samandaridin, this
substance is eight times weaker^ and therefore the fatal dose is about
6 to 7 mgrms. per kilo.
§ 625. The Water Salamander (Triton criWo^w^). — Vulpino (1856)
and (Japparelli (1883) have, to a certain extent, investigated a thick
creamy-looking secretion in the skin glands of the water salamander.
Capparelli obtained 40 grms, of the secretion from three hundred Tritons.
The secretion wa& acid ; the active constituent could be extracted from
the acid solution by ether, was nitrogen-free and volatile at the ordinary
temperature* The Triton poison has a haemoly tic action on the red blood
corpuscles — increases the blood pressure and paralyses ultimately the
heart ; its action on the circulation agrees generally with that of
Bufotalin, to which it may be chemically allied,
§ 626. Poiaons of the Toad {Bu/o rmlf}aru),^'The toad secretes a
poison from its skin which has received considerable attention, aud has
been investigated by Fornara (1817), Calmels (1884), Heuser {I902j,
E. S* Faust, and others.
Faust * was successful in obtaining two very definite substances — the
* Die Thkrtjmhtn Qi/U, Bmutjsehwtiig, 1906.
§ 6^70
POISONOUS AMPHIBIA,
48s
one crjatalline, Bufonin (C^H.^O^) ; the otber araorpbouB, Bufotalin
Bufonin erjs^talliaea out of an alcohol tc extract of tho toad^s skin in
fine ueedles or in thicker prisms ; after repeated crystallisation the in,p.
is 152"*, Bufonin is soluble In cljloroform, benzene, and hot alcohol i not
very aohible in ether, nor in water, nor in cold alcohol. A little
bufonin dissolved in chloroform, and then strong sulphuric acid added,
80 as to form two stritta of the liquids, gives at the point of contact u
deep red zone. On mixing the chloroform solution this becomes dark
red and, finally, purple red. The aeid shows a green fluorescence.
Bufonin disjsolve*! in acetic anhydride and, mixed with strong sulphuric
acid, gives the snme pl«y of colours as cholesterin^the final colour
is dark green. FhisaliK and G. Bertrand, * however, consider bufonin
as simply cholesterin mixed with a little bufotalin.
Bujotalin is obtained from the same alcoholic extract After sepa-
rating the bufonin, by treating the residue with water, adding lead
acetate to purify, getting rid of the excess of lead by the addition of
just sufficient sulphuric acid, and precipitating the bufotalin by
mercuric potassium iodide, the precipitate is treated with silver oxide
and shaken with chloroform ] from the chloroform solution the bufotalin
may be obtained by precipitating with petroleum ether.
Bufotalin is easily soluble in alcohol, chloroform, acetic acid, and
ucetone ; it ia not very soluble in water, about 2 J per million ; it is
insoluble in petroleum ether. The reaction in water is acid, and it
forms sobible comiwuuds with the alkalies. It is precipitated by tannin,
but from such precipitate cannot be recovered, forming apparently fast
compounds with the stinc or lead oxide, the reagents ufiuiiUy used to
decompose tannates,
Bufonin and bufotalin po^ess similar [)oi so no us properties ; but the
action of bufonin is much weaker than that of bufotalin.
These substances are heart poisonj^] and have a similar, if not an
identical, action to the digital ins ; in this connection it is interesting to
observe that the digitalis group has but little action on the toad, and
that the blood of the toad contains probably the same poisons, i.€,
bufonin and bufotalin. The lethal dose of bufotalin, according to
Faust, for mammals is \ mgrm, per kilo, of body weight (1 per two
million) if injected subcutaneously j but very much larger doees may
be taken by the mouth. When swallowed, bufotalin excites considerable
irritation of the mucous membrane of the altmentary tract, causing
sickness and diarrhasa ; if applied to the conjunctiva, the eye becomes
red and inflamed,
I 62T. The Heloderma.^The Mexican limrd Hdodempi h&rrulum, as
d
486 POISONS : THEIR EFTOCTS AND DETECTION. f § 628.
well as //. tfuspedumj have furrowed teeth and an enormously developed
submaxillary gland, so that on anatomical grounds one would surmise
that their bite was poisonous. Experiments have shown that the secretion
is highly toxic, killing small animals, such as rabbits, in a very few
minutes, in subcutaneous doses equal to 10 mgrms. of the dried poison.
It is apparently a heart poison, but nothing is known of its composition.
Sautesson,* from a partial chemical examination, believes that the poison
is partly a nuclein-holding substance and partly an albumose.
IL— The Poison of the Scorpion.
§ 628. There are several species of scorpions. The small European
variety {Scorpio europcpus) is found in Italy, the south of France, and
the Tyrol; the African scorpion (Bothtis a/er, L.), which attains the
length of 16 cm., is found in Africa and the East Indies ; Androdoniis
funestus is found in north and mid Africa, and attains a length of 9 cm. ;
and the Androdonus occitanus, 8*5 cm. long, in Spain, Italy, Greece,
and North Africa.
In the last joint of the tail the scorpion is provided with a poisonous
apparatus, consisting of two oval glands, the canal of which leads into a
round bladder, and this last is connected with a sting. When the
sting is inserted, the bladder contracts, and expels the poison through
the hollow sting into the wound. The smaller kinds of scorpion sting
with as little general effect as a hornet, but the large scorpion of Africa
is capable of producing death. There is first irritation about the
wound, and an erysipelatous inflammation, which may lead to gangrene.
Vomiting and diarrhoea then set in, with general weakness and a fever,
which may last from one to one and a half days ; in the more serious
cases there are fainting, delirium, coma, convulsions, and death.
According to G. Sanarelli f the blood corpuscles of birds, fishes, frogs,
and salamanders are dissolved by the poison ; only the nucleus remain-
ing intact ; the blood corpuscles of warm-blooded animals are not
affected. W. H. Wilson J found that in guinea-pigs the poison caused
hyper-secretion and death from asphyxia. The coagulability of the
blood was not altered.
Valentin made some experiments on frogs with the Androdonus
occitanua. He found that soon after the sting the animal remains quiet,
but on irritation it moves, and is thrown into a transitory convulsion ;
♦ Faust, Die Thierisehen Oifl^^ BrannKchweig, 1906.
t G. Sanarelli, BolUt, delta Soe, delta $ez dei cult, delle Scienze me J,, v., 1888,
202.
t Proe. Physiol. Soc, 1904.
§ 629.]
POISONOUS FISfL
487
to this follow twitch iiigs of ainglo muscular bimdlea. The frog is pro-
gressively paralysed, and tbe reflex irritability is gradually extiiiguiBhed
from behind forwardis ; at first the muscles may be excited by electrical
stimuli to the nerves, hut later they are ouly capable of cod traction by
direct lilituuU, Scorpion poison haa but little, if any^ eflect taken by
the mouth ; experiments have beeu made on dogs by BlaDchafd allow-
ing that they can eat scorpion a without injury.
1 1 L— Poisonous Fish.
j5 629. A large number of fish possess poison our properties; in some
cases the poison is local, in others the poison is in all parts of the body.
The Muntna helena has a sort of pouch connected with four strong
conical erectile teeth or fatiga, not dissimikr to the poison apparatus
of a suake ; its bite ia said to cause toxic symptoms in man.
Many fish are provided with poison glands in connection with the
fins or special weapung, and sncli are used for purposes of defence, For
example, Symmeeia brack w is provided with a back fin consiating of 13
spines, each of which has two poison reservoirs ; the reservoirs are
connected with 10 to 12 tubular glands which secrete tbe poison, a
clear feebly acid blui*ih fluid, exciting in a concentrated condition local
gangrene; the constitutional effects, according to Pohl {Pm^er nied,
Wodnfuchrifi, 1893), in frogs experimentally injected with the poison
are mainly referable to the action of the jioisou on the hearty which
it directly paralyses. Jiottard haa recorded 6ve fatal cases in man.
The Fugu-Poiflon of Japan.— Tbe Japanese chemists have given the
name of Fugu-poisun to that which is found in the ovaries of various
species of Tetrodon^ a common fish in Japanese waters* Although con*
centrated in the ovaries^ small quantities of tbe poison have been found
in the liver and the blood. The various species known of Tetrad on are,
with the exception of Tetrodon adansuM^ all poisonous, but in unequal
degrees. The most poisonous are : — Tetrodon ekry$op^, pardalis^
tferijiiculai'ia, nud poei'Uonotiis ; w Idle less poisonous are Tetroffwi iiibnpsif^
pcrpht/rmiSj ittictonoiti^^ and rirulatm; it ia believed that the sftmt
poison existB iu all the iiahes named. D. Takahashi and G. InokOt'*' in
I890p began a chemicul research upon the poison of the Tetrodon genus ;
and G. Tahara, in 1894, separated two principles, tbe one crystalline, the
other amorphous — Tetrodonin and Tetrodonic acid. The fresb roe of
the fish, after being mashed, is submitted to dialysis; the dialysate
is purified by lead acetate, and then precipitated by alcohol ; a
crystalline mass results, being a mixture of tetrodoniu and tetrodonic
* £^ii$chtifL d. mtd, Gu. in Toitttf, viii.
48S
poisons: THBIR El'FKCTS AND DETECTION.
[§ 630.
acid. The latter is separated by diBBolviDg in water and convertmg it
by meaiiB of silver acetate ioto a eUver salt; the tetrodouin is then
preoipitated by alcohol.
Tetrodonin ia crystalline, neutral in reaction, solnble in water ; the
aqueous solution not precipitable by the usual group alkaloidal reagents.
It is iusoluble in ether, benzene, and carbon disulphide; it is with
difficulty soluble in alcohol ; 50 mgrms. of this substance injected into
a dog weighing 1*9 kjlogm. killed it in half an hour.
Tetrodonic acid is amorphous atid hygroscopic \ 10 mgrms* per kilo,
apparently kills dogs in about thirty minutes.
The action of the poison on animals consists in a rapid paralysing
effect on certain regions of the central nervous syetenj, firBt the respira-
tory centre and then the vaso-motor centre being attacked ; at the same
time a cnrarin-like paralysis of the peripheral ends of the motor nerves
is observed, which in frogs may be very complete. The lieart is not
affected directly, and continues to beat after the cessation of the
respiration. The blood-pressure sinks on account of the paralysis
of the vaso-motor centre. The symptoms in man are similar to those
in animals, and may be gathered from the following account of &
typical case recorded by Takahashi and Inoko.
A man in Kinshin (Japan), at 2 p.m., ate five pieces of n Tetrodon
(species not known). Four hours afterwards he complained of an uneasy
feeling in the epigastrium j the pulse at that time was normal* Yomit^
ing was excited by tickling the hack of the throat. Quite suddenly the
patient was incapable of walkings and he was soon conipleti4y paralysed.
Motion of the tongue was difKcult, and his speech was indistinct. Later,
cyanosis, diminished frequency of breathing, and dilatation of the pupil
were observed. The coroeal reflex disappeared, and the body tempera-
ture sank. Artificial respiration aud injection of camphor and strychnine
gave no relief, and de-ath quietly followed five hours after the meal.
Neither in animals nor in man are the post-mortem appeara^nces
distinctive.
§ 630, Other PoisonouB Fish. — Some fishes are poisonous on account
of the food they live upon ] the Mdetla venenosa is only poisonous when
it feeds upon a certain green monad ; Clupea thrissa, 0. veneiiosa^ aud
certain species of Scams neither possess poison glands nor poisonous
ovaries, but also derive their poisonous properties from their food.
In the West Indies it is well known that fish caught off certain coral
banks are unwholesome, while the same species caught elsewhere may be
eaten with safety,
A good many shell-fish, especially mussels, occasionally cause intense
poisonous symptoms ; those usually noticed are high fever, nettle-rash,
dilated pupils, aud diarrhcea. It may be that in these cases a toxin e,
S 630A ]
POISDKOUS SPIDKRS 4ND INSECTS,
489
the product of bacterial action, haa been ingested. To the agency of
bacteria has been ascribed iUness produced in Russia by a good many
fish of the sturgeon species. The symptoms are those of cerebro-spinal
paralysis. The ** Icthyismus gaatricus " of Germany may belong to the
same type. Prochorow * has described illness from ingestion of Pelra-
mt/zan jfuviaiili^ in Russia. Whether the tiah waa eaten raw or cooked,
the effect was the same, producing a violent diarrhoea, dyBenteric in
character. Even the broth in which the fish bad been boiled produced
symptoms. Fresh blood of tlie eel is stated to be intensely poisonous ;
this property is apparently due to a toxalbumin ; PennaTaria t relates
the case of a man who took, in 200 ex. of wine, 0'64 kilo* of fresh eel
blood, and suffered from diarrhoea with symptoms of collapse.
In the Linnean Tramadiorns for 2fovember, 1860, is recorded a fatal
accident, which took place on board the Dutch ship Postillion at
Simon's fiay, Cape of Good Hope, The boafcawain and purser's steward
partook of the liver of the toa<iJish (Tetrodon Honkengo^ Bloch) ; within
twenty minutes the steward died. In ten minutes the boatswain was
violently ill ; the face flashed, the eyes glistening and the pupils con-
tracted I there was cyanosis of the face^ the puStse was weak and inter-
mittentj and swallowing was difficult ; the breathing became embarrassed,
and the body generally paralysed. Death took place in seventeen
minutes. The liver of one fish only is said to have been eaten. This
might weigh 4 drachms. If the account given is literally correct, the
intensity of the poison equals that of any known snbfitance.
The poisonous nature of the goby has also led to several accidents,
and we possess a few experiments miide by Dr. Collas, } who fed chickens
with different parts of the fish^ and proved that all parts were alike
pobonous. The effects were slow in developing; they commenced in
about an hour or an hour and a half, and were well developed in
five hours, mainly consisting of progressive muscular weakness and
prostration. Death occurred without convukious.
IV.— Poisonous Spiders and Insects.
g 630a. The most tmpurtant species of spiders known to be
poisonous are : —
Neijunma (UM^menlana^ the Miuier spider of Costa Rica, is lielieved
to belong to this class, ixnd is said to cause great injury to horses, o^teu,
and other domestic animals ; Thsraphom am'wian^, the bird spider of
• Fhftrmae. Ztg,, 1885. i R f^ttrmfrndt Ilidiatw, xii, 188S.
t Soc. Set, lUv., July 19, 1862 ; BHL and For. Med. Chir. Rev,, October 18fi2,
490
POT60N5: THEIR EFFECTS AND nrTKCTlOH [§ 63OA.
the Bi'azils } Theraphma Blond ii, the buah spider of South America and^
the West hidiea ; and Therapham Javanensiif^ n big red-brown spider foutjd
IQ Javn^are all i^iant tropical hairy spiders, posaessiiig large poison
gland Bf and who^e bite is (Capable of causing serious symptoms.
Tlie Malmignette {Lathrodeftm tre^iecifrhguttaius) is only S-12 mra.
long ; it has a blackish body ; on the underpart of the abdomen are to
be found thirteon triangular or half- moon shaped spots (hence the name) ;
it IB found in Tuscany, Corsica, Sardinia^ and the lower Volga. The
nomadic tribes in South Russia are said to have lost 70,000 cattle, in
1838 and 1839, through the bite of this small insect.
K variety— the Kara-Kurt of the Tartars = ** black wolf"— is Laihro-
dectes luguhrig^ common in South Russia, and attaining a length of 2 cm.
The Kara,- Kurt |K)ison is not only to be found in special glands, but
is also diffused through the body. According to Kobert, who has
investigated this poison, it is a generic type of the poij^on of spiders ;
the active principle is neither a glucoside, an acid, nor an alkaloid. It
does not dialyse, and drying destroys its activity ; it has the characters
of a toxalbnmin, and has much siaiilarity to the action of Ricin and
Abrin. The Kara-Kurt poison dissolves the colouring matter of the red
blood corpuscles, even with a dilution of 1 : 127,000 ; it has a paralysing
effect on the heart, either due to action on the motor ganglia, or, possibly,
a direct action on tlie muscle itself. The blood- pressure siuks, the walls
of the smallest arteries and capillaries become so changed, as to allow
the transudation of blood and serum^ producing pun cti form haemorrhage a
and <Bdenm, This is best seen iu the lungs, Fhe poison also has a
pamlysing action on the central nervous system, but it is not clear as to
whether this action is primary, or whether it depends on the circulation
troubles.
The fatal dose of the poison injected subtnitaneously, or intniveuously,
is eitremely small. Cats are killed by qu an titles equal to 0^2 to 0'S5
mgrm. per kilo, body weight. Repeated injections of non- fatal doses
confer immunity.
The Epeira diadema^ the ordinary cross-spider, so called from cross-
shaped whitish spots on the abdomen^ is common in Europe generally.
Kobert has iuvetjtigated the poison it [lossesses and finds it of the same
class as that of the Kara-Kurt^ but sliglitly weaker ; he states, however,
that in a single female cross-spider there its enough poison to kill a
thousand cats.
Lycom tarantula^ a spider from 3 to 3 '5 cnK longj occurs in Italy,
Spain, and Portugal ZangrilH has observed several cases of tarantula
bite ; soon after the occurren<.^e the part bitten is anaesthetic, after a few
hours there are convulsive shiveringa of the legs, cramps of the muscles,
inability to stand, spasm of the pharyngeal muscles, quickening of the
§631-634-1
CANTHAEIDES,
491
pulse, and a three days' fever, with voniithig of yelTow bilious mutter ^
recovery follows after copioiii perspiration, in one case there waa tetanus,
and death on the fourth daj. The extraordiuarj effects attributed to
the bite of the tarantula, called tamnh'h^m in the Middle Ages, are well
detailed by Hecker;* this eiciteraent was partly hysterical and partly
deliriousj and bag not been obserTcd in modern times,
Dax has described the effects of the bite of the L. malmigiudtiH ; it
occasioned headache, muscular weakness, pain in the back, cramps, and
dyspno&a ; the symptoms disappeared after several days.
^ 63 L The kutipo is a amall poisonous spider confined to New
Zealand. Mr, W, H, Wright has recorded the case of a person who, in
1865, was bitten by this spider on the shoulder. The part rapidly
became swollen, and looked like a large nettle-rash wheal ; in an hour
the patient could hardly walk, the respiration and circulation were both
afieobed, aud there was great muscular prostration ; but he recovered in
a few hours. In other cases, if the accounts given are to be relied upon,
the bite of the spider has produced a chronic illneea, aceom[)anied by
wasting of the body, followed by death after penods varying from six
weeks to three months, t
% 632. Ants, — The various species of ants possess at the tail special
glands which secrete forjutc acid. Certain exotic species of ants are
provided with a sting, but the common ant of this country has no special
piercing apparatus. The insect bites, and then squirts the irritating
secretion into the wound, causing local symptoms of swelling and
infammation,
§ 633, Wasps, etc.^ — Wasps, bees, and hornets all possess a poison ^bag
and sting. Josef Lauyer (Arehiv /, exp. Pathol.^ 1897) collected the
stings and poison-bags of 25,000 bees. These were treated by a modified
Staa-Otto process, and ultimately a substance obtained which gave pro-
nounced alkaloidal reactions. Intravenous injection of 6 ccm, of 1'5
per cent solution of the natural poison killed a dog weighing 4*5 kilos. ;
there were general convulsions^ with trismus, and nystagmus rising to
emprosthotonos, and the animal died from the cessation of respiration.
The poison dissolves the blood corpuscles, and the post-mortem appear-
ances show strong hypenemia and haemorrhages.
!§ 634, Cantharides.— Commercial c^mtharides is either the dried
entire, or the dried and powdered blister-beetle, or Spanish liy
{GanUmru miiadoria). The most common appearance is that of a
greyish'brown powder, containing shining green particles, from which
* "The Ipidemicfi of the Middle Ages/' by J. F. C. Becker, tmnaUted by
B, G, Babingtonp M.D., F,R.S, ( The Dmmng Mania, chap. Jl. etr,)
t Traiiaac. qf tJw Nrw Zealand Insi., vol, il, 1869 ; BrU. ami For. Mtd, Vhir,
Beview, July ISTl^ p. 230,
492
POISONS: THKIB KFFKCTB AND DSTECTION.
[§ 635-
cantharUUn h readily extracted by exhausting with chloroforni, driviiig
off the chloroform by diBtillation or evapomtbnj and Bubsequently
treating the extrnet with bi3ul[>hide of oarhoiij which dtssolveB the futty
iiaatters only. Finally, the catitharidin may be recrystalhaed from
oliVoroforo>, the yield being "380 to "570 per cent. Ferrer found in the
\vtngii and their cobeflj 082 per cent, ; in the head and antennie, "088 ;
in the legs, '091; in the thorax and abdomen^ *240 per cent. Wolff
lound in Li^tta mpertf^ '815 per cent. ; Ferrer in MylahrU eichorttj
*1 per cent. J hi M^pundumf 't^^j ^^d in M . ptuitulata^ '33 per cent.
of euntftari*h'n,
§635. CaQtharidin (CjoH^gO^) has t^o crygtallitie forms---{l)
Right-angled four-sided columns with four surfaces, each surface
being beset with needles; and (2) flat tables. It was at one time
considered an acid anhydride, but H. Meyers* researches have
shown thiit it m a /^-lactone of a ketonic acid, the structural formula
of which is : —
OH
1\ .CH»-COOH
\K
CHal
CHji
,>
CO
CHj
It is aolnble in alkaline liquids, and can he recovered from them by
acidifying and shaking up with eiher^ chloroform^ or hertzene ; it is
almost completely insoluble in water. 100 parts of alcohol (99 per
cent) dissolve at 18° n"125 part^ 100 of bisulphide of carbon, at the
same temperiiturej 0 06 part; ether, '11 part; chloroform, 1*2 jmrt ;
und benzene, *2 part. Canthiiridin C4iii be completely sublimed,
if placed in the subliming cell (described at p* 259), Hon ting on
mercury ; a scanty sublimate of crystals may be obtaiued at so low
a temperature as 82'5° ; at 85', and above, the sablimation is
rapid. If the cantharidin is suddenly heated, it melts ; but this is
not the case if the tempemtnre is raised gradually. The tube
meltinj^-j^wint is as high as 218°- Potassic chromate with sulphuric
acid decomposes cantharidin with the production of the green
oxide of chrondura. An alkaline solution of permanganate, iodic
acid, and sodium amalgam, are all withont influence on an alcoholic
solution of cantharidin. With bases, cantharidin forma crystalHsable
salts, and, speaking generally, if the base is soluble in water^ the
^^ mnfharidaie*^ is also soluble; the lime and magnesic salts dissolve
readily. From the soda or potash salt, mineral acid will precipitate
crystals of cantharidin ; on heating with pentasulphide of phosphorus,
chxylol is produced.
§636-638,]
CANTHARTDKS.
493
^ 6^6, Fhantiaceuttcal Freparations of C&Qtharides.— The P.B,
preparationa of cautbarideB are — Acetum cantharideSt or vinegar of
cantbaridey, containing about '04 per cent, of cantharidin.
Tincture of earUhut'id&f containing about '005 per cent* of
cautbarldin.
A solution of cantbarides for bliatoring purposes^ Liquor eptMpadicus^
a strong solution of the active principle in ether and acetic acid,
oontaining about 16 per cent, of oantharidin.
There jure ako — An otTihnmii a blistering paper, Charta ephpa^iica \
a bli&teriog plaster, Emplctdrum catitharides ; and a warm plaster,
Emplmtrtim calefaciem.
^ 637- Fatal Dose. — It is difficult to Btate tbe fatal dose of can-
tharidin, the unassayed powder or tincture having mostly been taken,
A young woman died from 1^63 grna« (25 grains) of the powder, which
is perbaps equivalent to 6'4 mgrma* (1 grain) of cantharjdin, whiUt the
smallest dose of the tincture known to have been fatal is (according to
Taylor) an ounce, Thia would be generally equivalent to 1 5 mgrnis,
("24 grain). Hence the fatal dose of cantharidin may be approximately
stated as from 6 mgrma. upwards. But, on the other hand, recovery
has taken place from very large doses.
^ 638, Effects on Anlmale. — Animak are unequally susceptible to
the action of oatitharidin. For example, hedgehogs and swallows are
able to take large relative doses with impunity. Ellinger ba^ shown
that the whole of the poison is excreted unchanged by means of the
kidneys of the hedgehog, therefore the kidney cells must be highly
resistant to can th arid in ; other '* kidney poieous," such as potasaie
chromate, cause as much change in the hedgehog's kidneys as in other
animals, m that the immunity is one for cantharidtn alone. The
reEiiatance is not absolute; O'l grm. causes nephntia, and, in a few daya,
death. Radecki * found that cantharidin might even be injected^ in
quantities equal to 15-30 mgrins, into the blood of fowls without
any injury, and frogs also seena to enjoy the same inmvunitj ; w^hile
dogs, cats, and other animals are sensitive to the f^oison. Galippe
ascertained that after the injection of 5 mgrma« into the veins of
a dog, there was exaltation of the sexual desire; the pupils quickly
dilated, the dog suught a dark place, and became sleepy. Animals
when poisoned die in asphyxia from paralysis of the respiratory centre.
Schachowa t made some observations on the efieot of canlhartdes on the
renal exuretion of a dog fed daily with 1 grm. in powder. On the third
day, pus corpuscles were noticed ; on the fifth, bacteria ; on the
thirteenth, the urine contained a large quantity of fatty matters, and
* Dk Oanthfxridin Vcrtjifl.^ Disa., Dorpat^ I SOB.
t Uni€ra. uber dU Nieren, Di&s,, Bern, 1S77 ; C&inil, V?az. MM,^ 13S0,
494
POISONS: THEIR RPFKCTS AND KETECTION.
[§ 639^
several caate ; and on the Beveateeiith, red shri veiled blood corpusGles
were obsen^ed.
'EU^ts on Han, — Heinrich* made the following eiperimeDts upon
himself: — Thirty living blister-beetles were killedi aod digested, without
drying, in 35 grms. of alcohol for fourteen days ; of this tincture ten
drops were taken. There ensued immediately a feelmg of warmth in
the mouth and stomatih, salivation, the pulse was more fretjueiit than in
health, there was a pleasant feeling of warmth about the body, and
iome sexual excitement lasting three hours. In half an hour there was
abdominal pain, diarrha^a, and teneemus, and frequent painful nilcturi'
tton. These symptoms subsided in a few hours, but there was a want of
appetite, and pain about the kidneys lasting until the following day*
In the second experiment, on taking 1 cgrm. of canthandin, there were
very serious symptoms of poisoning. Blisters formed on the tongue, and
there was salivation, with great difficulty in swallowing, and a general
feeling of illness. Seven hours after taking the poison, there were
frequent micturitions of bloody urine, diarrhoea, and vomiting. Twenty
hours after the ingestion the face was red, the skin hot, the pulse twenty
beats beyond the normal pulsation, the tongue was denuded to two-tliirds
of its extent of its epitheliunj, and the lips and mucous membrane were
red and swollen ; there was great pain in the stomach, intestines, and
in the neighbourhood of the kidneys, continuous desire to micturate,
burning of the urethra, and swelling of the glands. There was no
sexual excitement whatever ; the urine was ammoniacal, and contained
blood and pus ; the symptoms gradually subsided, but recovery was not
complete for fourteen days.
!^ 639* The foregoing is a fair picture of what may be expected in
cantharides poisoning. It is remarkable that the j>opular idea as to the
influence of cantharidin in exciting the sexual passion, holds good only
as to the entire cantharides, and not with cantharidin. It is very
possible that cantharidin is not the only poisonous principle in the insect.
The symptoms in other eiiaes, fatal or not, have been as follows ; — Imme-
diate burning in the mouth and throat, extending to the stomach and
alimentary canal, and increasing in intensity until there is considerable
pain. Then follow salivation, difficulty in swallowing, and vomiting, and
generally diarrhcea, pain in the kidneys, irritation of the bladder,
pnapism, and strangury, are all present. The pulse is accelerated, the
breath iujti disturbed^ there are pains in the head, and often mydriasis,
giddiness, insensibility, delirium, and convulsions ; trismus has been
noUced« The desire to micturate frequently is urgent^ the urine is
generally bloody, and contains pus. Pregnant women have been known
to abort. In a few of the cases in which a different course has been
• Sohroff, E^iUekrift d. (h». d, A«r^ in mm, 13, 56.
mi
§640,641]
CAJTTHARIDES.
495
ran^ the oerrotis symptoms have predominaled over those of gttatro^
txit«stiiial irritation, and the p&tient has sunk in a kind of ooUa|Me^
In a case of chronic poisoning bj canfcharides, ei tending over three
months, and recorded by Tarcbioni Bonfanti,* after the tint dose
appeared tetanic convulsions, which subsided in twenty-four houts,
tiiere was later cystitis, and from time to time the tetanic couvulaiona
returned ; gastFO-enteritts followed with frequent vomit iug, when, can-
tharides being found in the matters ejecteil^ the otherwise ^ibseure
nature of the illness was shown.
In a caae recorded by Sedgwick, t following the gastro-eoterio
symptom^ there were epileptic convulsions; in ibis iu stance also was
noticed an unpleiu^nt smell, recalling the notion formerly held that
canthandes imparted a peculiar odour to the breath and urine, hi
a case ol chronio poisotiing related by Tardieu, six students, during
several moDtha, used what they thought was pepper with their food,
but the substance proved to be really powdered can thar ides. The
quantity taken each day was probably small, but they suffered from
pain about the loins, and also irritation of the bladder. There was no
sexual excltement-
g 640. Post mortem Appearances. —In a French criminal ease^ iu
which a man poisoned his step-brother by giving cautharldes in soup, the
pathological aigua of inflaramation of the giiatro-inteatiual tract were
specially evident, the mouth was swollen, the tonaili ulcerated, the
gullet, stomach, and intestines were inflamed, and the mucous membrane
of the intestines covered with purulent matter. In another case there
waa an actual perforation 3 inches from the pylorus. The luffHrnumtury
appearances, how*evcr, are not always bo severe, being cOii fined to
swelling and iuHummation without iilcenition. In all oaaes there has
been noted inflammation of the kidneys and urinary pigsagee, and this
is seen even when cantharidiu is administered to animals by fiubcuta-
ueoui injection. Iu the urine will be found blood and fatty epithelial
casts, as well as pus. The contents of the stomach or the iiitci^tines will
probably contain some remnants of powdered cautharides, if the powder
itself has l>een taketu
§ 64 L Testfl for Cantharidin, and its Detection in the Tissues,
etc. — The teats for cantharidin are — (I) Its form, (2) its action in
the subliming cell, and (3) its power of raising a bliaten
The most convenient method of testing its vesicating properties, is to
allow a chloroformic solution of the substance supposed to be cantharidin
to evaporate to dryness, to add to this a drop of olive oil (or almond oil),
and to take a drop up on the smallest possible quantity of cotton wool,
and apply the wool to the iuside of the arm, covering it with good oilskin,
* Ga^. M^. Mi, L&mk, 18S3, 1^ Med. Time^, 1361.
496
POISONS: TireiR effects and detection.
[§641.
and strapping the whole on by the aid of sticking-plaster In about an
hour or more the effect is exam hied. The thio skin of the lips 18 far
more easily blistered than that of tha arm, but the application there ia
inconvenient.
Dragendorff has ascertained that cantharidin is not present in the
contents of a blister raised by a cantharlde^ plaster, although it has been
found in tlje urine of a person treated by one ; and Petteukofer has also
discovered cantharidin in the blood of a boy to whose spine a blister had
been applied*
The great ini^olubilitj of cantharidin in water has led to various
hypotheses as to its absorption into the system. It is tolerably easily
dissolved by potash, soda, and ammonia solutions, and is also taken np in
small proportion by sulphuric, phosphoric, and lactic acids. The result*
ing compounds quickly diffuse themselves through animal membranes.
Even the salts with lime, magnesia, alumina, and the heavy metiUa, are
not quite insoluble. A solution of salt with ca nth arid in ^ put in a
dialysing apparatus, separates in twenty^four hours enough oanthariditi
to raise a blister.
Cantharidin has actually been discovered in the heart, brain, muscles.,
contents of the stomach, mte^tineS| and fsBoes (as well as in the blood
wnd urine) of animals poisoned by the substance. A urine containing
cantharidin is alkaline and albuminous. Cantharidin, although readily
decomposed by chemical ageuta, Is so permanent in the body that it has
been detected in the corpse of a cat eighty-four days after death.
In any forensic case, the defence will not improbably be set up that
some animal (e.y. a fowl poisoned by can thar ides) has been eaten and
caused the toxic symptoms^ for cantharides is an interesting example of
a substance which, as before stated, for certain animals (such as rabbits,
doga, cats, and dncks) is a strong poison, whilst in others (e.g. hedge-
hogs, fowls, turkeys, and frogs), although absorbed and excreted, it
appears, save in large doses, to be inert. Experiment has shown that a
oat may be readily poisoned by a fowl saturated with cantharides ; and
in Algeria the military surgeons meet with cystitis among the soldiers,
caused by eating frogs in the months of May and June, the frogs living
in these months almost exclusively on a species of Cant bar i^.
Dragendorff recommends the following process; — The finely-pulped
substance is boiled in a porcelain dish with potash4ye (1 part of potash
and 12 to 18 of water) until the fluid is of a uniform consistence. The
fluid, after cooling, is (if necessary) diluted with an equal bulk of wnter,
for it must not be too thick ; then shaken with chloroform in order to
remove impurities ; and after separation of the chloroform, strongly
acidified with sulphuric acid, and mixed with about four times its volume
of alcohol of dO to 95 per cent* The miiture is kept for some time at a
§641]
CAHTITARIDES.
497
boiling temperature, filtered hot, anti ilie alcoliol distilled from the fil-
trate. The water J fluid is now again treated with chlorofornij as above
described. The chloroform extract is washed with water, the reaidue
taken up on some hot almond oil, and its blistering properties investi-
gated. The mass^ heated with potash in tt^e above way, can ako be
submitted to dialysis, the diffusate supersaturated with sulphuric acid,
and shaken up with chloroform.
In order to test further for cantharidin, it can be dissolved in the
least possible potash or soda-lye* The solution^ on evaporation in the
water-bath, leaves crystals of a suit not easily soluble in alcohol, and
the vv^atery aoUitiou of which gives with chloride of calcium and Imryta
a white prcjcipitate ; with sulfihate of copper and sulphate of protoxide
of nickel, a green ; with cobaltous sulphate^ a red ; with sugar of lead,
mercury chloride and argentic nitrate, a white crystalline precipitate.
With palladium chloride there occurs a yellow, hair-like, crystalline
precipitate ; later crystalsj which are isomorphous with the nickel and
copper salts.
If the titicture of cantharides has been used in considerable quant ity,
the urine may be examined ; in such a case there will collect on the
surface drops of a green oil^ which may be e^ctracted by petroleum
ether ; this oil is not blister-raising. Cantharides in powder may, of
course, be detected by its appearance ,
To the question whether the method proposed would extract any
other blister-producing substance^ the answer is negative, since ethereal
oil of mustard would be decomposed, and the active constituents of the
Euphorhlm do not withstand the treatment with KHO. Oils of
auemone and anemonin are dissolved by KHO, and s^ain separated
out of their solutions ; but their blistering property is destroyed. They
are volatile, and found in anemone and some of the Ranwiodaemx, In
the Aqim jmlsatUla there is an oil of anemone, which may be obtained
by shaking with ether] but this oil is not permanent, and if the Agtia
pttimtilla stand for a little time, it splits up into anemonic acid and
anemonin, and then canuot be reobtained. A blistering substance,
obtained from the Anacardia orienialia txtid the fruit of the Ajiacardium
ocdderUaf^ and Semecarptis anacardiunit is not quite destroyed by a
efaort lie t ion with potash, but is by one of long duration ; this substance,
however, cannot be confused with cantharidin, for it is ollyj yellow^
easily soluble in alcohol and ether, and diflers in other respects.
\^
498 POISONS: THEIR KFFKCTS AND DETECTION. [§ 642,643,
v.— Poisonous Snakes.
§ 642. The poisonous snakes are classified as follows : —
A. CoLUBRIDiE, VENENOSiB.
I. Opistoglypha (suspected snakes, ** serpenies suspedi "). — Furrowless
teeth in the fore-part of the upper jaw, behind one or several poison
fangs. They are almost all poisonous, but seldom dangerous to man
or the larger animals. They are represented by HomcUopsincB, the
water snakes ; Dipsadomorphinoi, whip snakes ; and Elachistodontinas.
II. Proteroglypha, — Furrowed teeth. The teeth in the fore- part of
the upper jaw are provided with a deep groove or furrow, in combination
with very often highly developed poison glands. This division includes
the sea-snakes Hydrophince and the Elapince.
B. ViPBRIDiE.
I. Crotalinm (pit vipers). — Head very broad. On both sides of the
head, between the eyes and nostrils, a deep depression or pit ; hence the
name.
II. ViperincB (vipers). — Head very broad, but possessing no pit like
the Orotalince.
The Opidoglyphm are poisonous to small animals, and species belong-
ing to this order have occasionally caused illness in man.*
The Proteroglyphoe include most of the poisonous snakes other than
vipers ; to this order belong : —
The seorsndkes (HydrophinsB), common in the Indian Ocean and in
the Pacific. The poison of the Enhydrina bengalensis has been investi-
gated by Leonard Rogers ; he found it less resistant to heat than the
cobra poison ; its physiological action strongly resembled that of the
cobra, but since the lethal dose for birds was so small as '05 mgrm. per
kilo., it appeared to be ten times stronger or more concentrated.
Fraser and Elliott have also made some observations on the poison
of Enhydrina valakadien, and found that the dried poison killed cats in
the proportion of *02 mgrm., rabbits *06 mgrm., and rats '09 mgrm.
per kilo, of body weight.
§ 643. The Poison of the Cobra. — The poison excreted from the
salivary glands of the cobra di capello is one of the most deadly animal
fluids known. When first ejected, it is an amber-coloured, rather
syrupy, frothy liquid, of specific gravity 1*046, and of feeble acid
reaction ; it dries rapidly on exposure to air to a yellow film, which
readily breaks up into brilliant yellow granules, closely imitating
* J. J. Queloh, Proceedings qf the Zoological Society, 1898.
§ 643.]
COBKA POISOK,
499
orystalB. The yellow powder h very acrid and pungent to the nostrila,
and excites a painful (though transitory) infiainmation, if applied to
th& mucous memhrane of the eye; the taste is bitter, and it raises
little blisters on the tongue. It ia perfectly stable, can be heated
to 100" C, without decomposition for a short time, and preserves its
activity for an inde^nite time. The dried poison as described is
perfectly sol\ible in waterj and if the water is added in proper
proportions, the original lluid is without doubt reproduced, the solution
usually depositing a sedimeut of epithelial dc^bris, and often containing
little white threads.
The poison haa been examined by several chemist&i with various
results. The senior author isolated, iu 1876, a crystalline principle as
follows: — The yellow granules were dissolved iu water, the albumen which
the venom so copiously contains coagulated by alcohol, and separated by
filtration ; the alcohol was then driven off at a. gentle heat, the liquid
concentrated to a small bulk, and precipitated with basic acetate of
lead. The precipitate was separated, washed, and decomposed in the
usual way by SHgp and on removing the lead sulphide, crystals having
toxic properties were obtained. The authors have been unable^ through
want of material, to deal with the suggestion of F, N orris Wolfenden that
the crystals wore those of gypsum, their toxic properties being due to
adhering impurities.
Pedlerj^ precipitating the albumen by alcohol, and then to the
alcoholic solution adding platinic chloride, obtained a semi -crystalline
precipitate, which from an imperfect combustion he thinks may have
sometliiijg like the composition PtCl4{C|-Ho5N40^HCl)2.
The latest observer of the cobra poison, Edwin Stanton Fatist,t claims
to have shown that the essential constituent of the cobra poison is a
nitrogen-free substance, belonging pharmacologically to the group of
the picrotoxins, sajiotoxinsj and sphacelo- toxins. To this substance he
gives the name of '* ophiotoxin'^ ; ho has obtained it iu a<]^ueoim solution,
bat directly the aqueous solution is concentrated in a vacuum, the
white residue obtained is in most eases inactive. The solution froths
on shaking ; if injected subcutanconsly it has but little action j on the
other hand, if injected intravenously the ordinary effects of cobra
poison are produced. Hence E^'anst appears tu believe that the poison of
the cobra is some compound of his ophtotosLin and an albuminoid body :
the combination being easily dissolved. He thinks that there is some
analogy between the cobra poison and the jalapin-elaterin group, in
which the free acids and their salt^ are inactive ; while, on the other
band, the Kuhydridea are active.
• Proe, Hof. 5at'., vol. xjivtL p» 17.
t Die ihUrisckin Gi/te, Bimuaschwei^, 1&0€.
Soo
POISOiiS : THEIR EFFBCTS AHD DETECTION. [§ 644- 645.
Tbo blood of the cobm is also poJsonouB. A Calmette* has
found that 2 c,c^ of fresh oobra blood inject ted into the periboueum
of a rabbit weighing 1"5 kilo,, cauees death in mx hours; the same
doae of the defibrinated blood iojeeted into the veins is fatal in three
minutes,
S 64 4» Fatal Dose. — From one of the senior author*s experiments on
catJB^ rubbiti, and birds^ it seeraft probable that the least fatal dose for cats
and rabbits lies between '7 and *9 mgrm. per kilo., and for birds some-
where about '7 mgrra. por kilo* of the dried |>oison; the venooi contains
about 60 per cent* of albuminous matter, and about 10 per cent, of
poisonous substance ; therefore, the lethal power is represented bj
something like '07 to *09 mgrm. per kilo.^ if the pure toxic principle
free from albumen and diluting impurities be considered* Calmette
calculated the fatal dose for a man at 10 mgrms., Fraser 31*7 mgrms,,
and Elliott about 30 mgrms,
g Gi5. Efifacts on Animals. — There has been much exact phjsto>
logical work done on the cobim poison since the last edition of this
work. One of the most complete researches is that bj H, E. Elliott ;t
he lias confirmed the fact that cobra veuoni raises the blood-presaure ;
this action can be traced in the vessels of the frog, down to dilutions of
1 in tea million. If the solution is couceutrated^ it acts directlj on
the isolated frog'a ventricle, killing it in systole; but if the solution is
weakf the action of the heart is stimulated ; this brings cobra venom
into line, pharmacobgicallyt with the glucosides of the Strophantin
group. Elliott found that atropine sulphate and cobra venom in the
same solution intensify each other.
Cobra veuom acts pow^erfull y on the mammalian heart ; the action
is dual«
(1) A direct action on the muscular fibres or on the nerve endings*
(2) An action on the iutra-eardial vagal mechauirtui.
Concentrated solutions cause irregular and extreme cardiac escita-
tiou, with earl j death in systole; with less concentrated solutions, the
early singe of excitement yields to a prolonged pbiise in which the
tonic action of the poison in tlie tieart is most pronounced, the beat is
regular, steady, aiid strong.
When given aubcutaneously in low lethal doses, death occurs from
pamlysis of the reHpiratory centre; there is a gradually increasing
venoaity of the blood, and if life is prolonged beyond the usual term
(five hours) the phrenic and other motor nerves may become paralysed.
If a la^ge dose be given intravenously, the respiration may cease
almost at once* By applying cobra venom direct to the exposed
in©lulla oblongata of the rabbi t^ Elliott has shown that the respiratory
• Omit^ii. rend, Soc, da Bid, ^ 1864, t FhU, Tmm., 1905.
§ 646]
COBRA POISON,
50 r
centre can be paralyBod without th« phreEic nerve ends or the heart
being appreciably affected .
If very large doaea be given, the direct actioti of the poiaon on the
heart may produce death by cardiac failure. Such large doses cause (a)
a fiiiddeu fall of blood-preesure ; (6) a sulosequeut risCf if the dose has
not been too large ; {c) a final fall to zero.
Cobra pci&oUj in common with that of most of the Ooiubrifl^, prevents
the coagulation of the blood, in eon trad i&ti notion to the viper poisons,
which strongly coagulate blood ; both clasaes of poison appear to dis-
solve out the red colouring matter of the blood.
The poat-morteni appearances are not very distinctive; at the
point of injection, there is often a slight hoemorrhagic oedema.
The liver and the spleen show on their surfaces circtimscribed
hcemorrhagic spots; the peritoneum, the meninges, endocardium,
pleura, and mucous membranes show frequently eochymoses^ and
the blood ia Huid and dark.
§ 64G. EffectB on Man.— By far the best account hitherto published
of the efiecte of the cobra poison is a paper by Dr, Wall,^ in which
he points out the very close similarity between the uymptoma produced
and those of gIoaso-|jharyngeal paralysis. This is well shown in the
following typical case :— A coolie was bit ten on the shoulder about
twelve at midnight by a cobra ; he immediately felt burning pain at
the spot bitten, which increased. In fifteen minutes afterwards he
b^an, he said, to feel intoxicated, but he seemed rational, and
answered questions intelligently. The pupils were natural, and the
pulse normal ; the respirations were also not accelerated. He next
began to lose power over his legs, and staggered, In tlurty mi on tea
after the bite hia lower jaw began to fall, and frothy viscid mucous
saliva ran frum bis mouth i he spoke indistinctly, like a man under
the influence of liquor, and the paralysis of the legs increased.
Forty minutes after the bite, he began to moan and shake his bead
from side to side, and the pulse and respirations were somewhat
accelerated ; but he was still able to answer questions, and seemed
conscious. There was no paralysis of the arms. The breathing
became slower and slower, and at length ceased one hour and ten
minutes after the bite, the heart beating for about one minute after
the respiration had stopped.
There is often very little sign of external injury, merely a scratch or
puncture being apparent, but the areolar ti^^ue lying beneath is of a
purple colour, and infiltrated with a large quantity of coagnlablc, purple,
* ** On tlie Din'ereDoe of the PUysiolo^c*! Effects Produced by tijo Poi&oii of
Indian Yefiymoui> Snifckea." by A. T. W&Il, M.U, Proe. Ho^^ So^t 1881, rol. xxxii
poisons: THEIK KFFECTS ANB DETECTION.
blood-like Huid. In udditiou, the whole of the neighbtmriug vessel » are
intensely injected, the injection gradually diminishing as the site of the
poisjoned part is receded from, so that a bright scarlet ring aiirronnds a
l>urple area, and this in its turn fades into the nornml colour of the
neighbouring tissues. At the margin is also a purple blood-like fluid,
replaced by a pinkish serumj whieh may often be traced up in the
tissues surrounding the vessels that convey the poison to the system,
and may extend a considerable distance. These appearances are to be
accounted for in great part by the irritant properties of the cobra
venom. The local hy|i€r£emia and the local pain are the first symptoms.
In man there follows an interval (which may be m sliort as a few
minutes, or so long as four hours) before any fresh sym[itoms appear ;
the average duration of the interval is, according to Dr. Wall, about an
hour* When once the symptoms are developed, then the course is
nipidi and, as in the case quoted^ a feeling Itke that of intoxication is
Brst produced, and then loss of power over the legs. This is followed
by a loss of power over the speech, over swallowmgi and the movement
of the lips ; the tongue becomes raotiotiless, and hangs out of the
mouth ; the saliva ia secreted in large quantitleSt and runs down the
face^ the patient being equally unable to swallow it or to eject it, and
the glosao-pharyngeal paralysis is complete.
§ 647. Cobra Anti-toxin.— All the so^alled antidotes, such as gold
chloride, potassic permanganate, and others, have proved to be uselesi ;
for, although chemical agencies may make the poison clinging to the
wound inerfcj such reagents fail to neutralise the absorbed poison. It
had long been known that animals dosed subcutaneously by quantities
of cobra or other snake venom, insufficient to kill, acquired a certaiu
degree of immunity against the same poison ; this induced Calmette to
endeavour to obtain an anti-venom serum on the same principle, as to
preparation, as the well-known commercial anti-toxin for diphtheria. In
this Calmette, working in the Lille Institute, has been to a great
extent succeaaful Horses and dookeys are the animals selected to
produce the immunising and curative serum ; these animals are injected
with ever-increasing doses of cobra poison, until they bear without
reacting two hundred times the otherwise deadly dose — ejj. the fatal
dose for a horse is about 10 mgrms, of the dried cobra venom, and a
horse after successful treatment will bear the injection of a quantity
equal to no less than 2 grms, Many animals during the pi'ocess die of
endocarditis or nephritis, which affections must therefore be considered
as true sequel® to chronic cobra poisoning. The serum obtained from
the blood of an animal which is considered highly resistant is tested
by mixing a definite quantity of it with an equally definite quantity of
i cobra Tcnom, and injecting it into aome small auinmL The serum is
I 647A.i
F0IB0N0D8 SNAKES.
SO3
considered anflictaBtly active if 2 c*e* of aerum mixed with I mgrtn. uf
cobra venom produces no poisonous ijmptoniB when injected into a
rabbit, and if 2 c.c. of the ierum injected Into a rabbit 2 kilogmmmes
in weight protects it from the effects of 1 mgrm, of cobra venom iu-
jected aubcutaneously an hour later.
The semm is preserved with strict antiseptic precautioHB in IQ-c.c.
tubes ; it is said not to lose ita activity for two years or even longer.
Another method of preserving the ierum is drying it at a low tempera*
tura; it then appears in commerce as light dry yellow scales, which for
subcu tan eons use are dissolved in water at the time. For ten years
now the Pasteur Institute at Lille has prepared this form of ant i -toxin ;
at first it was hoped that in such a substance was to l^ found a general
remedy for, or protection against, snake bite, but this is not so ; its action
is confined to either the particular species of snake venom, or species
nearly allied| against which the horse was immunised. Experiments are,
how even being mad© in order to obtain if possible a general sort of
serum, hy operating with mixtnrea of venoms ; whether success will be
attained time alone can show.
§ 647a, Other Colubrine BmkeB,—Bungarm fasciatm^ or the Banded
Krait, acts similarly to the cobra poison ; but since its activity is
destroyed by heating from 7 3 "-7 5*, it is less stable.
Buugams asnUeus^ or the Krait^ one of the most dreaded of the
Indian snakes^ is said to be even more virulent than the cobra.'*
Naja Bungarus^ or the Hamadryad, possibly the largest poisonous
snake in the world, grovviug to over 13 feet in length j the Naja haje
(Cleopatra*s asp) ; IClaptt torallinu^^ the brilliant red coral snake of
Am erica; the Elapinm of Australia — all jtossess a venom having a
physiological act tun similar to that of the cobra.
The Viperidse. — The chief poisonous snakes belonging to the
Viperndwj besides the trne vipers, are the American rattlesnakes,
belonging to the genus Crotalm — ^via., the LacJi^m muta (Oroialuts
mtUua)^ commonly called the surucucu, or bush master of the Dutch
colonists of Surinam, one of the largest venomous snakes ; the Copper^
head, also known under the name of Chunk-head; Deaf Adder and
Pilot snake (Tngofiocepknim conioriui) ', various species of Bothrops In
the Draziln. There Is also a species of 7*nmeresurus in one of the
Japanese islands, which appears to be specially aggressive, and killij
some 48-70 hours after the bite*
The poisons of these snakes appear to be different from that of the
cobra and more analogous to the poison of the true vipers.
* Leonard Rogsn, M,D., PhiL Tr<snixae^, 1901* MAJor E. H. Elliott and
W. G. Sillar. M.B., ibid. Smi\e Oimrwdi<mM 0^ the Ftfisfm iff tht Banded KraU
{Bun§arm fwtciaim), hy Qa^U George Lkinb, M.D. Glaa, CkleuttA, IdOl.
So4
POmONS: THEIR EFFECTS AND DETECTION. [§647^,647^
§ 647b, Buboia Emeellii — The Ihilma r-w^seilu or litmiell'M mjwr m
one of the best knowu and moat deadly of the Indiau viper*. The
potson of the Ttper difiera from that of the cobra in causiug greater
lot-al effect ; it also coagulates the blood inatead of miikitig it more fluid.
Viper poison appareotlj digeits fibrin ; it is not very siiible, as a heat
of about B0'-85* destroys it The efl'ecU of the poison of this viper
are also different from those of the cobra. The action coaimenct-s by
violent geueral coiivukioti^, wliich art; often at once fatal^ or may be
followed by rapid paralysis and death ; or these symptoms, again, may
be recovered from, and death follow at a later period. The couvulsionB
do not depend on aspliyxia, and with a small dose may be absent. The
paralysis is general, and may precede for some time the extinction of
the respiration ; the pupils are widely diJafcedj there are bloody dis-
eharges, and the tirine is albuminons. Should the victim survive the
iirst effects, then blood-poisoning may follow, and a dangerous illness
resuk( often attended with copious hcBmorrhages. A striking example
ol this course is recorded in the Indian Med. Gaz., June 1, 1872.
A Mahommedan, aged 40^ was bitten on the finger by Russeire viper ;
the bitten part was soon after e^tcised, and stimulants givt^n^ The hand
and arm became much iwoUen, and on the aame day he passed blood by
the rectum, and also bloody urine. The next day he was sick, and still
passing blood from all the cliannels ] in this state be remained eight days,
losing blood constantly, and died on the uinth day. Nothing definite is
known of the chemical composition of the poisfjn ; it is probably qualita-
tively identical with " viperin.'*
S 647o. The Poison of the Commoii Viper. — Tlie common viper still
abounds in certain parts of (^reat Britain, as, for ej[ample, on Dartmoor.
The venom was analysed in a partial ujanner by Yaletitin. In 184 3
Prince Luoien Bonapurte separated a gummy varnish, inodorous,
glittering, and trans j)arent, which he called eehidnin or vtjmHn; it was
a neutral nitrogenous body without taste, it arrested the coagulation of
the blood, and, injected into animals, produced all the effects of the
bit* of the viper, Phisalix and G, Bertraud have studied the symptoms
produc€^d in small animals after injection. A gmnea^pig, weighing
500 grms.j was killed by 0*3 grm. of tlie dried venom dissolved in
5000 parts of saline water; the symptoms were nausea, quickly passing
into stupor. The temperature of the body felL The autopsy ihowed
the left auricle full of bloml, the intestine, lungs, liver, and kidneys
injected. The blood of the viper is also poisonous, and produces the same
symptoms as the venom.* I'he puff adder ( Viijera arieiam) Is found in
south and equatorial Africa; the Hottentots use either the crushed head
or the poison glands as an arrow poison.
* Compi. rmd, Sog. de Biol,^ L v. 907.
1 647D.]
MAMMALIAN POISON.
50s
VI. Mammalian Poison.
§ 6 4 7 D, E pinephrin { adrenal in - Bupraroni u ), C^jH ^^O^ N . — This sub-
stiince WHS Brat bolated in an impure condition from the gu[>rarenal gland
by Abel and Crawfonl in 1897, and has received much attention since
that date on account of its cstraordinarj physiological activity. The
researches of a number of chemists— e.(?. Von Furth, Pnuly, Jowett* —
have now settled the constitutional formula of epiuephriu, showing it to
be a methyl ami no^erivative of cateohol ;
OH
CHtOH)
On oxidation with permanganate, forniic and oxalic acids are obtaiiied
and methylamiue ; on fusion with KUH, the resulting product con-
tains proto^atechuic acid ; on curaplete methylation and subsequent
oxidation with permanganate, it yields trimetbylamine and veratric acid.
All these rejictions are cousistcnb with the above formula*
Jowett and Barger have further confirmed the constitution c»f
epinepbrin by the synthesis of a methylene ether :
CH.OH
which, on treatment with HCl at 150*, yields a substance having the
chemical and physiological properties of epinephrin {Joum. OhmrL 6'qc.^
Transit LB05). H. IX Dakin has ahown that^ starting with cateeholp
a body may be prepared having the same formula as epinephrin and
having the same reaction, and of ^reat physiological activity, but it is
optically juacti^'e. A number of allied substances have also been
prepared which cause a rise In the blood-pressure {Froc Fhydol. SoCf
1905. J. Phifsiot XXX ii.}*
Epinephrin is obtained from the suprarenal glands by precipitating
the aqueous extract by lead acetate or alcohol to get rid of impuritieSp
and finally adding ammonia. From the ammoniacal liquid, small crystals
ultimately separate ; these are dissolved repeatedly in acid and
precipitated by ammonia: it has also been obbiined pure by first
* ^*The Constitution of Epin^phriiit*/* by HtKiper Albert Dickinioii Jowatt^
J^um^ CAtf/it. Sacv Tram*. 11^04,
S06 POISONS: THEIR EFFECTS AND DETECTION. [§ 647 £,648.
converting epinephrin into a salt, dissolving in alcohol, and fractionally
precipitating with ether.
Epinephrin is soluble with difficulty in cold water, but better in hot ;
it is insoluble in chloroform, amyl-alcobol, carbon disulphide, ether,
acetone, and petroleum ether; in alcohol it is slightly soluble. The
caustic alkalies dissolve it, but neither the carbonates of the alkalies nor
ammonia.
It is not precipitated by the group alkaloidal reagents ; it reduces
Fehling's solution, and also ammoniacal silver solution. It forms soluble
salts with acids, reacts feebly alkaline to litmus paper, and its aqueous
solution becomes red on exposure to the air, turning later to brown.
The addition of ferric chloride to such solution produces a characteristic
green colour. £pinephrin polarises ; its specific rotation, according to
Jowett, is[a]D= - 32•0^
§ 647b. Physiological Action of Epinephrin. — The primary action is
on the blood-vessels and the heart. Applied to the skin or to a mucous
membrane, it produces an extraordinary contraction of capillaries and
arteries, so as to diminish greatly the blood supply; hence its great
use in surgery. If injected intravenously, fractions of a mgrm. cause
in dogs or nibbits a large sudden increase of the blood-pressure ; but Id
consequence of destruction or change of the poison, this increased blood-
pressure is of very short duration. After subcutaneous doses of
epinephrin, glycosuria has been observed. W. Erb, junior,* has found
that if from 0*1 to 1 mgrm. of epinephrin is injected into rabbits for a
length of time — e,g. 10-60 days — disease of the aorta and other large
arteries is induced.
Death occurs from heart paralysis or arrest of the respiration.
There is great danger in treating human patients with subcutaneous
injections of epinephrin, if the heart is already weakened by disease ;
in such a case death may occur, probably from the sudden stress put
on the circulation from the increased blood-pressure.
DIVISION II.— PTOMAINES— ANIMAL TOXINES.
JJ 648. In the last edition of this work a ptomaine was defined as
a basic chemical substance derived from the action of bacteria on
nitrogenous sulistanccs. This definition can no longer be accepted, for
ptomaines may W produced by the action of enzymes, without the
intervention of Ivicterial life. The woni *' ptomaine ' itself is open to
objection, and although still used in newspapers and popular diction
• Architf, r-rp. I\%tk. w. PharmakoUMfU, 1905.
§ 649, 6so.]
ANIUAL TOXINES.
$0?
18 getting lure in the stricter language of retieiit pharmacology and
phy Biology. It will be beet at present to clarify the eo-ciiUed ptonmiuea
ai "aoimal toxiues," a large number of which appear to be the pro-
duction of special biicteriH— in some^ and indeed in most eases, they
appear to be the excretory products of the bacteria j on the other hatid,
it has been ahowu Lhat the typhoid bacilhia, the Badlltm roli eommufm,
the BaciUu^ euiet^^itidis^ (mertner, and the Bacillus d^^miimm^ all contain
etido-toxines, which have a simikr physiological actioHf eauMtug in the
rabbit great lowering of the body teniperatore, duxrrhoeuj prostration,
with sudden eollapae and death, I'he foul smelling bodies occurring in
putrefactive proceasea^ eontrary to general belief, have but alight
physiological aotion*
Isolation of Animal Toxines.
§ 649; Gautier'B ^ Process. — The liquid is acidified with oialic acidi
warmed, filtered, and distilled in a vacuum.
In this way pyrrol, skatol^ phenol, indol, and volatile fatty acids are
aeparated and will be found in the diMtillate, The residue in the retort
IB treated with lime, filtered fnjm the precipitate that forms, and distilled
in a vacunm^ the distillate being received in weak sulphuric acid. The
bases accompanied with ammonia distil over. The distillate is now
neutralist^ by sulphuric acid f and evaporated nearly to dryness,
separating the mother liquid from sulphate of ammonia, which crystalUsee
out. The mother liquids are treated with absolute alcohol, which dis-
Bolves the sulphates of the ptomaines. The alcohol is got rid of by
evaporation, the residue treatml with caustic soda, and the bases
shaken out by successive treatment with ather, petroleum ether, and
chloroform. The residue remaining in the retort with the excess of
lime is dried^ powdered, and exhausted with other ] the ethereal extract
Is separatodi evaporated to dryne^^ the dry residue taken up in a
little water, slightly acidulated, and the bases precipitated by an
alkali.
I 650. Biieger'a Process.— Brieger \ thus describee his process :—
The matters are Unely divided and boiled with water feebly acidulated
with hydrochloric acid.
Care must be taken that, on boiling, the weak aoid reaction is
retained, and that this manipulation ot]ly lasts a few minutes.
• PUfttmim*^ L^itcumaut^j E. J. A. Uautier, Pjiiia, 1886*
i The fir»t i^dd appiireatly h ^ dilute thiit the diintiikto more than iieutraliisee
it^ hence more wuljihuric ofid h a^Mad to com]tlpt4^ neutniliHiitiott.
^ Unicntu^angen. Ub^r Hmnaimf Tlieil iiL, Berlin, 1888.
So8
POISONS: THBIR EFFECTS AND DETECTION.
[§ 650-
fi%
The insoluble portion h filtered otT^ and the filtratt? evaporated, either
iu the gaa-oveu or 00 the wjiter4jiitli, to sijrupj comistency. If the
subs Lai ices are offenBivey as alcoholic and watery extmcta of flesh usually
ure, the use of Boeldiseh*8 simple apparatus (see diagram) is to bo
recommended. The filtrate to be evaporated m
jdKued iu a Htisk provided with a doubly por*
fo rated caoutt^houc cork carrying two bent ttibe:^ ;
the tul)e i/ terminates near the bottom of the
tlaffk, while the tul>e a tor mi nates a little above
the level of the fluid to be evaporated. The
tul>e a iu ooimeeted with a water pump which
sucks away the escaping steam. In order to
avoid the running back of the condenHed water
ftirming in the cooler part of the tube, the end
of the tul>i a is tw^btcd into a circular form.
Through the tube />, which has a fine capillary
bore, a stream of air is allowed to enter, which
/f kenps the fluid in eojistant agitation, continually
/ destroying the scum on the surface, and avoiding
sediments collecting at the bottoraj which may
cause fracture of the flask. According to thu
regulation of the air current, a greater or smaller vaeuum am lie pro-
duced. The iuid, evaporated to the consistency of a ayrup, is treated
with 96 per cent* alcohol, filtered, and the filtmte precipitated with
lead acetate.
The lead precipitate is filtered off, the filtrate evaporated to a syrup,
and the syrup again treated with 96 per cent, alcohol. Tliis is again
filtered, the alcohol got rid of by evaporation, water added, the lend
thrown down by SH^ and the fluids after the addition of & little
hydrochloric acid, evaporated to the consistence of a syrup j this symp
is exhausted with 96 per cent alcohol, and precipitated with an alcoholic
solution of mercury chloride, Tlic mcrcmy precipitate is boiled with
water, and by the tli Keren t s<jlnbility of the mercury baits of certain
ptomaiue^i some seiwitration takes place. If it is ausj>ected that some of
the basic toxincs may have Iw^eii sepirated with the lead precipitate,
this lead precipitate ciui be decomposed by SH^ and investigated. ** I
have only (s^iys Brieger) in the ease of mussels been able to extract from
the lead precipitate small quantities of pttimaines,"
The mercury filtrate is freed from mercury and evaporated, the
excess of hydrochloric acid being carefully neutnilised by means of soda
(for it must only he slightly acid) ; theri it is agnin treated with alcohol,
BO as to separate as much as possible the inorganic conetituents. The
alcoholic extract is evaporated, dissolved in a little wat«r, ueutmliaed
§65 1 J
ANIMAL TOXlSKa
f^09
with soda, acidulated with nitric acid, and preeipiuted with pUi>si>lio
molybdic acid. The phosphomolybdic acid pret^ipitAte \& decomfH^sed
with neutrid lead acetate, which process may be facilitated by heating on
the water-bath. After getting rid of the lead by treatment with SH^,
the fluid is evaporated to a syrnp and aJcohol added, by which process
many basic toxincs may be eliminateil as hydrocblor?ites ; or they vmu
bo converted into double salts (of platinum or gold) for the purpose of
separation. In the filtrate from pbospho-molybdate, bases may ako be
found by treating with lead acetate to gi>L rid of the pbospho-molybdic acid^
and then adding certain reactives. Since it is but seldom that the hydro-
chlorates are obtained in a state of purity, it m preferable to convert the
aubetanoe leparated into a gold or platinum salt or a picrate, since the
greater or less scjlobility of these compounds facilitates the purification of
iudividnal members; but which reagent is heui to add, must be learned
from experience. The melting-point of these salts must always be
taken, so that an idea of their purity may h^ obta^ined. It is also to be
noted that many gold gaits decompose on warming the aq neons ^lution ;
thia may be avoided by the addition of hydrochloric acid. The hydro-
chlorateii of these b^es are obtained by decomposing the mercury, gold,
or platinum combinations by the aid of BHg, while the picrates can be
treated with hydrochloric acid and shaken up with ether, which latter
solvent dissolves the picric acid*
Considerable difliculty in the purification of the bases is caused by
a nitrogenous, amorphonii, n on -poison mis, albumindike substance, which
passes into all solutions, and can only be got rid of by careful pre-
cipitation with an alcoholio solution of lead acetate, in which it is
soluble in excess. This albuminoid forms an amorphous compound with
platinum, and acts as a strongly reducing agent (the platinum compound
contains 29 per cent, platinum). When this albuminoid is ellniinalod,
then the hydrochlorates or the double salts of the bases crystallise.
g 65U The Benzoyl Chloride Method.— The fatty diamines in dilute
aqueous solutions, shaken with benzoyl chloride and smla, are converted
into insoluble di benzoyl derivatives ; these may be. ^separated from
benzamide and other nitrogenous products by dissolving the precipitate
in aloohr)!, and pouring the solution into a large quantity of water,*
Componnds which contain two araido groups combined with oue
and the same carbon atom, do not yield benzoyl derivatives when
shaken with benzoyl chloride and soda. Heuee this reaction can be
utilised for certain substances only. The solution mnat be dilute,
because concentrated solutions of creatine, creatinine, and similar bodies
also give precipitates with benzoyl chloride ; no separation, however,
Qocurs unless these bodies are in the proportion of five per thousands
* U V. Udriuiikjf and BAUlIlatlt^ J<t., xn, ^44.
5IO
POISONS: THEIH EFFECTS AND DETBCTION.
[§ 652.
The proc^B is specially applicable for the separation of ethylene-
diammo, pentaaietbylenediamiiie (cadaventie)^ and tetramethylenedia-
miiie (putrescine) from urine. In a case of cyatinuria Udrknakj and
K Baumann * have founrl 0 24 grm. of benzoyltetramethylenediaraine,
0"42 grm. of betizoylpentaraethylenedianiine ia a day. Di amines are
absent in normal ftecea and urine, Stadthageii and Brieger f have also
found, in a case of cystinnria dianiiues, chiefly pentamethyletjediamine*
The operation is performed by making the liquid alkaline with soda
80 that the alkalinity is equal to about 10 per cent,, adding benzoyl
chloride, shaking until the odour of benzoyl chloride disappears, and
then filtering j to the filtrate more benaoyl chloride is added, the liquid
shaken, and, if a precipitate appears, this is also filtered off, and the
process repeated until all diamines are separated.
The precipitate thus obtained is dissolved in alcohol, and the
alcoholic solution [xiured into a considerable volume of water and
allowed to stand over night ; the dibeuzoy] compound is then usually
found to be in a crystalline condition. The compound is crystallised
once or twice from alcohol or ether, and its melting-poiut and properties
studied. Mixtures of diamines may be separated by their diflerent
solubiUtiea in ether and alcohol*
A solution of 0 '00788 grm, of pentamethylenediamine in 100 c.c,
of water gave 0*0218 grra, of the dibenzoyl-derivative when shaken with
benzoyl chloride (5 o»c*) and 40 c.c* of soda (10 per cent.) and kept for
twenty-four hours, fn a second experiment with a similar solution only
0^0142 grni. of dibeiiaioyl'derivative was obtained; I hence the process is
not a good quantitative process^ and, although convenient for isolation,
gives, so far as the total amount recovered is concerned, varying res ults,§
S 652. The Amines. — The amines are bases originating from
ammonia and built on the samy type. Those that are interesting aa
poiionB are monaminee, diamines, and the quaternary ammonium bases.
Considered as compound ammonias, the amines are divided into
primary or amide bases, secondary or imid bases, and tertiary or nitrile
bases, according as to whether one^ two, or three atoma of hydrogen
have been displaced from the ammonia molecule by an alkyl; for
instance, metbylamine NHjCH^j ia a primary or amide base» because
* L, V, IJdr,\iiaky aod Baumunn, ZeiL /. pkysioh Chcm.^ xiii. 562.
t Arch. pathoL AntUoni.^ cxv, p. 8. t ^^»i 3tri. 2744.
§ J. Otori has sbowTi that most of the ^raineB oa well as betaliie, chciliDe, neunnr^,
aad lyBlne fona difficultly solublo comjiounda witlr picro -Ionic acid : benoi^ this acid
may be n&ed as a group reagent like benzoyl chloride. A« Loewy and C« Neiibei^
have shown thftt on ether solution of phenylisocyanato ia naefnl for the iip[»aratiou
of iisertaip dia0unGB| compounds with the dtamiii^ being readily formed. The
phenyl -diamine comjKJunda are dried, diBsol red in pjfTidiue so as to form a saturated
3*olution ; out of thi& acetone preci pita tea (if present) (mmediately the tetrametliylene
derivative, whereaa the others require hours to Hejjcirat*! {^eit.f. phyaiuL Ckenrnt tliu.}.
§ 652]
THE AMINES.
Sn
uulj one of the tliree atoms of H m NH^ bos beeu re [placed by methyl ;
similarly, dimethylamine is a secondary or imid base, and triniethyl-
amine is a tertiary or nitrile base.
The quaternary bases are derived from the hypothetical ammonium
hydroxide NH^OH, as, for etamplej t«tracthyl ammonium hydroxide
{aH,),N,OH,
The diamines are derived from two molecules of NH, and therefore
contain^ instead of one molecule of nitrogen, two moleciilea of nitrogen ;
in two molecules of ammonia there are six atoms of hydrogen, two,
fotirj or «ix of which may be replaced by alkyla ; as, for example,
c,H An -
n^.hAn
Ethyleufldiatulnti. DktU>leii«dUiiniJie, Triethyleiic^iAtnine
The monamines are similar to ammonia in their reactions ; some of
them are stronger bases; for ins tan ee, eth^damine expels ammouia from
its salts. The first membera of the series are corab^jstible gases of
puugeni odoiir^ and easily soluble in water ; the higher bomologues are
fluids ; and the still bigher members solids.
The hydrochlorides are soluble in absolute alcohol, while chloride of
ammonium is insoluble ; tliis property is taken Jidvantiige of for separat-
tijg amines from ainmonia. The amines form double salts with platiuic
chloride ; this is also utilised fur recognitiouj for the purpose of scpara-
tion, and for purification ; for instance^ ammonium-platinum-cbloride on
iguition yields 43^99 per cent of platinum, und methykmine-platinnm'
chloride yields 47 '4 of platinum. It is compara lively easy to ascertain
whether an amine is primary, secondary, or tertiary.
The primary and seeotidary amines react with nitrous acid, but not
the tertiary ; the primary amiues^ for instance, are converted into
alcohols, and there is an evolution of nitrogen gas ; thus methylamine b
deoompoaed itito methyl alcohol, nitrogen, and water.
CHaNHs + {OH)NO = CHa(0H) + N\+ H^O.
The secondary amines, treated in the same ^*B,y, evolve no nitrogen,
btit are converted iuto nitrosamines ; thus dimethylamine, when treated
with nitrous acid, yields nitroaodi methylamine,
(CH^lgNH + (OH)NO = (CHa),,(NO)N + H,0 ;
and the nitrosamines respond to the test known as Lieberman's nitroso-
reaction, which is thus performed : — The substance is dissolved in
phenol and a few drops of concentrated sulphurii^ acid added. The
yellow colour at first produced changes into blue by adding to the
acid liquid a solution of potash.
The primary amines, and the primary amines alone, treated with
512
POISONS: THEIR KFFBCTS AND DETECTION.
[§ 652.
chloroform aud alcoholic potauh, yield the peculiarly offensive smelling
carbylamine or isonitrile (Hofmann's test),
NH2(CH3) + CHClg + 3K0H = C^N^— CH3 + 3KC1 + 3H2O.
Again, the primary bases, when treated with corrosive sublimate and
carbon disulphide, evolve sulphuretted hydrogen, and mustard oil is
produced, e.f/.,
NH2(C„H5) + CS2 = CSIIN- C2H. + HgS.
Ethylaniine. Ethylmustaraoil.
Where a sufficient quantity of an amine is obtained, the primary,
secondary, or tertiary character of the amine may be deduced with
certainty by treating it with methyl or ethyl iodide.
A molecule of the base is digested with a molecule of methyl iodide
and distilled with potash ; the distillate is in the same manner again
treated with methyl iodide and again distilled ; and the process is
repeated until an ammonium base is obtained, which will take up no
more iodide. If three methyl groups were in this way introduced, the
original substance was primary ; if two, secondary ; if one, tertiary.
The quatemaiy bases, such as tetraethyl ammoniumoxhydrate, de-
compose, on heating, into triethylamine and ethylene ; the corresponding
methyl compound in like manner yields trimethylamine and methyl-
alcohol.
On the other hand, the primary, secondary, and tertiary bases do not
decompose on heating, but volatilise without decomposition.
The chief distinctions between these various amines are conveniently
put into a tabular form as follows : —
Primary,
Seconilanr,
Tertiary,
Quaternary,
NH.2R.
NHK^.
NK3.
NR4(0H).
On treating with methyl
iodide it takes up the
following number of
methyl group, . . .
Reaction with nitrous
3
2
1
acid,
Decom{>08e8
with evolu-
tion of ni
trogen gas.
Formation of
n i t r 0 s-
amine.
Mustard oil, Ac, on treat-
ment with CS2 and Kub-
limate,
Mustard oil
formed.
Chloroform and alcoholic
potash,
Formation of
0 a r b y 1-
amine.
...
...
Effect of strong heat, . .
Sublimes.
Sublimes.
Sublimes.
Decomposes.
On addition of acids, . .
Combines to
Combines to
Combines to
form salts.
form salts.
form salts.
§ 653-^59^1
THE AMINRB,
513
g 6&S. Metliylamine^ CHjiKH;,.— TbLs is a gas at ordinary t€mpemtiir«$ ; ft is
intlamDmbloj and jio^e^ses a strong auimomural odour. It has been found in herring
brinej and is present in uultiires of the comina bacillus; it has &\&3 hmn found in
poianQoua aaaaages, but it is not in iUelf toxic.
It formB crystalline salts, such as^ for exam pit), the hydroehlonde, the platino-
chloride {Pt = 11/4 j»er cent), and th<j aurocbloride (Au = i>3*3 jwr €cDt» when anhy-
drous). The best aalt for estimation is the platinochloride, insoluble in atutolule
alcohol and ttlier,
§051. Bimelhylumne, (CHjj),^!!. — Dimethylatnino alao is a gua ; it has be^n
found in various putrafying substances. It fonns ciyBtalline salts, such as the
hydrochloride, t\m platinochloride (?t^39*l per ocnt.)| and an aurochloride (An^
51*35 per cent.). It is not poisonous.
In Brieger*! process it niay occur in both the moreuric chloride precipitate and
filtrate. Front cadavcritto tt may be separated by pldtiuum chloride ; cadaverinc
platinochloride is T^-ith difficulty solublf* in cold water and cTystallisea from hot water,
while dimethyls mine remains in the mother liquor. From choline it may bo
separated by recryatallising the mereujic precipitate front hot water* From methyl'
amine it may be seiiaratal by converting into chloride and extracting with
chloroform ; dimethylnmine chloride b aoluble, methylamine chloride insoluble in
chlorofoiTU*
§ 655, Trimethylnmino, (CHj)3N, — Trimethylaniine in the free state h an
alkaline liquid with a tiahy odour, boiling at 9 '3"; it is not toxic save in large
doaet.
It occurs in a great variety of plants, and is also found in putrefying stibatances.
It is a product of the decomiu^sttion of choline ^ bet^nei and neuridiue, when thsse
aubstaiicca are distilled with potash.
In Brieger's process^ if an aqueous solution of mercuric chloride is U8«d as the
precipitant, trimethylannne (if j^reaeot) will be almost entirely in the filtratej from
which it can be al^teincd by getting rid of the mercury by SH^^ filtenng, evaporating
to dryness^ extracting with alcohol^ and precipitating the alcoholic solution with
platinic chloride. It forms crystalline salts with hydrochleric aciJ^ platinum
chloride, and gold chloride i the platinum double salt yields 37 jwr cent, of
platinum, the gold salt 49 4 f^r cent. gold. The gold salt i^ ^itly soluhlej and
this proi>erty permits its sei^iaration from choline , which forma a compound with
gold chloride soluble with difhimlty.
§650. Ethylftmin^, Q^Hj^NHg.— Ethylamine is in the free state an ammoniacal
liquid tjoiling at 187*. It is a strong base, mi^ible with water in every j>roiiortbD.
It has been found in putrefytiig yeast, in wheat flour^ and in the distillation of beet
sugar residue. It is not jK^isonous ; the hydrochloride forms deliquescent plates
melting at 7*j'-&0* ^ the platinochloride contains 39 '1 per cent of platiiiimi, and
the gold fcalt 51 "35 jier cent of gold. In other woids, the same i>ercentftgeii an the
ooiTespondirig S!tlt» of dinu*thylamine, with which, however, it cannot he confused.
I 057. Siethylaminej (iJ^jH^J^NH^ h an in^ammablf^ liquid boiling at fi7'&*; tt
forms salts with hydrochloric^ acid, platinum and gold, etc.; the gold salt contaiiis
47*71 i>er cent* of gold, and its melting- point w about 165*,
§ G£S. TriethylajniiLe, (C^Ha)-}N, is an oily bo^e but slightly soluble in water^ and
boiling at 89*-89"5*, It gives no precipitate with merouHc chloride in aqueous
aolntioii; it forms a platinochloride contaiuing 31 '8 |>er cent of platinum. It has
been found in putrid titih.
§659, propylamine. — There w« two propylamine; one, normal propylamine,
CHaCH^CH^NH^ boiling at 47'-48% and isO'pro]iylamine» (GHjf>/JH.NUg,
I boiling at 31 '5" ; both are ammoniacal fish -like smelling liquid jt- The hydro-
' chloride of normal propylanune melts at l^S^-l^S*, and iso-p ropy lam ino chloride
melts at 139 ^r.
514 POISONS: THEIR EFFECTS AND DETECTION. [§ 660-662.
It has been found in cultures of human fseces on gelatin. None of the aboye
amines are sufficiently active in properties to be poisonous in the small quantities
likely to be produced in decomposing foods.
§ 660. Iflo-amylamine, (CHj)2CH.CH2.CH2.NH2, is a colourless alkaline liquid
possessing a peculiar odour. It boils at 97*'-98*'. It forms a deliquescent hydro-
chloride. The platinochloride crystallises in golden yellow plates.
Iso-amylamine occurs in the putrefaction of yeast, and is a normal constituent of
cod-liver oil. It is intensely poisonous, producing convulsions.
DIAMINES.
§ 661. Bate of Formation of Diamines. — Diamines are formed in
putrefactive processes generally where there is abundance of nitrogen.
Garcia* has attempted to trace the rates at which they are formed by
allowing meat extracts to decompose, precipitating by benzoyl chloride
(see p. 509) the dibenzoyl compound, and weighing ; the following were
the results obtained : —
Time. Weight of benzojl compoand.
24 hours, 0*56 grm.
2 days, 076 „
3 days, 0*82 „
4 days, 073 „
5 days, 0*67 ,,
6 days, 0*68 „
§ 662. Ethylidenediamine.— Brieger found in putrid haddock, in the filtrate from
the mercury chloride precipitate: — gadinine, neuridine, a bas^ isomeric with
ethylenediamine C2H8N3 (but which Brieger subsequently more or less satis-
factorily identified with ethylidenediamine), muscarine, and triethylamine ; these
bases were separated as follows : —
The filtrate from the mercury chloride solution was freed from mercury by SHj,
evaporated to a syrup, and then extracted with alcohol From the alcoholic solu-
tion platinum chloride precipitated neuridine ; this was filtered off, the filtrate freed
from alcohol and platinum, and the aqueous solution concentrated to a small volume
and precipitated with an aqueous solution of platinum chloride ; this precipitated
ethylidene platinum chloride. The mother liquor from this precipitate was concen-
trated on the water-bath, and, on cooling, the platinochloride of muscarine crystal-
lised out From the mother liquor (freed from the crystals), on standing in a
desiccator, the gadinine double salt crystallised out, and from the mother liquor
(freed from gadinine after removal of the platinum by SHg) distillation with KHO
recovered trimethylamine.
From the platinochloride of ethylenediamine, the chloride can be obtained by
treating with SH3, filtering, and evaporating; by distilling the chloride with a
caustic alkali, the free base can be obtained by distillation.
Ethylidenediamine is isomeric with ethylenediamine, but differs from it in the
following properties: — ethylidenediamine is poisonous, ethylenediamine is non-
poisonous.
Ethylenediamine forms a platinochloride almost insoluble in hot water, while the
ethylidene salt is more easily soluble. The properties of the gold salts are similar,
ethylenediamine forming a difficultly soluble gold salt, ethylidene a rather soluble
gold salt.
* ZeiLf. phyaiol, Chemie, xvii. 6. 671.
§ 663.1
DIAMINES.
515
EtbylideDediamlne forma a hydrochloride^ CyjH^N^2HCI, crjBialli<iing iji long
gliatading noedlta, iHsoluhle itj abaolut* alcohol, mther soluble in water. The
hydrochloride gives i>r<K;ipitntt5 in aqueous solution with phosjiho-molybdic acid,
phoapho-antinionio acid, and potessium hiBiuutb iodidu j the latter m in the form of
red platea.
The plitinochloridei CgHaNa2HCLPtCl {Pt=63*6 per a«nt.), is in the form of
y«ilow plates, liot very aoluble in cold water
Ethylidenedkmiue, when subc titan eou sly injected into guinearpigs,
produucs an abuudant secretion from the mucoua membranes of the
noae, mouth and eyes. The pnpils dilate, and the ©jelmlls projetit.
There is actite dyspnom; death tftkea place after some twenty-four
hours, and tbo heart is stopped in diastole.
Trimethylenediamine is believed to have been isolated bj Brieger
from culti vat tons in beef broth of the comma bftcillus.
It occurs ill small quantity in the mercuric chloride precipitate, and
13 iaolated by decom|>oaing the precipitate with SH^, evaporating the
filtrate from the mercury sulphide to drynessp taking up the residue
with absolute alcohol, and precipitating by an alcoholic solution of
sodium picrate. The precipitate contains the picrate of trimethylene-
diamiiie, mixed with the picratea of cadaverine and creatinine. Cada*
verine picrate is insoluble in boiling absolute alcohol^ the other pierates
soluble ; ho the mixed pierates are boiled with absolute alcohol^ and the
insoluble cadaverine filtered oQ\ Next, the picratea of creatinine and
trimethylenediamine are freed from alcohol, the solution in water
acidified with hydrochloric acid, the picric acid shaken out by treatment
with ether, and then the solution precipitated with platinum chloride ;
the plattnocUoride of trimethylenediamine is not very soluble^ while
cr^tinine easily dissolves; so that separation is by this means fairly
^sy.
It alao gives a ditficultly soluble salt with gold chloride.
The picrate eonsists of felted needles, melting-point 198** Pbospho^
molybdic acid gives a precipitate crystallising in plates; potaastum
bismuth iodide gives dark-coloured needles,
It produces in animals violent convulsions and muscular tremors ;
but the substance has hitherto been obtained in too Bmall a quantity
to be certain as to it^ identification and properties-
g 663, Kenridine, C^H^Na, — Nenridine is adiamino^ and is apparently
the moat common basic product of putrefaction ; it haw been obtained
from the putrefaction of gelatin, of horseflesh, of fish, ami from the yelk
of eggs. It is usually accompanied by choline, from which it can be
separated by converting the bases into hydrochlorides, choline hydro-
chloride being soluble in absolute alcohol, neuridino scarcely so. Brieger
isolated neuridinc from putrid flesh by precipitating the watery extract
with mercuric chloride* He decomposed the mercury precipitate with
5l6 POISONS: THKIR EFFECTS AND DETECTION. [§664.
SHj, and, after having got rid of the sulphide of mercury by filtration,
he concentrated the liquid to a small bulk, when a substance separated
in crystals similar in form to urea ; this was purified by recrystallisation
from absolute alcohol, and converted into the platinum salt.
Another method which may be used for the separation and purification
of neuridine is to dissolve it in alcohol and precipitate with an alcoholic
solution of picric acid ; the pierate may be decomposed by treatment with
dilute mineral acid, and the picric acid removed by shaking with ether.
The free base has a strong seminal odour. It is gelatinous, and has
not been crystallised. It is insoluble in ether and in absolute alcohol,
and not readily soluble in amyl alcohol. It gives white precipitates with
mercuric chloride, neutral and basic lead acetates. It does not give
Hofmann's isonitrile reaction. When distilled with a fixed alkali, it
yields di- and trimethylamine.
The hydrochloride, C5H14N22HCI, crystallises in long needles, which
are insoluble in absolute alcohol, ether, benzol, chloroform, petroleum ;
ether, and amyl alcohol ; but the hydrochloride is very soluble in water
and in dilute alcohol.
The hydrochloride gives no precipitate with mercuric chloride, potass-
mercuric iodide, potass cadmium iodide, iodine and iodide of potassium,
tannic acid^ ferricyanide of potassium, ferric chloride, and it does not
give any colour with Frohde's reagent.
On the other hand, phosphotungstic acid, phospho-molybdic acid,
picric acid, potass-bismuth iodide, platinum chloride, and gold chloride
all give precipitates.
Neuridine hydrochloride is capable of sublimation, and at the same
time it is decomposed, for the sublimed needles show red or blue colours.
Neuridine platinochloride, C5Hi4N22HCl.PtCl4, yields 381 per cent,
of platinum ; it crystallises in flat needles, soluble in water, from which
it is precipitated on the addition of alcohol.
The aurochloride has the formula C5H14N22HCI2 AuClg ; it is rather
insoluble in cold water, and crystallises in bunches of yellow needles.
On ignition, it should yield 50*3 per cent, of gold.
The pierate, C5Hj4N2,2CgH2(N02)30H, is almost insoluble in cold
water, and crystallises in needles. It is not fusible, but decomposes
at about 230*.
Neuridine is not poisonous.
§ 664. Cadaverine (Pentamethylenediamine, C5H14N2 = NHgCHg—
CH2 — CH2 — CHgCHgNHj) is formed in putrid animal matters, and in
cultures of the genus Spirillum. It has been found in the urine and
fsBces in cases of cystinuria, and Roos * has separated it by the benzoyl-
chloride method from tlie faeces of a patient suffering from tertian ague.
* Zeit./.physiol.Chemie,j.vi.,lSd2,
§664-1
DIAMINES.
$'7
It maj be formed ajntbetically b^ dissolving trimethjlcjr^'nide iti
absolute filcohotj and then reducing by sodium (Mendius* reaction).
Cadaverme m a thick, oletiFj syrupy liquid, mtU a pecnltar coniine^ as
well aa a s@nieii4ike odour. It absorbs eagerly COa from the aifj at id
ultimately is converted into a solid crystulliue mass. IL volatilises with
the ste^m when boiled with water, and mixy be distiJled in the presence
even of the eauiitic alkalies and tlie alkaliue earth without deaomjKisitioii.
It does not give oil of mustard when treated with CS^j and mercuric
cbloride, nor does it give with chloroform and akoholi€ potash, earbyb
amine (iaonitrile). If deliydrated by KHOj it boils at from 115°-120'
( Driet/er),*
Wbeo cadaveriue is treated with methyl iodide, two atoms of hydrogen
may be replaced with methyl, forming the kise 0^H^.^{CH^)^N2 ] the
platinochloride of this last ba«e cryatalb»e8 in long red needles,
Cadaveriue forms well-deBned crystalline mlv^ a^ well as compouudB
with metals,
CadHverine hydiTKihloride, C^Hi^N^SHCl, crystallises in needles which
are deliquescent, or Jt may be obtained from an alcoholic solution in
plates. The crystals are insoluble in absolute alcohol, but readily
soluble in 96 per cent, alcohol Futrcscine hydrochloride, on the other
hand, m with difliculty solubb in alcohol of that Btreogth ; hence the
two hydrochlorides can be separated by biking advantage of their differ-
ence in solubility in 96 per cent, alcohol ; but the better method for
separation is the benzoyl-chloride process (p. 509). On dry distillation-
cadaverine hydrochloride decomposes into NH3,HC1 and piperidine
C^lJjjN. The compound with mercury chloride^C^Hj^Kg^HCljiHgClj
(Hg = 6354 per cent) ; meltiog-point, 214*-216'' — is insoluble in alcohol
and in eold water ; this property is also useful to separate it from putres-
cioe, the mercury compound of which is soluble in cold water. The platino-
chloride, C5Hj^N22HCl,PtC\ (Pt = 38-08 per cent,), crystallises in dirty
red needles ; but, hy repeated crystal I iaation, it may l^e obtained in clcfir
chrome yellow, short, octahedral prisms ; it is soluble with difficulty in
hot water, insoluble in eold water. The salt decomposes at 235'-236'.
The aurochloride— C5HnN22HC12AuCl (Au = 6b5 per cent), melt-
ing-point 188* — crystallises partly in culies and partly in needles, and
is easily soluble in water.
Other salts are the pierate, C£^HyN22C,.K^(N 02)3011, melting-point
221' with decomposition ; with difficulty soluble in cold, but dissolving
in hot water, and insoluble in alisolutc alcohoL There are also a neutral
oxalate, O^Hi^N^jH^C^Oi + 2H,jO, melting-point 160' ; and an acid oxalate,
C^H,^N.22H2CjO| + H^O, melting-point 143" with decomposition; both
those oxalates are lusoluble in absolute alcohoh
* Bri&ger has also giveu Iq the puiu h&m a boiling- ^oiatQt Vlli^.
5l8 POISONS: THEIR EFFECTS AND DETECTION. [§ 665.
Cadaveriuedibenzojl— C^Hip(NHCOCgH5)2, melting-point 129'-i30''
— crystallises in needles and plates, soluble in alcohol and slightly
soluble in ether, insoluble in water.
It is not acted on by hot dilute acids or alkalies, and when dissolved
in concentrated hydrochloric acid and alcohol it is, only after prolonged
boiling, decomposed into benzoic acid and the free base. The benzoic
acid after getting rid of the alcohol by evaporation, can be removed by
shaking up with ether ; then the hydrochloride can be decomposed by an
alkali and the free base obtained, or the platinum salt of cadaverine may
be formed by precipitation with platinum chloride. Should cadaverine
and putrescine be in the same liquid, the dibenzoyl compounds may be
separated as follows: — the crystalline precipitate is collected on a
filter, washed with water until the filtrate runs clear, and then dissolved
in warm alcohol ; this solution is poured into twenty times its volume of
ether and allowed to stand ; after a short time crystals form of the
putrescine compound, which are far less soluble in alcohol than those of
cadaverine dibenzoyl ; these crystals are filtered off and repeatedly
crystallised from alcohol until the melting-point is about 175*-176'.
The filtrate contains the cadaverine compound ; this latter is recovered
by evaporating oflF the ether-alcohol.
§ 665. Putrescine— Tetramethylenediamine,
C4H12N2 = NH2CH2CH2CH2CH2NH2.
The free base is a clear liquid, with a semen-like odour, boiling-point
135*. It is a common base in putrefying animal substances, and also
occurs in the urine in cases of cystinuria. It can be obtained syntheti-
cally by reducing ethylene cyanide by the action of sodium in absolute
alcohol.
The best method of separating putrescine is the benzoyl chloride
method already given.
Putrescine forms crystalline salts, of which the following are the
most important : —
Putrescine hydrochloride, C^H^g^g^HCl, forms long colourless
needles, insoluble in absolute alcohol, easily soluble in water.
The platinochloride, C4Hi2N22HCl.PtCl4 (Pt = 39-2 per cent.), is
with difliculty soluble in cold water. When pure, the salt is in the
form of six-sided plates.
The aurochloride, C4HJ2N22HCI.2AUCI3-1-2H2O (Au = 51 '3 per cent),
is insoluble in cold water, in contradistinction to cadaverine aurochloride,
which easily dissolves.
The picrate, C4Hi2N22CttH2(N02)80H, is a salt of diflacult solubility.
It crystallises in yellow plates. It browns at 230"*, and melts with
)lution of gas at 250*.
§666-669,]
DIAMINEB.
S"9
Dibenzoyltjutrescine^ C^Hg(KHCOC^H^)._„ forma silky pktes or long
needles, melting-point 17 5°- 176'* By boiling it for twelve hours with
alcohol and strong hjdrochloriu acid the compound may be broken up into
hydrochloride of putreaciue and free benzoic acid* Aa stated before, it
h less soluble iu alcohol than the corresponding compound of cadaverine*
Putreaciue is not poisonous. On the other hand, by repeated treat-
ment with methyl iodide, it takes up four methyl radicals^ and the
tetramethyl compound, C4Hg(CHg)4N2i produces symptoms similar to
those of muscarine poisoning.
§ ^%^. Metaphenylenediamine, ^e^A , ia »■ cryHtalHne sub-
stance, melting-point 63", boiling-point 276*-277". The ctystak are easily
soluble in alcohol or ether, with difficulty in water* The least truce of
nitrous acid strikes a yellow colonr from the formation of triamidobenseol.
§ 667* Paraphenylenediamijie, OhE^m\ « ^** "^ the form of
tabular crystalsp melting-point 1 40", boiUng- point 267°* If thiii subBtunce
is oxidised with ferric cblondeor manganese blnoiideand sulphuric {leid,
chinone is produced; if treated with SH., and ferric chloride, a violet
sulphur- hold jug colouring matter^ aUied to metliylene blue, is formed ;
these react ioniii are tests for the presence of the pim- com pound.
Both these diamines are poisonous* Metapheuytenediamine pro-
duces, in the dog, the symptoms of an aggravated influeUKa with con-
tinual sneezing and hoarse cough, which, if the dose is large enough^ ends
in coma and death. Panvphcnylenediamine produces exophthalmia,
the tissues of the eye undergoing complete alteration,*
Both compounds, iu doses of 100 mgrms, per kilo., t^use more or
less salimtion, with diarrhea. The para-compouud is more poisonous
than the motacompouud. So far, neither of these diamines have
been separated with certainty from the urine of sick persons, nor from
products of decomposition,
§ 66B* Hexamethylenedianiine, C^H,,^N^. — Hezamcthylenediamine
has been found by A. Garcia t iu a putrefying mijcture of horse-flesh
and pancreas*
§ 669* Dietbylenediamiiie, C^Hj^N.,, is a crystalline substance,
melting-point 104', boiling-point 145°-H6°* After melting, it solidifies
on coolings forming a hard crystalline mass. It is eitreuvely soluble in
water, and is deposited from alcohol in large transparent crystals* A
technical product called **spermin piperaridin '* or *' pi[>eraxine " has
been found by A, W. v. Hoffmann j to be identical with diethylene-
■ (hmtda Eend.^ cvii. 533-535, t ^tiL/. phf$iol, Ch^mie, xvH 513-565*
X Btr, , xxiii- 3297-3303.
520
POISONS: THEIU EFFECTS AND DSTECTION. [§670,671.
diamine. The hvdrochloride crystal Uses iu colourless needles, insoluble
in alcohol, readily soluble in water* The ttlatiuochloride, C^HjjjNgHg
FtCl^, IB in gmall yellow needleSf and ie fairly easily soluble in hot
water, but dissolves but slightly in hot alcohol. The mercuro-chloride,
C^HnjNjjRgHgCI^, orygtdllisea in concentrically g^roupcd needles^ and is
readily soluble in hot water, but is reprecipitated on adding alcohol.
The pi crate, C4HJPN2, CgHg(N03}30Ht crystallises from water in yellow
needles, almost insoluble in alcohoL*
g 670, Mydaleine is a ix)isonous base discovered by Brieger in putrid
animal matters. It is probably a diamine, but has not been obtained in
sufficient quantity for accurate chemical study. The platiuochloride is
extremely aolublc in water, aud only comeij down from an absolute alcohol
solution. It has been obtained in a cryst^illine form, giving on analysis
38'T4 per cent, of platinum, C. 10'83 per cent, H. 3 23 per cent.
Mytlalciiie is very poisonous. Small quautitiea injected into guinea-
pigs cause dilatation of the pupil, an abundant seci'etion from the nose
and eyes, and a rise of temperature. Fifty mgrms, cause death. The
post-morteju appeiirauevs are not distinctive ; the heart is arrested in
diastole; the intestines and bladder are contracted. In cats it causes
profuse diarrbcBa and vomiting.
§ 67 L Guajiidine, — Guauidine may be considered to have a relation
to urea ; for, if the oxygen of urea is replaced by the imide group NH,
guanidine originates thus : —
Urea =
Guauidine = KHC/
L = Oiz:C<
Hence giiantdine from its strnctural formula is a carbodiamidimide.
Gmvuidine may be formed by the action of oxidising agents, such as
potaHsic chlorate and hydrochloric aoid, on guanine; or by heating
amide cyanide with ammonium chloride^ and so forming guauidine
chloride. It is also produced from the oxidation of albumin. Wbcn
boiled with baryta- water it deeompo^s into urea and ammonia. It com-
bines with acids to form salts; the gold salt, CH^NgHCltAuCl^, is in the
form of long yellow needles, with difficulty soluble in wafcen Guanidine
nitrate, CH^N^HNO,, is also almost insoluble in cold water and similar
to urea nitrate- Bj dissolving equivalent parts of phenol and guanidine
in hot alcohol, triphenylguanidine is formed ; on adding picric acid to a
solution of tripheuylguanidino, phenylguanidine picrate, CH^Ph^NgC^Hj
{N02){|0H, is formed^ and falls as a precipitate of slender needles, melting-
point 208° ; this picrate is very slightly soluble, 1 part dissolving in
12^220 parts of water at 15^ Guanidine Is poisonons.f
• Siober, J,, Btr,, iiiii. 326-327.
t 0. FHiiigfr, Monai^^t xUl 97-100*
§ 672.]
MKTHTLGUANIDINE.
S2I
A method of aeparating guanidints from xvcine has been worked out by
Gergers and Baumann.* The principle of the method is based upon
the fact that guanidiDe ie precipitated by mercuFOUS oxide. The
urine is precipitated by hydrate of baryta, the precipibite filtered
oW, the alkatine liltrate neutraliBed by bydroeblorie acid, and the
neutnil filtrate evaporated to a syrup on the water-bath; the syrup
ii exhausted by absobite alcohol, aud the aleoholic solution filtered ;
this filtrate is freed from alcohol by distillation^ the alcohol free
residue dissolved in a little water, shukeu up with freshly precipi-
tated mercury oxide, and allowed to stand for two days in a warm
place; the precipitate formed is collected, acidulated with llCl and
treated with 8H^ j the mercury sulphide thus obtained is separated by
filtration, the filtrate evaporated, and the residue dii^golved iu absolute
alcohol This aoJutiou is precipitated by platinum chloride, filtered,
separated from any platinum ammotiium salt, atid evaporated to a small
volume. After long standing the guauidinc salt crysttUlises out. The
best method to identify it appears to bo, to ascertnin the absence of
ammotiia and of urea, and theti to gently warm the supposed guauidine
with an alkali, which breaks guauidine up into ammonia and urea,
according to the following et|Uation :
The physiological effects of guanidiue are as follows :—
A cetitigrm. of guanidine salt injected into the lyo>ph siicin the back
of frogs pr<xluces, after a few miuutesj muscular convulsions : first, theire
are fibrillar twitchings of the muscles of the Imck ; nest, these spread
generally fio that the whole surface of the frog seems to be in a wave-like
motion. Irritation of the limbs produces tet-mns. There is, at the same
time, increased secretion from the skin. The breathing is irregular. In
large dosos there is piraljsis and death. The heart is found arrested in
diastole. The fatal dose for a frog is 50 mgrms. ; hut 1 mgrm. will pro-
duce symptoms of illness. In dogs there is paralysis, convulsions,
vomiting, and difiicult breathing.
NlLCHg
g 672. Methylguanidine, N:nBC/^ . — Methylguauidine has
been isolated by Brieger from putrefying horseflesh ; it has also been found
in impure cultures in beef broth of Fiukler and Prior*8 Spirillum Fin/derL
Bockliach isolated it, working witli Brieger's process, from th** mercuric
chloride precipitiite, after removal of the mercury ami coneer>tration of
the filtrate, by addirjg a solution of sodhun picratc* The precijutate
contained the picrate of cadaverine, creattniue, and m ethylg nan i dine ;
cadaverine picrate, insoluble in boiling absolute alcohol^ was sepiiratod
• Plluger'a Arthiv, xiL 205.
522 POISONS: THKIB ETFKTS AXD DBTKnOX. [5 673, 674.
bj filtering from a solution of the picrates of the bases id boiling absolute
alcohol ; the alcohol was eTapmmted from the filtrate and the residue
taken up with water. From this aqueous solution the picric acid was
remoTed and then the solution precipitated with gold chloride : methvl-
gnanidine was precipitated, while creatinine remained in solution.
Methjlguanidine aurochloride, CJi7N,HCLAuC]3 <Au — 47'7 per
cent.), forms rhombic crystals easily soluble in alcohol and ether:
meldng-point 198*. The hydrochloride, CH-NjHCl, crystallises in
needles insoluble in alcohol. The picrate, C.H.N,C«H«( N0^)20H,
oomes down at first as a resinous mass, but, after boiling in water, is
found to be in the form of needles soluble in hot absolute alcohol ;
melting-point 192*. The symptoms produced by methylguanidine are
rapid respiration, dilatation of the pupils, paralysis, and death, preceded
bj coDTulsions. The heart is found arrested in diastole.
§ 673. Sapiine, C^Hj^N*. — Saprine is isomeric with cadaverine and
nenridine ; it was found by Brieger in human lirers and spleens after
three weeks' putrefaction. Saprine occurs, in Briegers process, in the
mercury precipitate. Its reactions are very similar to those of cadaverine ;
the main difference being that cadaTcrine hydrochloride gives a crystal-
line aurochloride, saprine does not ; the platinum salt is also more
soluble in water than the cadaverine salt. It is not poisonous.
§ 674. The Cholme Group. — ^The choline group consists of choline,
neurine, betaine, and muscarine.
All these bodies can be prepared from choliue ; their relationship to
choline can be readily gathered from the following structural formuhe : —
CHjOH
CH,
COjH
CH.OH
j
1
CHj
1
CH
1
CHj
CHOH
\(CH,VOH
X(CH,)^OH
X(CH,)rOH
X(CH,VOH
CboUDe.
Seoiae.
Brtaine.
Uiucmrioe.
Choline is a syrup with an alkaline reaction. On boiling with water, it
decomposes into glycol and trimethylamine. It gives, when oxidised,
muscarine. It forms salts. The hydrochloride is soluble ui water and
absolute alcohol ; neurine hydrochloride and betaine hydrochloride are
but little soluble in absolute alcohol, therefore this property can be
utilised for their separation from choline. The platiiiochloride is in-
soluble in absolute alcohol ; it melts at 225* with effervescence, and
contains 31*6 per cent, of platinum. The mercurochloride is soluble
with difficulty even in hot water. The aurochloride (Au = 44*5 per cent.)
is crystalline, and with difficulty soluble in cold water ; but is soluble
in hot water and in alcohol ; melting-point 264* with decomposition.
Choline is only poisonous in large doses.
§675.6;6]
TFTE CHOLINE GROUP.
523
§ 675, Keurme (Trimetbjl^iuyl-flmraouium liydrate), Cj^H3N(CHjj)g
Oil* — Neurine is one of the products of decompoeition of choline, it ia
poisonouB, and hm been sepamted bj Brieger and others from deooiii
posing animal matters. In Brieger^s process, neurine, if present j will
he for the most part in the mercuric chloride precipitate, and some
portion will als^ be in the titrate* The mercury precipitate is decooi'
posed bj SHj, the mercury sulphide filtered off, and the filtrate, con-
oent rated, treated with abaoluLe alcohol and then precipitated by
platinum chloride. It is usually accompanied by eholiue ; the pi at) no-
chloride of chuline is readily soluble in water, neurine platiuochloride
is soluble with difficulty ; this property m taken advantage of, and the
platinoc blonde crystallised from water until pure. Neurine has a
strong alkaline reaction,
Neurine chloride, C/^Hi^NXI, crystallises in Rne needles. The pla-
tinochloride, (Cj^Hi^NGljqPtCl^ (Pt=33*6 per cent.), crysUilliscs in
octahedra. The salt is soluble with di^culty in hot water
The aurocbloride, C^Hi^NClAuClg (Au-46'37 per cent), forms flat
prisms, which, according to Brieger^ are soluble with difhculty in hot
water.
Neurine is intensely poisonous, the symptoms being similar to those
produced by muscarine.
Atropine is an antidote to neurinci relieving iu suitable doses the
effects, and even rendering animals temporarily immune against the
toxic action of neurine.
When a fatal dose of ue urine is injected into a frog there is iu a
short time pamlysis of the extremities. The respiration stops first, and
afterwards the heart, the latter in diastole.
The symptoms in rabbits are profuse nasal secretion and salivation
with paralysis, as in frogs. Applied to the eye, neurine causes con-
traction of the pupil ; to a less degree the same effect is produced by
the ingestion of neurine.
Trimetbyloxyammomuni hydrocbloride causes similar symptoma to
neurtue, but the action is less powerful. — V. Cervello, Arrh. Hal. Bio!.^
vii, 232-233.
g 676. Betame. — Betaine may be separated from a solution in alcohol
as large deliquescent crystals ; the reaction of the crystals is neutral
Distilled with potash, trimethylamine and other bases arc formed,
Betaine chloride, C^Hi^NO^Cl^ forms plates permanent in the air
and insoluble in absolute alcohol A solution of the chloride in water
gives, with potassium mercuric iodide, a light yellow or whitish yellow
precipitate, soluble in excess \ but on rubbing the sides of the tube
with a glass rod, the oily precipitate crystallises as yellow needles;
probably this is cbai'acteristic.
524
POISONS: THEIE KFFKCTS AND DETECTION. [§677,678.
The iiurouhloride (Au = 43*l per cent,) foniis fine cholesteme plates,
soluble in water; meUing-point '209°. Bctaine is not poisonous.
g 677. Peptotoxme. — Briefer submitted to the action of fresh gastric
juice moist fibrin for twenty-four hours at blood heat. The liquid was
eva|K>ratod to iv syrup and boiled with ethjlie alcohol, the ethylic
alcohol was evaporated, the res^idne digested with aniylic alcohol, and
the amy I alcohol in its turn evaporated to dryness ; the residue was a
brown amorphous (naas that was poiaonous. It was further piurilied by
treating the extract with neutral lead acetate and then filtered ; the
filtrate w^as freed from lead by SlI^ aud treated with ether, the ethereal
extract being then separated and evaporated to dryness ; this last residue
wjis tjiken up witfi amy J alcohol, tlie alcohol evaporated to dryness, and
the residue finally taken up with water and filtered. The filtrate is
poisonous. The poisonous substance, to which Brieger gave the pro-
visional name of peptotoxine, i^ a very sUible substance, resisting
the action of a boiling temperature, and even the action of strong alka-
lies. It gives precipitates with alkaloid al group reagents, and strikes a
blue colour with ferric chloride and ferricyanide of potajssium. The
most characteristic test seems to be its action with Mi lion's reagent
(a BoUitiou of mercury nitrate in nitric acid containing nitrous acid) ^
this gives a white precipitate which, on boiling, becomes intensely red.
It ia poisonouSj killing rabbits in dosea of 0*5 grm. per kilogrm,, with
symptoms of pamlysis and coma. The nature of this substance requires
further elucidation.
I 678. Pyridiiie Alkaloid from the Outtle FibIl — O. de Coninck*
has obtained, by Gau tier's procesa, an alkaloid from the cnttle fish, of
the formula CgHj^N^ in the form of a yellow, mobile, strongly otloroua
liquid, very soluble iu alcohol, ether, ami acetone, boiling point 202\
It quickly absorbs moisture from the air. It forms two merctirie
chlorides, one of which has the formula (CgHj|N,HCl)3HgCU; this
compound crystallises iu small white needles, slightly soluble in water
and dilute alcohol, but insoluble iu absolute alcohol, and decomposing
when exposed to moist air. The other salt is a aesqui-salt, forming
long yellowish needles, insoluble in ordinary solvents, and decomposing
when e?( posed to moist air. The alkaloid also forms deliquescent very
soluble salts with hydrochloric and bydrobroniic acids. A platinum salt
ia also formed, {CjiH^^N)3HgPtCi|i ; it is of a deep yellow colour, ahuost
insoluble in cold, but soluble iu hot water ; it is decomposed by boiling
water, with the formation of a very insoluble comixmnd in the shape
of a brown powder, {CgHj^N^^PtCU. Coninck's alkaloid, on osidation
with potassic perman^uate^ yields a gummy acid ; this acid, on purify-
ing it by conversion into a potassium salt and then into a cupric salt, was
* Cmi^pUa Emd., Qvl S&8, 8Slj 1604-1605 ; criiL £8-59, 60d-810.
§ 679. "^So-l
TBTAmNB — ^TKTANOTOXrNE.
52s
found to be nieotinic acid ; ao that tUe alkaloid is iindoubtedly a pyri-
dine compoimd ; indeed, the acid, distilled with lime, yields pyridine,
g 679, Poisons connectai with Tetantis.^-Bri^er, in 1887, isolated
a base of uukoowii compositioi*, to wijich he gave the name of **spa8ttio-
toiine." It wad produtied in cultures of the tetanus bacillus in beef broth.
Two more definite siibstancea have also be«u discovered, viz., tetatiiDe
and tetanotoxine*
Tetanine^ C^^MgoNjO^, is best isolated by the method of Kitasato and
Weyl^ Their uiethod of treating broth cultures of the tetanus bacillus
is ns follows :—
The broth ia digested with 0-25 per cent. HCl for some hours at
460", then rendered feebly alkaline, and distilled in a Tacuum, The
residue in the retort is then worked up for tetanine by Brieger^s
method ; the distillate contains tetanotoxine^ ammonia, indol, hydrogen
sulphide, phenol, and butyric acid^ On treating the contents of the
retort by Brieger^s mercury chloride method, the fijtrate contains moat
of the poison. The mercury is removed by SH^, the filtered solution
evaporated and eathautjted by absolute alcohol, in which the tetanine
dissolves. Any ammonium chloride is thus sepiratod, ammonium
chloride being insoluble in absolute alcohol* The alcoholic solution,
filtered from any iuaoluble s^uhstanco, is next treated with an alcoholic
solution of platinum chloride, which precipitates creatinine (and any
ammonium salts), but does not precipitate tetaiiine. The platinum
salt of tetanine may, however, be precipitated by the addition of other
to the nlctvholic solution. The platinum salt, as obtained by precipita-
tion from ether, is very deliquescent; it has, therefore, to be rapidly
filtered off* and dried in a vacuum* It can then be recrystallised from
hot 96 per cent, alcohol, forming clear yelbw plates ; these plates, if
dried in a vacuum, become with ditficulty soluble in water.
Tetanine may be obtained as a free base by treating the hydrochloride
with freshly precipitated moist silver oxide* It forms a strongly alkaline
yellow syrup, and is easily decomposed in acid solution, but is permanent
in alkaline solutions.
The platinochloride, as before observedj is precipitable by ether from
alcoholic solution \ it contains 28 '3 per cent, of platinum, and decom-
poses at 107*.
The base produces tetanus.
^ 680. Tetanotoxine nmy be distilled, and be found in the distillate
with other matters. It forms an easily soluble gold salt, melting-
point 130% The platinochloride is soluble with difhculty, and decom-
poses at 240". The hydrochloride is soluble in alcohol and in water,
melting-point aliout 205',
* M^,/. Uygimtf vilL 104.
526
POISONS: THEIR EFFECTS AND DETECTION. f| 68l, 682.
Tetauatoiiut? produces tremor^ tijen parulyeia, and lastly, violent
convulsions.
§ 68L Mydatoxine, C^HjaNOg.^— A base obtained by Brieger from
liorae-flesh in a. putrefaetive condition and other subitaiicea. It ie found
in the mercuiy chloride pre<3ipitate. The free bftse is an alkaline ayrnp,
isomeric with the base separated by Brieger from tetanuB cultures. Tlie
hydrochloride m a dcliqiiesceat synip, not forming any compound with
gold chloride, bnt uniting with phoHpho-molybdic acid in forming a
compound crystalliBing in cubes. It forma a double salt with gold
chloride, sparingly soluble in water. The platinochloride (Pt ^ 29 per
cent.) in very soluble in water, but not soluble in alcohol; raelting-poiufc
195** with decomposition.
The base in large doses is poisonous, causing lachrymation, diarrhoea,
and oonvulsions,
g 682. The FoiBOn of Mussels. — Annually a certain number of
people are seriously affected after eating mussels. One of the most
thoroughly investigated series of cases occurred among the stevedores
in 1885,* at Wilhelmhafen. A number of the men collected mussels
Etdhering to some of the vessels in the harbour, took them home, boiled
them, and they and their families partook of the same- There were nine-
teen serious cases of illness, of which four died. The syraptoms occurred
a few hours after the mesL There was a choking sensation, buniing
and tingling of the hands and feet. The speech was diliicultj and there
was vomiting and diarrhoea. The post-mortem appearances of the fatal
cases showed intense congestion of the mucous membmano of the intes-
tines* and hoDmorrhagic spots in the liver,
A^arious views have been advanced as to the cause of mussel poisoning,
but it is still obscure ; from the experiments of Bchmidtmann t a-ud others
it would appear that the mussel derives its toxic properties from tlje water,
for poisonous mussels taken from stagnant waters and placed in pure sea
water lose the property, to regain it when returned to the same water,
Salkowski foimd that the poison could be extracted by alcohol, and
could be heated up to 1 10'' without loss of power, but warm sodic carbon-
ate solution destroyed the poison ; % he found that the alcoholic solution
of the non-(>oisonous musfiela was quite clear and colourless ; on the other
hand, the liver of poisonous mussels yields a yellow colouring matter
which is changed by eoncentrated nitric acid into a grasa-green colour,
Brieger isolated a substance to which he ascribed the formula
C^HijiNt>2 and named myiiMoxirm ; his process was as follows : —
The mussels were boiled with water acidified by hydrochloric acid;
the liquid was filtered, and the filtrate evaporated to a syrup, and tlie
• lMui4chtMaI. Woehinsthr,, 1886.
t Viwliow'a -inrAiP, 1888, J Ihid,^ 1885,
§ 6^3]
THE POISON OF MUSSELS,
S27
Bjrup waa re}>eatedly extracted! with alcohal It was found advisable
to eihauBt thoroughly with altjohol, otherwise much poison remained
behind. The alcoholic solution was treated with an akoholic solution
of lead acetate. The filtrate was evaporated and the residue tjxtractod
with alcohoh The lead was removed by SH^, the alcohol diatiUed off,
water added to the remaining syrup, and the solution decolorised by
boiling with auimal charcoal. The solution was neutralised by sodium
carbonate, acidulated with nitric aeid, and precipitaterl with phospho-
molybdic acid. The precipitate was then decompoied by warming with
a neutral solution of lead acetate, and the filtrate (after the removal of
the lead by the action of SH^j) was acidulated with HCl and evaporated
to dryness. The residue was then extracted with alj^ioluto alcoholj
filtered from any insoluble chloride, e,;/*, be tain e chloride, and pre-
cipitated by mercury chloride in alcohol.
The free base has a most peculiar odour, whicli disappears on
eatposure to air ; at the same time, the poisonous properties also diminish.
The base is destroyed by boiling with sodium carbonate ; on the other
hand, the hydrochloride may be evaporated to dryness or be Ijoiled
without decomposing*
The hydrochloride crystallises in tetrahedm; the aurochloride
crystallises in cubes (Au = 4r66 per cent,). Its melting-point is 182%
Thesen, operating oti large quantities of poisonous mussels by
Brieger's process, however, failed to isolate mytilotoxine, and it is doubt-
ful whether thU substance, presuming it to exist, is the real poison.
g 683, Tyrotoxicon (Dia^obenKol, C^jH^K^^OH)), — ^It appears, from
the researches of Yanghan and others, that diazobonzol is liable to be
formed in milk and milk products, especially in summer time. It is
Gonftdently asserted by many that the summer diarrhoea of infants is
due to this toxine ; however that may be, it ia well established that
diazobenzol is a violent poison, causing sickness, diarrhcea, and, in large
doses, ati acute malady scarcely distiugtiiajhable from cholera, and which
may end fatally. There will always be difficulty in detecting it, because
of its instability. The following is the beat process of eitraotion from
milk. The milk wiU probably be acid from decomposition ; if so, the
whey must bo separated by dilution and filtration ; without dilution it
may be found impracticable to get a clear filtrate. In order to keep the
bulk down, 25 c.c^ of the milk may be diluted up to 100 c.c.^ and,
having obtained a clear filtrate from this 25 cc. thus diluted^ the filtrate
is used to dilute another 25 c,c. of milk, and so on. The acid filtrate is
neutralised by sodium carbonate, agitated with an equal volume of ether,
allowed to stand in a stoppered vessel for twenty-four hours, and the
ether then separated and allowed to evapoiate spontaneously. Tht
residue is acidified with nitric acid and then treated with a saturated
528 POISONS: THEIR EFFKCTS AND DETECTION. [§684,685.
solution of potash, winch forms a stable compound with diazobenzol, and
the whole concentrated on the water-bath. On cooling, the tjrotoxicon
compound forms six-sided plates. Before the whole of this process is
undertaken, it is well to make a preliminary test of the milk as follows :
— A little of the ether is allowed to evaporate spontaneously. Place
on a porcelain slab two or three drops of a mixture of equal parts of
sulphuric and carbolic acids, and add a few drops of the aqueous solu-
tion ; if tyrotoxicon be present, a yellow to orange-red colour is pro-
duced. A similar colour is also produced by nitrates or nitrites, which are
not likely to be present under the circumstances, milk having mere traces
only of nitrates or nitrites ; it may also be due to butyric acid, which,
in a decomposed milk, may frequently be in solution. Therefore, if a
colour occurs, this is not absolutely conclusive ; if, however, no colour
is produced, then it is certain that no diazobenzol has been separated.
That is all that can be said, for the process itself is faulty, and only
separates a fractional part of the whole.
§ 684. Toxines of Hog Cholera.— Toxines have been isolated by F. G.
Novy* from a cultivation of Salmon's bacillus in pork broth. The
fluid possessed a strong alkaline reaction. For the isolation Brieger's
method was used. The mercury chloride precipitate was amorphous and
was converted into a chlorine-free platinum compound, to which was
assigned the composition of CgH^^N^PtOg. After separation of this com-
pound, the mother liquor still contained a platinum salt, crystallising in
needles, and from this was obtained the chlorhydrate of a new base, to
which was given the name of susotoxine; it had the composition of
Cij^H2gN22HCl,PtCl4. Susotoxine gives general alkaloidal reactions,
and is very poisonous.
§ 685. Other Animal Tozmes. — Besides the animal toxines which
have been already described, there are a number of others ; the follow-
ing may be mentioned: i8oamylamine,t (CH3)2CH.CH2.CH2NH2 ;
butylamine, CH,CH2CH2CH2NH2; dihydrolutidine,+ CyHnN; hydro-
collidine,§ C^H^jN ; CjoHj^N (a base isolated by Guareschi and Mosso ||
from ox-Hbrin in a state of putrefaction by Gautier's method ; it forms a
crystalline hydrochloride and an insoluble platinochloride ; its action is
like that of curare, but weaker) ; II aselline, CjgHjgN^, isolated from cod-
liver oil ; typhotoxine,** C7H17NO2, isolated from cultures of Eberth's
bacillus. So far as the published researches go, it would appear that
other crystalline substances have been isolated from the urine, from the
• 3fed. News, September 1890. f Hesse, Chijn. Jahresk, 1857, 403.
X Gautier, A., and Morgues, Compt. Rend., 1888.
§ Gautier et Etard, Bidl, Soc. Chim., xxzviL, 1882.
II Guareschi et Mosso, Les ptomaines^ 1883.
IT Gautier, A., et Morgues, CompL Rend., 1888.
•• Brieger, 1885, Ptomaines, iii.
§ 68d] FOOD POISONING* ^^^^ 529
tissues, and from the secretions of patients suflTefing from various dis-
eases] the quantity obtainetl in each case has, however, been, under the
uiost favonmble circumstances, less than a gramme; often only a few
miHigrnas* To BpeeificalJy declare that a few milligrms. of a substance
is a new body, requires immense e.xperience and great skill ; and, even
where thode quaUhcationa are present, this ia too often impossible.
This lieing so, the long list of named animal toxines, such as erysipeline,
varioline, and others, must have their existence more fully confirmed by
more than one observer before they can be accepted as separate entities.
DIVISION III.— FOOD POISONING.
§ 680* A large number of cases of poisoning by food occur yearly ;
some are detailed in the daily press; the great majority are neither
recorded in any jonrnal, scientific or otherwise ; nor, on account of their
slight and passing character, i^ medical aid nought, Thi greatest portiou
of these cases are probeibly due to toxines existing in the food before
being consumed ; others may be due to the action of unhealthy fermeota-
tiou in the intestinal eanul itself ; in a tinrd claaa of cases, it is probable
that a true zymotic infection is conveyed and develops in the stifTerer ;
the latter class of cusea, aa^ for instance, the Middlesbrough epidemic
of pie uro- pneumonia, is outeide the scope of this treatise.
The develop meat of poisonous toxines in food is largely dependent
on the conditions under wliich food is kept Con tsimi nation in the
smallest degree of certain articles of food in summer time may easily
give rise to severe and even fatal diarrhoea, for it may be proved that
seeding sterile broth with healthy excreta, converts the broth, on incubat-
ing at blood heat, into a liquid which is fatal to rodents, the animals
dying from gastroenteritis.
Confining the attention to cases of food poisoning in which the
symptoms have been closely analysed and described, the reader m referred
to thirteen cases of food poisoning investigated by the medical officers
of the Local Government Board between the years 1878 and 1891, as
follows : —
1376. A Case of PoisoBing at Whitehurch from eating Boast Fork.
— Only the leg of pork wai poisonous ; other parts were eaten without
injury. Two persons died after alK^ut thirty hours' illuess. The pork
itself, on a particular Suutky, was innocuons ; it became poisonous
between the Sunday and the Monday ; the toxicity appeared to gradually
increase, for those who ate it for dinner on the Monday were not taken
ill for periods of from seven to nineteen hours, while two persons who
ate of it in the evetiini; were attacked four hours after eating.
i
S30
POISONS: THim EFFECTS AND DETECTION,
[§ 686.
1880* The Welbeck Epidemic, due to eating cold boiled ham- Over
fifty parsons affected. Symptoms commenced in from twelve to forty -
eight hours.
1861. A Series of Poisoning &om eating Baked Pork, Kottingham.
— Protuibly the gravy was tbo cause and not the pork itself* Many
persons seriously ilL One died.
188L Tinned American Sausage, ^A man in Chester died from
eating tinned American sausage. Poison found to be unequally diatri-
bated in the eausage.
1 882. PoiBoning at Oldham by Tinned Pigs' Tongues. — Two families
affected. Symptoms commenced in about four hours* All recovered*
After a few days' keeping it would appear that the poison liad been
decomposed.
1882. A Family Poisoned by Boast Beef at Bishop Stortford, —
Only a particular piece of the ribs seemed to be poisonous, the reit of
the carcase being innocuous. Symptoms did not commence until
several hours after ingestion.
1882. Ten different Families at Whitchurch poisoned by eating
Brawn, — First symptoms after about four hours.
1884, Tinned Salmon at Wolverhampton. — Five persons^ two being
children, ate of tinned sjilmon at Wolverhampton. All sutFered more or
less. The mother's symptoms began after twelve hours, and she died in
five days ; the son died in three days, the symptoms commencing in ten
hours. The post-morteni signs were similar to those from phosphorus
poison ingj viz., fatty degeneration, ft! ice fed on the material also
sufferedi and their organs showed a similar degeneration.
1886. The Carlisle A Case. — At a wedding breakfast in Carlisle
twenty-four persons were poisoned by food which had been kept in
an ill -ventilated cellar. The articles suspected were an American ham,
an open game pie, and certain jeUies. The bride died. Symptoms
commenced in from six to forty -three hours,
1886, Poisoning by Yeal Pie at Iron Bridge. —Twelve out of fifteen
ate of the pie ; all were taken ill in from ^ix to twelve hours,
1887. Poisoning at Batford of Eighty Persons from eating Pork
Pie or Brawn. — Symptoms commenced at various intervals, from eight
to thirty-six hours.
1889, The Carlisle B Case. — Poisoning by pork pies or boiled salt
pork. Number of persona attacked^ about twcntyfive.
189L Poisoning by a Meat Pie at Portsmouth — ^Thirtecn persons
suffered from sei-ious illness. Portions of the pies were poisonous to
• Te these (uBy be added the Chadderton case invcatiguUid by Dr. DurlmiUH Thirty-
^ye peraoufl were Attut^ked in Chadderton, with tiirec deaths ; twflWe ia OldhEun^ one of
§ 686.] Foojj POISONING. ^^^^ S3^ ^|
The symptoms in all tbejse cases were not precisely alike : but tbey ^^|
were so far identical as to show as great a siniiUmty as in cases when a ^^U
number of persons are poisoned by the same chemiiml substance. Arsenic, ^^M
for instance, produces several types of poisoning ; so does phosphorus, ^^|
Severe gastro-entenc disturbance, with more or less affection of the ^^M
nervous system, were the main characteristics. These symptoma com- ^^M
me need, as before stated, at various intervals after ingestion of the food ; ^^|
but they came on with extfcme suddenness. Itigors, prost lotion, giddi- ^^M
ness, offensive diarrhcoa, followed by muscular twitcbinga, dilatation of ^^M
the pupil, drowsiness, deepening in bad ca^es to coma, were commonly ^H
observed. Tbe post-mortem appearances were those of enteritis, with ^^H
inflammatory changes in the kidney and liver. Convalescence was slow ; ^^H
sometimes there was desquamatior^ of tbe skin. ^^|
In many of these cases Dr. Klein found bacteria whtoh, under certain ^^|
conditions, were capable of becoming pathogenic ; hut in no case does ^^|
there seem to have been at the same time an exhaustive chemical ^^M
inquiry ; so that, although there was evidence of a poison passing ^^U
through the kidney, the nature of the poison still remains obscure. ^^M
The deaths in England and Wales from im wholesome food during ten ^^|
years were as follows : — ^^|
DEATHS IN ENGLAND AND WALES FROM UNWHOLEfiOME FOOD ^|
DURING THE TEN YEARa lS0S-lfig2. ^H
liSS.
188i.
a'
9
8
laas.
1880.
S
T
IS^: 1891.
1
6
1
33
1
2
4
1
2
I 1
1
1
4fi
Poisououa fifth, . . .
Unwholettomo bmwii, .
Tumeci Httlmou, ♦ . ,
FutKd TXiGtLt, . . .
Diseased food, ....
MusseK .... *
Tiniifld foods, , . , .
WhdK
Winkles, .....
vPtonmine^
1
2
2
...
i
r
fi 4
1
5
6
H
Since 1892, deaths from foods have not been regularly and systematic
mlly extracted by the Registrar General's Department. A few in some
rearii appear imder the diarrhosal class of disease : the rest apparently
lave been registered in various ways ; hence no precise knowledge of
.he actual number of deaths ascribed to food is available.
rhieh wa» futal. Dr. Durham s<?em» to have fai rly well i'^tubliBbad a <!oimc>oti(Kti (letwee
he outhrei^k imd veal pjes iuft^ct^ by the Btiriibm enkriiidm B* M^^d. Jtrnmait 1 898
J
532
rOISONS : TlIKTIl EFFECTS AND DETECTION-
f§ 687.
§ 687. Gemmn Sausage Foisoniiig — A series of caBes may be picked
out from the aocouuts of eansage poisoning in Germany, all of which
evidently depend upon a poison producing the same symptoms^ and the
essentially distinctive mark of which is extreme dryness of the skin and
mucous membranes, dilatation of the pupil, and paralysis of the upper
eyelids (ptosis)* Jn an uncertain time after eating sausages or some
form of meat, from one to twenty four hours, there is a gcnciul feeling
of uneasiness, a sense of weight about the stomach, unuBea, and soon
afterwards vomitiugj and very often diarrhoea* The difxrrham is not
severe, never aasumea a choleraic form, and is unaccompanied by cramps
ill the muscles. After a considerable interval there is marked dryness
of the mucous membrauG (a symptom which never faik), the tongue,
pharynx, and the mouth generally seem actually destitute of secretion ;
there is also an absence of perspiration, the nasal mucous membrane
participates hi this unnatural want of secretion^ the very tears are dried
up. In a case related by Krmttzcrj* the ptitient, losing a sou, was much
troubled, but wept no tear* rhis dryness leads to changes in the
mucous membrane ; it sbrivels, and partly desquamates ; aphthous
swellings may occur ^ and a diffuse redness and diphthentic-hke patches
have been noticed. There is obstinate constipation, probably from a
dryness of the mucous lining of the intestines. The breatli has an
vnipleasant odour, there is often a croupy cough ; the urinary secretion
alone is not decreased but rather augmented. Swallowing may be so
difficult as to rise to the grade of aphagia, and the tongue cannot be
njanipulated properly, so that the speech may be almost unintelligible.
At the same time, the motor nerves of the face are affected, the
patient^s sight ia disturbed, he sees colours or sparks before his
eyes ; in a few cases there has beeii transitory blindness, in othera
diplopia. The pupil in nearly all the cases has been dilated, but in
exceptional instances it has Ihjou contracted. The hmtior palp^hra,&
supe}%oris m paralysed, and the resulting ptosis completes the picture.
Consciousness remains intact almost to death ; there is excessive weakness
of the nuiscles, perhaps from a general paresis. If the patient lives
long enough, he gets wretchedly thin, and dies from marasmus. In
more rapidly fatal cases, death follows from reapiratory paralysis, with
or without convulsions.
The post mortem appearances which have been observed are — the
mucous membrane of the mouth, gullet, and throat is white, hard, and
parchment-like ; that of the stomach is more or less injected with
numerous hemorrhages: the kidneys are somewhat congested, with
some effusion of blood in the tubuli ; the spleen is large and very fidl of
blood, and the lungs are often oedematous, pneumonic, or brouchitic,
* Quoted by HuB«maDTi, t^ergi/tung durch iFursigift {M&schkai'i Handbook).
PART VIIL-THE OXALIC ACID GROUP OF POISONS.
§ 688. Oxalic acid is widely distributed both tii the free state and
in combination with bases thmughout the vegetable kitigdoui^ and It
also occurs in the animal kingdom. In combmation with potaah it is
found in the Ge}*anifUH aretmitm (L.), Spinaria oleracea (L.), Phijtolacca
derandra {L,)j Hheiim palmafum (L,), Rtime^ aceiona^ Airopa Mlmlonnaf
and several others; in combination with sodii in di tie rent species of
iiahola mid Saliconiia ; and in combination with lim6 in most plants,
especiallj in the roots and bark. Many lichens contitin half their
weight of calcic oxalate, and oxalic acid, either free or combined ^ is
(according to the observationa of Hamlet and Plow right *) present in all
mature non-microseopio fungi. Crystals of oxalate of lime may bo
frequently seen by the aid of the microscope in the cells of plants.
According to Schmidt, t this crystallisation only takea place in the fully
mature cell, for in actively growing cells the oxalate of lime is entirely
dissolved by the albumen of the plant.
In the animal kingdom oxalic acid is always present In the intestinal
contents of the caterpillar. In combination with lirne^ it is constantly
found in the allantois liquor of the cow, the urine of man, swine, horses,
and cats. With regard to human nrine, the presence or absence of
oxalate of lime greatly depends upon the diet, and also upon the indi-
vidual, some persona almost invariably secreting oxalates, whatever
their food may be.
g 689. Oxalic Add, H3ajO4^H2O(90^36), specific gravity 1^64,
oceurs in commerce in prismatic crystals, very similar to, and liable to
be mistaken for, either raaguesic or dncic sulphates. The crystiUa are
intensely acid, easily soluble in water (I part reqviinng at 14 '5* 10*46
parts of water) ; they are also tsoluble in 2| parts of cold, and readily in
boiling, alcuhob Oxalic acid is slightly soluble in cotd absolute ether ;
but ether, although extracting most organic acids from an aqueous
solution, will not extract oxalic acid,
* Chttth AVttt, fol- juxvi. p. 93,
f Aniu Chm^ Fharm,, voL 1x1 p, 297i
5JJ
534 POISONS: their effects and detection. [§ 690.
Oxalic acid sublimes slowly at 100*, but rapidly and completely at
ISO"*; the best means of obtaining the pure anhydride is to put a
sufficient quantity of the acid into a strong flask, clamp it by suitable
connections to a mercury pump, and sublime in a vacuum ; in this way
a sufficient quantity may be sublimed a little above 100**. It is well to
remember, not only its low subliming temperature, but also that an
aqueous solution, if kept at lOO*", loses acid ; hence all evaporating or
heating operations must not exceed OS"*, or there will be some loss. The
effect of heat is first to drive off water, then, if continued up to about
190**, there is decomposition into carbon monoxide, carbon dioxide,
water, and formic acid ; the two reactions occurring simultaneously —
C2H2O4 = CO2 + CO + HgO.
CgHjO^r^COg + CHgOj.
Heated with sulphuric acid to 110°, the following decomposition
takes place : —
H2C204=H20 + C02 + CO.
Oxalic acid decomposes fluor spar, the phosphates of iron, silver, zinc,
copper, and the arseniates of iron, silver, and copper. It may be used
to separate the sulphides of iron and manganese from the sulphides
of zinc, cadmium, uranium, cobalt, mercury, and copper — dissolving
the former, not the latter. Many minerals and other substances are
also attacked by this acid.
If a solution of oxalic acid in water is boiled with ammonio or sodio
terchloride of gold (avoiding direct exposure to light) the gold is
precipitated —
2 AuClg + 3H2C2O4 = 6CO2 + 6HC1 + Au2.
When black oxide of manganese (free from carbonate) is mixed with
an oxalate, and treated with dilute sulphuric acid, the oxalic acid is
decomposed, and carbon dioxide evolved —
Mn02 + H2C2O4 + H2SO4 = MnSO^ + 2H2O + 2CO2.
A similar reaction occurs with permanganate of potash.
If to a solution of oxalic acid, which may be neutralised with an
alkali, or may contain free acetic acid, a solution of acetate of lime be
added, oxalate of lime is thrown down. This salt, important from an
analytical point of view, it will be well to describe.
§ 690. Oxalate of Lime (CaC204H20), 1 part = -863 crystallised
oxalic acid. This is the salt which the analyst obtains for the quantita-
tive estimation of lime or oxalic acid ; it is not identical with that occur-
ring in the vegetable kingdom, the latter containing SHjO. Oxalate
of lime cannot be precipitated for quantitative purposes from solu-
tions containing chromium, aluminium, or ferric salts, since somewhat
soluble compounds are formed. It dissolves in solutions of magnesium
§ 691-695]
OXALIC ACID.
si$
and maiigfinese Baits,* and citrate of soclaj and ia also decompoaed hy boil-
ing with solutions of copper, silver, lead, cadmium^ ztnc, nickel, cobalt,
strontium, or barium salts. It ia insoluble in aohitions of chlorides of
the alkalies and alkaline earths, and in water^ in alkaline solutions, or
in acetic acid ; and is soluble in mineral acid only when the acid is
strong and in considerable eroess. It is unalterable in the air, and
at 100*. When carefully and slowly ignited it may be wholly converted
into carbonate of lime ; if the heat is not properly managed {that is, if
excessive), caustic lime may be formed in greater or smaller quantity,
^ 69L ITfie in the Arts, — Oxalic acid is chiefly used by dyers and
calico-printers, but also by curriers and harness- makers for cleaning
leather, by marble masons for removing iron stains, by workers in
straw for bleaching, and it is applied to various household purposes, t
sncb as the whitening of boards, the removing of iron-mould from
lineu, etc. The hydropotassic oxalate (binoxalate of potash), under
the popular names of *^ ei^seJitial salt of lemmis^* and salts of sorrel, is
used for scour hi g metaJa and for removing ink st*iins from liueu.
§ 692. HydropotasBic Oxalate, Binoxalate of Potash, KHC^04{HaO),
is a white salt, add iu reaction, soluble in water, and insoluble in
alcohol. Heater! on platinum foil tt kaves potassic carbonate, which
may be recognised by the usual tests. It^ aqueous sol ut ion giveSt
with a solution of acetate or sulphate of lime, a precipitate of calcic
oxalate inyoluble in acetic acid.
I 693, Statistics. — Poisoning by oxalic acid is more frequent in
England than in any other European country. In the ten years ending
December 1903 there wore registered in England and Wales 171
oxalio acid deaths. Of these 55 (27 males and ^8 females) were
accidental, 1 1 4 (65 males, 49 females) were suicidal, and there were
two cases of murder. Oxalic acid occupies about the tenth place among
poisons arninged iu ordi^r of frequency.
^ 694. Fatal Dose. — The smallest dose of oxalic acid known to have
destroyed life is, according to Dr. Taylor, 3*88 grms. (60 grains) ; but
recovery iuis taken place, oti prompt administration of remedies, after
eight times this quantity has been swallowed.
With regard to oxalate of soda, or binoxalate of [totash, 14^2 grms.
(half an ounce) have been taken without fatal result, although the
gymptoms were very serious ; and it may be held that about that
quantity would usually cause death. Oxalic acid is not used in
niedicitie, save as a salt, ei,?;., oxalate of ceriimi.
^095, Effects of Oj^alic Acid and Os^aktes on Ajiiinals.—^The first
cases of poisoning by oxalic acid occurred early in the nineteenth
* Hut It IB rapriecipitated unaltered hy excess of lilki^Hno oxabte.
t A *^ liquy Blue,'' mvd for laundry purp<»i<:s, coutains much free uxalic acid*
$J6
POISONS: THEIB EFFECTS ANn DSTTECmON.
[§696.
century, a little more than fifty years alter ita disjcovery, Thompeon*
was the first wha attempted, by experiment on animal life, to elucidate
the action of the poison ; he noted the caustic action on the stomach,
and the effects on the heart and nervous ejetem, which he attribnted
simply to the local injury through the sym|mthetic nerves, Urfilat
was the next who took the matter up, and he made several experimentB ;
but it was Robert Christison | who distinctly recognised the important
fact that oxalic acid was toxic, quite apart from any local eftuots, and
that the soluble oxalates, such as sodic and potassio oxalates^ w^ere
violent poisons,
g 69C, Robert and Kiissner§ have made iome extended researches
on the elTecta of sodic oxalate on rabbi tia, oatSj dogs, guineiipigs, hedge-
hoi^ frogs, ctc^the chief results of which are as follows : — On
injection of sodic oxalate solution in moderate doses into the circula-
tion, the heart's action, and, therefore, the pulse, become arhythmiCj
and a dicrotic or tricrotic condition of the pulse may last even half a
day, while at the mime time the freipiency may be uninfiuenced. The
biood'presaure also with moderate doses is normal, and with snmll
atoxic doses there la no slowing of the respiration, On the other hand,
toxic doses paraljae the respiratory apparatus, and the animal dies
asphyxiated. With chronic and snlmcute poisoning the respiration
becomes slower and slower, and then ceases from paralysis of the
respiratory muscles. The first sign of poisoning, wiiether acute or
chronic, is a sleepj contlition ; dogs lie quiet, making now and then
a noise as if dreaming, mechanical irritations are responded to with
duluess. The hind extremities become weak, and then the fore. This
paresis of the hind extremities, deepening into complete paralysis,
waa very constant and striking. Take, for example (op, eit.}, the
experiment in which a large cat received in six days five subcn-
tftueous injections of 5 c.c* of a solution of sodic oxalate {strength
1 :30), equalling -16 grm, ; the cat died, as it were, gradually from
behind forwards, so that on the sixth day the hinder extremities were
fully motionless and without feeling. The heart beat strongly. The
temperature of the poisoned animal always sinks below the normal
condition* Convulsions in acute poisoning are common, in chronic
quite absent ; when present in acute poisoning, they are tetanic or
strychniC'like. In all tlm experiments of Robert and Kiissner, lethal
doses of soluble oxalates caused the appearance of sugar in the nriue.
J. Uppmain|f made forty-nine experiments on dogs, in which he
• Liind. Med, M^p,, vol iii. p. 382, f TraiUfk T^me&logk,
t Min. Mf!d. mnd Surg. Journ., 1823,
j ** Exjper. Wirkurigim der Oialaaare,'* Virch* jirthiv, Bd- lixvij, S. 208,
II AUg M^L centml Zt^j., 1S77.
§ 697, 69S.]
OXALIC ACID,
537
adrainiBtered relatively large doses by the stomach ; no poisonous effect
folJowcd. Emil Pfeiffer* gave a dog iu three auccessive days "2, '5, and
lastly 1 grm. oxalic acid with meat^ but no symptooifi resulted. Yet
tlmt oxalic acid, as aodic oxalate^ is poiaonouB to dogs, if it once gets
into the circulation^ cannot be disputed. The accepted explanation h
that the large amount of lime phosphates in the digestive canal of dogs
is decomposed by oxalic auid^ and the barm leas limo oxalate formed.
Oxalic acid is absorbed hito the blood, and leeches have been known
to die after their application to a person who had taken a large dose.
Thus Chrietison t quotes a case related by Dr, Arrowamith, in which
this occurred :— " They were healthy, and fasten^ immediately ; on
looking at them a few minutes after, I remarked tlmt they did not seem
to fill^ and on touching one it felt hard, and instantly fell off motionless
and dead ; the others were in the eame state. They had all bitten, and
the marks were conspicuous, but they had drawn scarcely any blood.
They were applied about six hours after the acid bad Ijeen taken."
§ 697, Effects of Vaporised OzaUc Acid.— Enlenberg has experi-
mented on pigeons on the action of oxalic acid wheu breathed. In oue
of his experiments, '75 grm. of the acid was volatilised into a glasji
shade in which a pigeon bad been placed ; after this had been done five
times in two minutes, there was uneasiness, shaking of the head, and
cough, with increased mucous secretion of the nasul membrane. On
continuing the transmission of the vapour^ after eight niinutea there
was again restlessness, shaking of the head, and cough ; after eleven
minutes the bird fell and was convulsed. On discontinuing the sub-
limation, it got up and moved freely, but showed respiratory irritatiotL
On the second day after the experiment, it was observed that the bird*8
note was hoarse, on the fourth day tlierc was slowness of the heart's
action and refusal of food, and on the sixth day the bird was found dead.
Examination after death showed slight injection of the cerebral mera-
branea ; the cellular tissue in the neighbourhood of the trachea contained
in certain places extravasations of blood, varying from the size of a pea
to that of a penny ; the raucous membrane of the larynx and trachea
was swollen and covered with a thick croupous layer; the lungs were
partially hepatised, and the pleura thickened ; the crop as well as the
true intestines still contained some food, J
g 698. The Effects of Oxalic Acid aad Hydropotassic Oxalate on
Han. — The cases of oxalic poisoning hivve been invariably due to either
oxalic acid or hydropotaasic oxalate^ the neutral sodic or potassic oxalates
having hitherto in no instance been taken. The symptoms, and even
the locally destructive action of oxalic acid and the acid oxalate, are so
* Arrhw dtr Pharnu (3 VL), Bd, xi\L K &44, 1S7S-
538
POISO^fS: THKIE EFFECTS AND DKTKOnON.
[§698.
similar that neither from clinical nor poflt-mortem signs could thej be
differentiated by anyone not having a previous knowledge of the case*
The external applicatioo of oxalic acid does not appear to cause
illness ; workmen engaged in trades requiring the constant use of the
acid often have the uails white, opaque, and brittle ; but no direct injury
to health is on record.
A large dose of either causes a local and a remote e fleet ; the local is
very similar to tbut already described as l>elonging to the minerul acids ;
i,e. more or less destructive of the raucous membrnnoa with which the
acid comes in contact The remote effects may only be developed after
a little J they consist essentially of a profoimd influeuce on the nervous
system. Though more than 120 cases of oxalic acid poisoning have
occurred suice Chris tison wrote his treatise, his graphic description still
holdH good. **lfj" Bays he, **a peraoti immediately after swallowing a
solution of a crystalline salt, which tasted purely and strongly acid, is
attacked with burning in the throat, then with a burning in the stomaeli,
vomiting, particularly of bloody matter, imperceptible puke, and
excessive languor, and dies in half an hour, or still more, in twenty,
fifteen, or ten minutes, 1 do not know any fallacy wliicli can iiitcifere
with the conclusion that oxalic acid was the cause of death. No i*arallel
disease begins so abruptly, and terminates so aoon ; and no other
crystalHue poison has the same effect.'^ The local action Is that of a
Bolvent on the mucous tissues. If from 10 to 30 grms. are swallowed,
dissolved in water, there is an immediate sour taste, pain, burning in
the stomach, and vomiting. The vomit may be colourless, greeuishj or
black, and very acid ; but there is a considerable variety in tha
symptoms. The variations may be partly explained hy saying that, in
one class of cases, the remote or true toxiu effects of the poison pre-
domiuate ; in a second, the local and the nervous are equally divided ;
while in a third, the local effects seem alone to give rise to symptoms.
in a case at Guy 'a Hospita], in 1842, there wtis no pain, but vomiting
and collapse, lu another case which occurred in 1870, a mule (aged 48)
took 10*4 grms* (162 grains) ; he had threatening collapse, cold sweats,
white arid red patches on the tongue and pharynx, difficulty in swallow-
ing, and contmcted pupils. Blood ^vas cfthsed from the mouth and anus ;
on the following day there were convulsions, conia, and death thirty- six
hours after taking the poison. In another case, there was rapid loss of
consciousness and comaj fol levied by death in five hours. Death may be
very rapid; e.^,, in one case {Med, Times and Gaz.^ 1868) it took place
in ten minutes ; there was bleeding from the stomach, which doubtless
accelerated the fatal result, Orfila has recorded a death ahuost as rapid
from the acid oxalate of potash j a woman took 15 grms. j there was no
vomiting, but she suflered from fearful cramjw, and death ensued in
I 699-]
OXALIC ACia
$39
fifteen miiiutes. In another case, also recorded by Orfila^ there weis
marked slowing of the pulse, and aoporific tendencieB- With both oxalic
acid and the acid oxalate of potash, certain DGrvous and other sequelae
are more or less constant, always provided time is given for their
development, From the experiments already deUiiled on aijimala, one
would expect some paresis of the lower extremities, but this has not
been observed in man. There is more or less inflammatiou of the
stomach, and often peri ton itia ] iu one case {Brit. Med. Journal^ 1873)
there were cystitis and acute congestion of the kidneys with albuminuria.
In two cases quoted by Taylor there was a temporary loss or en-
feehlement of voice ; in one of the two the aphonia lasted for eight
days. In the other, that of a man who had swallowed about 7 grme,
(J oz.) of oxalic acid, his voice, naturally deep, became in nine hours
low and feeble, and continued so for more than a month, during the
whole of which time he suffered in addition from numbness and ting-
ling of the legs. As a case of extreme rarity may be mentioned that
of a young woman,* who took 12 grms. (185 grains) of the acid oxalate
of jyotash, and on the third day died ; before death exhibiting dehrium
so active and intense that it was described as " madness/'
§ 699. Physiological Action. ^Putting on one side the loml effects
of oxalic acid, and regarding only its true toxic effects, there is some
difference of opinion as to its action. L, Hermann considers it one of
the heart poisons, having seen the frog's heart arrested by subctttaneous
doses of sodic oxalate, an observation which is borne out by the experi*
mentfi of Cyon,t and not negatived by those of Kohert and KUssner,
The poieon is believed to act on the extracardial ganglia. Onsum{ held
at one time a peculiar theory of the action of oxalic acid, believing
that it precipitated as oxalate of lime in the lung capillaries, causing
embolic obstruction ; but this view is not now accepted— there aro too
many obvious objections to it, Kohert and KCisancr do not consider
oxalic acid a heart poison, but believe that its action is directed to the
central nervous system, as attested by sinking of the blood -pressure, the
arhythm and retardation of the pulse, the slow breathings the paralytic
symptoms, and the fibrillary muscular contraction ; but, with regard to
the latter, Locke § has observed that a frog's sartorius, immersed jn 075
sodium oxalate solution^ becomes in a few seconds violently active, much
more so than in Biederman's normal saJino solution. After thirty to
• Jijwnt. d4 Chim. MM,, 1S3&, p. 664.
+ Vircbow'B Ar<^hiv, Bd. xx. 3. 283,
t Almeii afterwtrdfl aui>|iorted OtiEUni's view^ he made a numher of raiero&eopiciil
observations, Mid ap}>ears to hav^ lifjen thi^ first who identified oxi^Iate of lime in the
kidneys (Upaala, Lfthtre/or^ninffitfQrhafidL. Bd- ii. Hft iv. S* 205).
I F* 3. Locke, J. Phys.^ xv* 119 ; Joitm. Ck^m, 3oc,, l&m, 480,
540
POISONS: THEIR EFFECTS AND DKTKCTION. [§ 7OO, 7OK
forty-five minutes it loses its irritability, which, however, it partially
recovers by imQierfiion in 0 6 sodium cliloride solution. He thinkii this
may explain the symptoms of fibrillary muscular contraetioo observed
by Kobert and Klissner, which they ascribe to an sietioii on the central
uervona system*
g 700, Pathological Changes. — Kohert and Kussner observed that
w^hen oxalate of soda was subcutaneously injected into animals, there
was often absicefiw, and even gangrene, at the Beat of the injection. If
the poison were injected into the peritoneal cavity, death was so rapid
m to leave little time for any coarse lesions to manifest themselves.
They were not able to observe a cherry- red colour of the blood, nor did
they !iiid oxalate of lime crystals in the lung capillaries ; there were
often embolic processes in the lung, but nothing typical. They came,
therefore, to the conclusion that the state of the kidneys and the untie
was the only typical sigii. The kidneys were dark^ full of blood, but
did not show any microscopic hcBmorrhages* Twelve hours after taking
the poison there is observed in the cortical snbstan<je a fine striping
corresponding to the canaliculi ; in certain cases the wliole boundary
layer is ooloun^d white. If thu poisoning lasts a longer time, the
kidneys become less blood-rich, and show the descrihed white striping
very beautifully; this change persists several weeks. The cause of this
strange appearance is at once revealed by a microscopical examination ^
it is due to a deposition of oxalate of lime ; no crystals are met with in
the glomeniles* Both by the microscope and by chemical means it may
be shown that the content of the kidney in oxalates is large,* So far
as the tissues generally are eoneemed, free oxalic acid is not likely to
be met with ; there is always present sufiicient lime to form lime oxalate*
The urine was always albuminous and contained a reducing substance,
which vanished about the second day after the dose. Hyaline casta and
deposits of oxalates in the urine never failed, t
5 701. Observations of the pathological effects of the oxalates ou
man have been confined to cases of death from the corrosive substances
mentioned, and henue the intestinal tract has been profoundly aficc ted-
In the Museum of Sti Thomas* Hospital is a good example of the
etlects produced* The case was that of a woman who had taken a large,
unknown quantity uf oxalic acid, and was bruught to the hospital dead,
• The importiint fifcct of the oxalate -content of kidneys and urlnej uud the eipnl*
don of cAsts, WHS first obasTved by Mitscherlicb in 1854* He noticed in a mljbit> to
which bid lK?en given 7*5 grtnB* of oxalic acid, and which bad died in thirtfiCii
Tuiimtua, *' ten£3 p{tididurn tnafjl^ sanguine repUle vid^ia^Uurt in urina miilUt corpora
t Riibuteau has diacovered by e^cperiment that even the oxalates of iroji and
copper aru decomposed and wparatad by the kidney*. Qa^. Mi^* de Pcim, 187 i-
§ 702, 703.]
OXALIC ACID.
S^x
The mucous memhrano of the gullet is much cornigaietl mid divided
into numerous i>aralk4 groovebj these again by little transverse gr<j<n'es,
m that the intersection of the two aystems makea a sort of raised
pattern,. It iB noted that tu the recent state the mucous membrane
could be removed in flakes ; in the upper part it was whitish, in the
lower slate-colonTed, The stomach has a large perforation, but placmg
the Epecrmen lieside another in the same museum which illustrates the
effect of the gastric juice, in causing an after-death solution of a portion
of the stomach, it was difticult to differentiate between the two. The
mucous membmne had the same shreddy tiocculent appearance » and is
soft and pale. The pyloric end is said to have been of a black isli colour,
and no lympk was exudetl
§702, The pathological changes by the acid oxalate of potash are
Identical with those of oxalic acid^ in both, the gullet and stomach
being nearly always more or less iu flamed or corroded ; the inflammation
in a few caseg heis extended right through intn the intestiaal canal ^
there are yenoua hypenemia, haemorrhages, and swelling of the mucous
membrane of the stomach. The haemorrhages are often puuctiform, but
occasionally larger, arranged in rows on the summits of the mgm ; some-
times there is considerable bleeding. In the greater number of eafies
there is no actual erosion of the stomach, but the inner kiyer appears
abnormally transparent. On examining the mucous membratie under
the microscope^ Lesser * has described it a« covered with a layer which
Btrongly reflects light, and is to be considered as caused by a fine preci-
pitate of calcic oxalate. Lesser was unable to find iu any case oxalic
acid crystals, or those of the acid oxalate of potash. There are many
cases of perforation on record, but it is questionable whether they are
not all to be regarded as post-mortem effects, and not life- changes ■ at
all eveuts, there is little clinical evidence to support the view that
these perforations occur during life* In the case (mentioned ante) in
which death took phu^e by coma, the brain was hyperremic. The
kidneys, as in the case of animals, show the white zone, and are con-
gested, and call be proved by microscopical and chemical means to he
rich in oxalates,
§ 703. Separation of Oxalic Acid from Organic Substances, the
Tissues of tJie Body, etc. — From what has been stated, no investigation
as to the ca^use of poisou, when oxalic acid is suspecterh can be con-
sidered compfete unless the analyst has an opportunity of examining
lx>th the urine and the kidneys; for although in moat cases — when the
acid itself, or the acid potasaic salt has been taken— there may be ample
evidence, both chemical and pathological, it is entirely diflferent if a
ease of poisoning with the neutral sodic salt should occur. In this event
• VirchoVs jircAtV, Bd. Ixxxiii. S. 218, 1881,
542
poisons: their effects and detection.
[1 703-
there may be no congested appearance of any portion of the intestinal
canal, and the evidence mnat mainly rest on the urine and kidnejB,
Oxalic acid being so widely distribtited in the v^ege table kingdom, the
expert must expect, ia any criminal case, to be cross-examined by
ingenious connsel as to whether or not it was possible that the acid
could have entered the body in a rhubarb-pie, or accidentally through
sorrel mixed with greens, etc. To meet these and similar questions it
is important to identify, if possible, any green mattei^ found in the
stomach. In any case, it must be remembered that although rhubarb
has been eaten for centuries, and every schoolboy has occasionally
chewed small portions of sorrel, no poisoning has resulted from these
practices. When oxalio aeid has been taken into the stomach, it will
invariably be found partly in combination with lime, soda, ammonia,
etc, aud partly free ; or If such antidotes as chalk has been administered,
it may be wholly combined. Vomiting is nearly always present, and
valuable evidence of oxalic acid may be obtained from stains on sheets,
earpete, etc. In a case of probably suicidal poisoning, the senior author
fonnd no oxalic acid in the contents of the stomaoh, but some waa
detected in the copious vomit wliieh had stained the bed-clothes. The
urine also contained a great excess of oxalate of lime — a circumstance
of little value taken by itself, but confirmatory with other evidence.
If a liquid is strongly acid, oxalic acid may be separated by dialysis
from organic matters, and the clear fluid thus obtained precipitated by
sulphate of lime, the oxalate of lime being identified by its microscopic
form and other characters.
The usual general method for the separation of oxalic acid from
organic substances or mixtures is the following : — Extract with boiling
water, filter (which in some cases must be difficult or even impossible),
and then precipitate with acetate of lead. The lead precipitate may
contain, besides oxalate of lead, phosphate, chloride, sulphate, and
varions organic substances and acids. This is to be decomposed by
sulphuretted hydrogen, and on filtering off the sulphide of lead, oxalic
acid is to be tested for in the filtrate. This process can only be
adopted with advantage in a few cases, and is by no me-ana to be
recommended as generally applicable. The best general method, and
one which insures the separation of oxalic acid, whether present as a free
acid, as an alkaline, or a calcic oxalate, is perhaps the following :^ — The
substance or fluid under examination is digested with hydrochloric aoid
until a fluid capable of filtration is obtained ; the free acid is neutralised
by ammonia in very slight exee^ and permitted to deposit, and the
fluid is then carefully decanted, and the deposit thrown on a filter. The
flltrate is added to the decanted fluid, and precipitated with a slight
excess of acetate of lime — this precipitate, like the first, being collected
§ JO}.]
OXALIC ACID.
543
on a filter. The first precipitate contains all the oxalio acid which was
in conibiimtioa with lime; the aecoiid, all that which wns, in the free
condition. Both precipitates ahuuld be wasljed with acetic acid. The
next stop 18 to identify the precipitate which ib supposed to be oxalate
of lime. The precipitate is washed into a heakerj and dissolved with
the aid of heat by adding, drop by drop, pure hydrochloric acid ; it ia
then repreci pita ted by ammonia, and allowed to subside completely,
which may take some ttme. The supernatant fluid is decanted, and the
precipitate washed by subsidence ; it is lastly dried over the water- bath
in a tared porcelain dish^ and its weight taken. The substance is then
identified by testing the dried powder as follows* —
(a) It is whitiMi in colour, and on ignition in a platinum dish leaves
a grey carbonate of lime. All other organic salts of lime— viz.^ citrate,
tartrate, etc, — on ignition become coal-black.
(b) A portion suspended in water, to which is added some sulphuric
acid, destroys the colour of permanganate of potash— the reaction being
similar bo that on p. 534 — -a reaction by which, as is well known, oxalic
acid or an oxalate may be conveniently titrated. This reaction is so
peculiar to oxalic acid, that there is no substance w^itb which it can be
confounded. It is true that uric acid in an acid solution equally de-
colorises permanganatep but it does so in a different way ; the reaction
i>etwecn oxalic acid and permanganate being at first slow^, and after-
wards rapid, while the reaction with uric acid is just the reverse — ^at
first quick J and towards the end of the process extremely slow.
(c) A portion placed in a test-tube, and warmed with concentrated
sulphuric acidj deTelops on warming carbon monoxide and carbon
dioxide ; the presence of the latter is easily shown by ndaptiug a cork
and bent tube to the test- tube, and leading the evolved gaeea through
baryta water.
Alexander Gunn* has described a new method of both detecting and
estimating oxalic acid ; it is based on the fact that a small trace of oxalic
acid, added to an acid solution of forrovis phosphate, strikes a persistent
lemon-yellow colour; the depth of colour being proportionate to the
amount of oxalic acid.
The reagents necessary for both quantitative and qualitative testing
are as follows : — -A standard solution of oxalic acid, of which 100 c*c-
equal 1 grm., and a solution of ferrous phosphate, containing about 12 5
per cent* of Fe32PO^, with excess of phosphoric acid.
Into each of two Nessler graduated glasses 7 '5 c,c. of the ferrous
phosphate solution are run and made up to 50 c.c. with distilled water ;
both solutions should be colonrlesa ; 1, 2, or more c.c, of the solution
to be tested are then run into one of the Nessler glasses ] if oxalic acid
' J'hartfu Jounmh 18^3, 408.
544
poisons: thkib effects and detection. [§ 704. 705.
1^ present, a more or less deep tint ib produceil ; tbis must be Jraitated
by running the stanflard ealution of oxalic acid into the second Xesslcr
cylinder — the calculation ia the same as in other coloriraetric estima-
tions, it docs not apear to be reliable qnantitatively, if alum is present;
and it is self- evident that the solution to be tested must be fairly free
from colour.
§ 704. Oxalate of Lime in the TTrme.— This well-knoivn urinary
sediment occurs chiefly as octahetira, but honr-glaas, contracted or
diimlvVjell-like bodies, compomid tjctahedraj and small, flattened, bright
discs, not unlike blood discs, are freqviently seen. It may be usually
identified under the fleld of the microscope by its insolubility in acetic
acid, whilst the ammonio mag. phosphate^ as well as the carbonate of
lime, are both soluble in that acid. From urates it is distinguished by
its insolnbllity tn warm water, A chemiail method of aepamtion is as
follows : — The deposit is freed by ifubsidence as mucli as possible from
urine, washed with hot water, and then dissolved in hydrochloric acid
and filtered ; to the filtrate ammonia is added in excess, The precipitate
may contain phoSf>hat€s of iroui magnesia, lime, and oxalate of lime,
On treatment of the precipitate by acetic acid, the phospiiates of the
alL^line earths (if present) dissolve ; the insoluble portion will be either
phosplmto of iron, or oxalate of lime, or both. On igniting the residue
in a platinum dish, any oxidate will be changed to carbonatej and the
carbonate of time may be titrated with d, n, RCl acid and cochineal
solution, and from the data thus obtained the 03falate estimated. The
iron can be tested qualitatively in the acid solution by ferrocyanide of
potassium, or it can be determined by the ordinary methods. If the
qualitative detection of oxalate of lime in the deposit is alone required,
it is quite sufficient evidence should the portion insoluble in acetic acid,
on ignition in a platinum dish, give a residue efTervescing on the addition
of an acid.
^ 705. Estimation of Oxalic Acid.— Oxalic acid is estimated in the
free state by direct weigh in^% or by titration either with alkali or by
potassic permanganate, the latter l>eing standardised by oxalic acid. If
(as is commonly the case) oxalic acid is precipitfited as oxalate of lime,
the oxalate may l>e —
(a) Dried at lOO"" and weighed directly, having the properties already
described,
(If) Titrated with dilute sulphuric acitl and permanganate,
(r) Ignited, aud the resulting carbonate of lime weighed ; or
dissolved in standard a^id and titrated back — one part of calcic carbonate
correspfmds to h2G part of cryatallised oxalic ncid, or 0'90 part of
HgC^O^ ; similarly, 1 c,o. of standanl acid equals "05 of calcic carbonate
(or 003 of crystallised otsMc acid).
§ 7o6.]
OXALIC BASES.
S4S
(d) The oxalate may be dlgsolved in the snmlkbt t^ossible amount of
hydrochloric acid, and boiled with ammonio chloride of gold, avoiding
exposure to Hght ; every part of gold precipitated corresponds to '961
part of crystallised oxalic acid.
(e) The oxalate may be placed in Geissler's carbonic acid apparatus^
with peroxide of manganese and diluted sulphuric acid. The weight of
the gas which at the end of the operation has escaped, will have a
definite relation to that of the oxalate, and if multiplied by 1*4318 will
give the amount of cryfitallised oxalic acid.
CERTAIN OXALIC B ASEB -OX ALMITHYLLHE-^XALP ROPY LINE.
g 70S. Hugh Sohnlis * and M&yer Iwvo contributad the resulta of aeme important
researches bearing upon a more ex&ct knowledge of the eJfeote of the oxalic group of
poisooa, aud u|)on the relation bettvi^ii chemical constitutioQ and plijsiological
eSflcta. They experimented upon axaimdhifline^ dilofroxalmtlhyUne, and Qxaipropif'
line.
OMoroxalmet hy line (CaHaClNa) is all quid, boiling at 205*, with a weakly narcotic
fiuiel], A solntioii of tlie hydrochl orate of the hma waa employed. Subcutaneous
iigectionfi of '05 grm. into frogs can.sed narcosis^ and both thi» and tbo ethyUo com-
pound demngied tlio htyirt-s action, decroaaiiig t!ie number of beats* Thus '05 grnu
decreaHod the number of the beata of the heart of a frog in the course of one and
thre«*qnarter hours as follows : 72, 60, 5S, iO, 44, 40, 35, D*
Oiulmothylliie produceijt ijiomewbat tuuilar syinptoms^ but the nervous system u
more atfectcd than in that which contains clilorine,
Oxalpropyline al^ causes narcofiis^ aud afterwards jmralyais of the hinder ex-
tremities skfid slowing of the heart
Tbo difrereuee between th« cbloriue^free and tlia obloruia-ooutAinmg o^tatic baaaa
are summarised as follows :
FB0G8,
CHLOBiNK-HoLDtHa BAaES. Cklomne^F&ki Bases,
Notabk narcosis ; no heightened reflex Namosia occurs* late, and in little pro-
action ^ muscular cramps, nor spontaneous nounced ; a notablo increase of re0e%
conTulsiousi. excitability ; more and more muscular
paralysis ; between times, muscular
orampfi.
GATS.
CttiiOEiifB HoLDixo Basks,
Notoble unrcoais and salivation ; no
mydrtasia ; convulsions aud tmralybis ; no
change in the respirations.
Great excitement ; genera] ahireringf
rising to pure clonic convulsions ; para-
lysia of the bind legs ; notable mydriasis,
jerking, and snp«rJicial respiration ; weak
DOGS,
Notable naroo&ia ; oocasionol Tomiting ; Narcosis evident - the rest as in cata^
tho rest as in cats.
* ^*BiitrBg Kur Kenntnisa dor Wirkung der Oxalbosen anf den Tbierkorjier,"
df^f. asper, Faih, u. Pharm^f 1S82,
PART IX.— INORGANIC POISONS.
I.— PRECIPITATED FROM A HYDROCHLORFC ACID SOLU-
TION BY HYDRIC SULPHIDE— PRECIPITATE YELLOW
OR ORANGE.*
Arsenic— Antimony— Cadmium.
1. ARSENIC.
§ 707. Metallic Arsenic, atomic weight, 75 ; specific gravity of amor-
phous arsenic, 4*7 ; of crystalline, 5*7; sublimes without fusion in small
quantities at 110' (230' F.) Ouy. It occurs in commerce in whitish-
grey, somewhat brittle, crystalline masses, and is obtained by subjecting
arsenical pyrites to sublimation in earthen retorts, the arsenic being
deposited in suitable receivers on sheet iron. There is an allotropic
variety, yellow arsenic As^, obtained by subliming arsenic in a current
of COj in the dark and condensing the vapours on a surface cooled to
0' ; yellow arsenic has an onion-like odour, is soluble in CSg, which
solution, on evaporation, leaves it in rhombohedral dodecahedrons isomor-
phous with crystals of white phosphorus; it is rapidly changed with
evolution of heat into ordinary amorphous arsenic. Metallic arsenic
is probably not poisonous, but may be changed by the animal fluids
into soluble compounds, and then exert toxic effects — volatilised metallic
arsenic is easily transformed in the presence of air into arsenious acid,
and is therefore intensely poisonous.
§ 708. Arsenious Anhydride — Arsenious Acid— White Arsenic —
Arsenic, As20g= 198 ; specific gravity of vapour, 13*85 ; specific gravity
* Fresenios has pointed out that sulphur may mask small quantities of arsenic,
antimony, tin, etc, and he recommends that the turbid liquid in which apparently
nothing but sulphur has separated should be treated as follows :— A test-tube is half
filled with the liquid, and then a couple of c.c. of petroleum ether or of benzene added,
the tube closed by the thumb, and the contents well shaken. The sulphur dissolves,
and is held in solution by the solvent, which latter forms a clear upper layer. If
traces of a metallic sulphide were mixed with the sulphur, thin coloured films
are seen at the junction of the two layers, and the sulphides may also coat the
tube above the level of the liquid with a slight faintly-coloured pellicle (Chem.
News, Jan. 4, 1896).
546
§ 7oS,]
ARSIHIC,
o( opaque variety, 3*699 ; specific gravity of transparerit variety, 3'7385.
Composition in 100 parts, A a 75*75, O 24*25 ; therefor© one jmrt of
metallic arBenic equals 1-32 of Ab20^. It is entirely volatilised at u
temperature of 204 '4%
In analysis it is obtaitied in brilliant octahedral crystals as a Bublimate
on discs of gkss, or within tnbee, the result of heating a film of metallic
arsenic with access of air. It ia obtained in commerce on a very large
scale from the roasting of arsenical pyrites. As thus derived, it m
usuaUj in the form of a white cake, the arsenious aeid existing in four
forms — an amorphous, a vitreous, and two crystal line— the cake l>eing
generally opaque oitDrnally, whilst in the centre it is transparent.
According to Kruger, this cbauge from the orystalliue to the amorphous
condition is dependent upon the absorption oF morsture, no alteration
taking place in dry ain The couditions under which three of the
forms of arsenic are produced are well shown by an experiment of
Debraj*e ; a sealed tube of A^M-^ is heated in a sand bath in such &
manner as to heat the lower part to 400* 0, the upper to 200* C. On
cooling, vitreous arsenic is found in the lower part* octahedral crystals
in the upper part, and in the middle prismatic crystals The varieties
of arsenious anhydride are acid to test-paper.
The solubility of arseuioua acid is often a question involving chemical
legal matters of great moment. Unfortunately, however, no precisely
definite statement can be made on this point, the reason being that the
varieties of arBenic occur in very different proportions in different samples.
The amorphous and crystalline varieties having very unequal solubilities,
every experimenter in succession haa given a different series of figures,
the only agreement amid the general discrepancy being tbat arsenic is
very sparingly soluble in water*
The statement of Taylor may, however, be accepted as very near the
truth, viz., that an ounce of cold ivater dissolves from hulf a grain to a
grain. According to M* L* A, Buchner,* one part of crystalline araenious
acid dissolves after twenty- four hours' digestion in 355 ptirts of water at
15' ; and the amorphous, under the same condition, in 108 of water. A
boiling solution of the crystalHne acid, left to stand for twenty- four
hours, retains one part of aotd in 46 of water ; a similar solution of the
amorphous retains one of arsenic in 30 parts of water ; f.e,, 1 00 parts of
water dissolve from 2 "01 to 3"3 parts of As-,Ou.
Boiling water poured on tbe powdered substance retains in cooling
a grain and a quarter to the ounce ; in other words, 1 00 parts of water
retain '14. Lastly, arscnious acid boiled in water for an hour is dis*
solved in the proportion of 12 grains to the ounce ; i.e.^ 100 partB of water
retain '2*t>.
* ButL dc la Socim Vkim. tk Parw, t. xx. 10, IS/JI,
548 POISONS : THEIB EFFBCT8 AND DETECTION. [§ 709.
K. Chodomisky * has investigated the soluhility of recrjstallised
arsenious acid in dilute acids, and his results are as follows : — 100 c.c.
of 1*32 per cent hydrochloric acid dissolves 115 grm. AsgOj at 18*5'.
100 c.c. of 6 per cent, hydrochloric acid dissolves 1*27 grm. at 18-5*.
100 c.c. of pure hydrochloric acid of the ordinary commercial strength
dissolves 1*45 grm. AsjO,. 100 c.c. of dilute sulphuric acid at 18*
dissolves about 0*54 grm.; at 18*5* from 0*65 to 0*72 grm.; and at
80* from 109 to M9 grm.
g 709. Arrine — Arseniuretted Hydrogen, H3A8.— Mol. weight, 78 ;
vol. weight, 39 ; specific gravity, 2'695 ; weight of a litre, 3*4944 grammes;
percentage composition, 95*69 As, 4*31 H ; volumetric composition, 2 vol.
HjAs » half vol. As + 3 vol. H. A colourless inflammable gas, of a foetid,
alliaceous odour, coercible into a limpid colourless liquid at ordinary
pressure of- 120* ; it solidifies at - 1 18'9', melts at - 113*5', and boils at
- 55*. The products of the combustion of arseniuretted hydrogen are
water and arsenious acid ; thus, 2H3AS + 3O2 = 3H2O + AsjOj. If sup-
plied with air in insufficient quantity, if the flame itself be cooled by (for
example) a cold porcelain plate, or if the gas pass through a tube any
portion of which is heated to redness, the gas is decomposed and the metal
separated. Such a separation may be compared with that of the deposit
of carbon fram ordinary flames, when made to play upon a cooled surface.
It may also be decomposed by the electric spark ; t e.^., if the gas is
passed slowly through a narrow tube 0*7 to 0*8 mm. internal diameter,
provided with wires 0*5 to 0*6 mm. apart, and a small induction coil
used connected with two large Bimsen's cells, then, under these conditions,
arsenic as a metal is deposited in the neighbourhood of the sparks. For
the decomposition to be complete, the gas should not be delivered at a
greater speed than from 10 to 15 c.c. per minute. The gas bums with
a blue-white flame, which is very characteristic, and was first observed
by Waokenroder. It cannot, however, be properly seen by using the
ordinary apparatus of Marsh, for the flame is always coloured from the
glass ; but if the gas is made to stream through a platinum jet, and then
ignited, the characters mentioned are very noteworthy.
Oxygen (or air) and arsine make an explosive mixture. Ohlorine
decomposes the gas with great energy, combining with the hydrogen,
and setting free arsenic as a brown cloud; any excess of chlorine
combines with the arsenic as a chloride. Sulphur, submitted to
arseniuretted hydrogen, forms sulphuretted hydrogen, whilst first
arsenic and then sulphide of arsenic separate. Phosphorus acts in a
similar way. Arseniuretted and sulphuretted hydrogen may be evolved
at ordinary temperatures without decomposition ; at the boiling-point of
* Chem. CerUrbl., 1889, 569.
t K. Klobrikow, Zeit. Anal, Chem,, xxix. 129-138.
I ;io, 7i'0
ARSENIC,
549
merctiry (350') they are decomi?o»edt sulphide of arsenic and hydrogen
being formed ; thus, ^H^S + SAsHg^ As^Sg-heHs, a reaction which is of
some importaocG from a practical point of view. Many metals have
alBi> the property of decomposing the gas at high temperatures, and
setting hydrogen free. Metallic oxides, agaiti, in like manner combiae
with araenic, and set water free; e.g.^ 3CuO + 2H3Aa^ CugAsj^ + SHgO.
A solution of copper sulphate ahsorhs arsine completely, and arsenide
of copper is precipitated, SSO^Cu + 2 AsH^ ^ SSO^H^ + As^CrUg,
Arsine acta on solutions of the noble metal a like phoai>hu retted
hydrogen, precipitating the metal and setting free argenious acid ; for
example, nitrate of silver is decomposed thna —
2[ABAg^ + 3N0j,Ag] + SH^O = ISAg + As^Og + 6N0gH,
This i^eaction admits of valuable practical application to the estimation
of arsenic ; for the precipitated silver is perfectly arsenic-free ; the
excess of nitrate of silver is easily got rid of by a chloride of sodium
solution, and the absorption and decomposition of the gm are Qomplet#.
In cases of poisoning by arsine, the blood when examined by the
spectroscope (a process the analyst should never omit where it is
possible), is of a peculiar inky colour, and the bands bet wean D and 0
are melted together, and have almost vanished. Such blood, exposed to
oxygen, remains unaltered,
§ 710. Arsine in the Arts, €ta— In the bronaing of brass, in the
desitverising of lead by zinc, and subsequent treatment of the silver zinc
with hydroohloric acid, in the tinning of sheet iron, and similar pro-
cesses, either from the use of acids containing arsaoiG as an Impurity,
or from the application of arsenic itself, arsine is evolved,
§711. Effects on AnimalB and Man of Breathing Arsitie.^Tbe
most general eftect on mammals is to produce jaundice, bloody urine,
and increase in the biliary secretion. In the course of numerous experi-
ments on dogs, Stadelmann* found that by making them breathe a dose
of arsine, which would not be immediataly fatal, icterus was always pro«
duced under these circumstances, and could be always detected by the
appearance of the ti^ues. The bile is remarkably thickened, and the
theory is, that in such cases the jaundice is purely mechanical, the gall-
duct being occluded by the inspissated bile. Rabbits experimented upon
similarly showed increased biliary secretion, but no jaundice ; while it
was proved that cats are not so sensitive to arsine as either mbbits or
dugs. There are not wanting instances of arsine having been breathed
by man— the discoverer of the gas, Gehlen, was in fact the first victim
on record. In order to discover a flaw in his apparatus he emelt
• " Die AraetiWteiMsrstofr-Vergiflang/* Archivf. ^tper. I^tk u. Pharm., Leipzig,
550 POISONS: THEIR BPFECT8 AND DETECTION. [§ 71 1.
strongly at the joints, and died in eight days from the eflFects of the
inhalation.
Nine persons, workmen in a factory, were poisoned by arsine being
evolved during the treatment by hydrochloric acid of silver-lead con-
taining arsenic. Three of the nine died ; their symptoms were briefly
as follows : —
(1) H. K., 22 years old ; his duty was to pour hydrochloric acid on
the metal. Towards mid-day, after this operation, he complained of
nausea, giddiness, and malaise. In the afternoon he felt an uncommon
weight of the limbs^ and an oppression in breathing. His fellow- work-
men thought that he looked yellow. On going home he lay down and
passed into a narcotic sleep. Next morning he went to his work as
usual, but was not capable of doing anything ; he passed bloody urine
several times throughout the day, and fell into a deep sleep, from which
he could scarcely be roused. On the third day after the accident, a
physician called in found him in a deep sleep, with well-developed
jaundice, the temperature moderately high, pulse 100. On the fifth
day the jaundice diminished, but it' was several months before he could
resume his work.
(2) J. T., «^ed 19, suffered from similar symptoms after five and
a half hours* exposure to the gas. He went home, vomited, was
jaundiced, and suffered from bloody urine ; in six days became con-
valescent, but could not go to work for many months.
(3) C. E. was very little exposed, but was unwell for a few days.
(4) L. M., 37 years old, was exposed two days to the gas; he
vomited, had bloody urine, passed into a narcotic sleep, and died in three
days from the date of the first exposure.
(5) J. S., aged 40, was exposed for two days to the gas; the
symptoms were similar to No. 4 ; there was suppression of urine, the
catheter drawing blood only, and death in eight days.
(6) M. K, 36 years old ; death in three days with similar symptoms.
(7), (8), and (9) suffered like Nos. 1 and 2, and recovered after
several months.
The chief post-mortem appearance was a dirty green colour of the
mucous membrane of the intestines, and congestion of the kidneys.
Arsenic was detected in all parts of the body.*
Two cases are detailed by Dr. Valette in Tardieu*s £tude,\ A
mistake occurred in a laboratory, by which a solution of arsenic (instead
of sulphuric acid) was poured on zinc to develop hydrogen. Of the two
♦ Trost, *• Vergiftung durch ArsenwasserstofF bei der technischen Gewinnuiig
des Silbers,'* Viertdjahrsschrift f. gericM. Med., xviii. Bd., 2 Heft, S. 6, 1873.
t Ambroise Tardieu, JSlude M6dteo-legale sur V Empoisonnement, OUs. xxv. p.
449.
§ 7I2-7U']
ARSKKia
S5I
auffereri, the one recovered after mi illness of about a week or i«n days,
the other died at the end of twentj -eight days. Tlie main symptoms
were yellofrness of skiu, vDiniting^ hloody urine, great depresBioiij slight
diarrhoea, headache, and in the fatal case a morbiliforro eruption. In a
case recorded in the Briiish Medical Jommtd^ November 4, 1876, there
were none of the usual ejmptoraa of gastric irritation* but loss of
memory of recent acta, drowsiness, and giddiness,
% 712- The Sulphides of Arsenic.— OF the sulphides of arsenic, two
only, realgar and orpiment, are of any practical importance. Eeaitjai\
A8gS3 = 214 ■ speciHc gravity, 3'544 ; composition in 100 parts. As 70 09|
S 2^*91 ; average composition of commercial product, As 75, B 25.
Realgar is found native in ruby -red crystals, and is also prepared arti-
ficially by heating together 9 parts of arsenic and 4 of sulphur^ or 198
parts of arsenious anhydride with 112 parts of sulphur, 2As20a + 7S =
SAs^g + SSO^. It is insoluble in water and in hydrochloric acid, but
IS readily dissolved by potas^ic di^^ulphide, by nitric acid, and by aqua
regia. It is decomposed by caustic potash, leaving nndiseolved a brown
sediment (Asj^S), which contains 96*5 |>er cent, of arsenic. The
dissolved portion is readily converted into arsine Ijy aluminium.
§ 713. Orpiment, or Ar&emc Trisulphide.^AsjSj = 246; a[>ecific
gravity, 3 46 ; compoaition in 100 parts, As 60^98, S 39*02 ; found
native in crystals, presents itself in the laboratory usually as a brilliant
yellow amorphous powder, on passing aulphuretted hydrogen through an
acid solution of arsenioua acid or an araenite. It is very insoluble in
water (about one in a milUon^ Fresenins:), scarcely soluble in boiling con-
ceatiated hydrochloric ncidj and insoluble generally in dilute acids. Red
faming nitric acid dissolves it, converting it into arsenic and sulphuric
acids; ammonia and other alkaline sulphides, the alkahes themselves,
alkaline carbonates, bisulphide of potassium, and aqua regia, all dissolve
it readily* In the arts it is used as Kiuj^^s yellow (sec p. 555)* Tanners
also formerly employed a mixture of 90 parts of orpiment and 10 of
quicklime, under the name of Bimma^ as a depilatory ; but the alkaline
sulphides from gasworks are replaciug this to a great extent.
g 714, Haloid Arsenical CompoundR.— The Chloride of Arsemc^
A8Clg=lbl'5; specific gravity liquid, 0* 2*205; boiling-point 134*
(273'2' F*), is a heavy, colourless, oily li<juid, which has been used as
an escharotio in cancerous affections {principally by quacks )* In one
process of detectiiig and estimating arsenic, the properties of this sub-
stance are utilised (see p. 54 )» It is immediately decomposed by water
into arsenious and hydrochloric acids.
The Iodide of Arsenic ( Asf^) i^ used occasionally in skin diseases, hut
is of little interest to the analyst ^ it is commonly seen in the form of
brick*red brilliant Bakes.
552 P0i«O5«: thuk dtects asd ditictiox. [§ 715,716.
S 715. Anenic in flie ArtfL— The metal b aaed in Tamoas allojB ;
for exampley specnlam metal is made of tin, copper, and a little arsenic ;
wliite copper w an alloj of copper and arsenic ; shot is composed of 1000
part« of lead mixed with 3 of arsenic ; the common Britannia metal nsed
for teapota, spoons, etc^ often contains arsenic ; and brass is bronzed
with a thin film of arsenic. It was formerlj moch employed in the
manufactore of glass, bnt is being grsdoallj superseded. It is also now
used to some extent in the reduction of indigo blae, and in that of nitro-
benasole in the maaufactnre of aniline.
In cases of snspected poisoning, therefore, and the finding of arsenic
in the stomach, or elsewhere, it maj be set up as a defence that the
an^nic was derived from shot used in the cleansing of bottles, from Uie
bottles themselyes, or from metal vessels, such as teapots, etc.
The arsenic in all these alloys being extremely insoluble^ any solution
to a poisonous extent is in the highest degree improbable. It may, how-
ever, be necessary to treat the vessels with the fluid or fluids which have
been supposed to exert this prejudicial action, and test them for arsenic.
The treatment should, of course, be of a severe and exhaustive character,
and the fluids should be allowed to stand cold in the vessels for twenty-
four hours; then the effect of a gentle heat should be studied, and,
lastly, that of boiling temperatures. The analysis of the alloy itself, or
of the glass, it would seldom be of value to undertake, for the crushed
and finely divided substance is in a condition very different from that of
the article when entire, and inferences drawn from such analytical data
would be fallacious.
Arsenious anhydride is also used for the preservation of wood, and
It thrown occasionally into the holds of vessels in large quantities to
prevent vegetable decomposition. In India, again, a solution of
arsenic is applied to the walls as a wash, in order to prevent the attacks
of insects.
§ 716. Pharmaceutical, Non-oflBdnal, and other Preparations of
Anenic— (1) Pharmaceutical Preparations. — The Liquor arsenicalis
(Fowler's solution), or solution of arsenic of the pharmacopoeia, is
composed of: —
.Oarbonate of Potash, . . 87 grains (^'64 grms.)
Anenioos Aoid, • . . . 87 „ (5*64 ,, )
Compound Tincture of Lavender, . . 5 drachms (17'72 c.c)
dissolved in 1 pint (567*9 c.c.) of water; every ounce, therefore, con-
tains 4*3 grains of arsenious acid (or 100 c.c. = '9As20jt) ; the strength
is therefore nearly 1 per cent. Chemically, it is a mixture of two
arsenites, As O^K^H and 2KAs02 + As^O,.
Liquor Ammonii Arsenitis (not officinal) is made of the same
strength, ammonium carbonate being substituted for potassic carbonate.
§ 7l6.] ARSENIC. ^^^ 553
The hydrOf^Monc mluti^n of arsenic h mm'pij arsenbua acid dis-
solved in hydrochloric acid j its streugth ghouJd be exacl^lj the same as
that of Fowler's solution,
A solixiion ot arMeniate of soda* contains the anhydrous saAt in the
proportion of 4 grains to the ounce {'9 in 100 c.c.) of water.
Liquor Arseim et Hydrargyri lodidl (Doooyan's Solution of
Arsenic). — This is not officinal, but is used to some extent in skiE
diseases ; it is a solution of the iodides^ of mercurj and arsenic ; strength
about 1 per cent, of each of the iodides*
Arseniate of Iron, Fe^As^Oj^, ig an amorphous green powder, used to
some extent in medicine. It should contain 33 '6 per cent, of metallic
anenie.
Clemen's SolutioiL — A solution of the bromide and arseniate of
potassium ; strength equal to 1 per cent, arsetiious acid. Officinal in
U.S., France, and Norway,
Filula Asiatica (not o^cinal) is composed of arsenious acid, extract
of gentian^ and black pepper. There is yVth of a grain (5'4 milligrama)
of arseniouB acid in each pill.
Dr. De ValanguiB' Solutio Bol^entes mineralie is composed of 30
grains of AsgO^ dissolved by 90 minims of HCl in 20 oz. of water ;
strength = 0*034 percent. As^^Og.
(2) Veterinaiy Arsenical Medicine,— Common veterinary prepara-
tions containitig arsenic are ; — A ball for worms, containing in parts —
CaJomel rs per eent.
Arsenioiis Addj * * * . . 1 *3 , ,
Tin Filiijgt, . . , , , 77*9 „
Venice Turpentine. t * , . . 19-5 ^^
A common tonic ball : J —
Ara«Diou» Add, , * 5 to 10 grains ( '32i to '648 grm*)
Antae«d, . . . } ok, {lA'lfH grm&.)
Opium 30 gmna ( I'M „ )
Treacle, * . * , q. »,
An arBcnical ball, often given by griKJms to horses for the pnrpoae
of improving their coats, contains in 100 parts : —
Anenloiis Add 2'5]^rc«nl,
Pimeiito, , , * « • . IQ'2 ,,
Extract of GetitiADp . . , . 73*S ,,
Another ball in use is compo6ed of ai^entc and verdigris (acetate of
* TbQ rDTmala for ArsontaU of 8od& ia If a^HAs047H^O, but it ^metimes eout&uifl
mote water.
t The Venice tur|iontlae m nrelj found in ordiiiAiy caramerce^ wliat is mid
Hndor tliat n&me consisting of blrwek rvmm md oil of turpentine,
t A aimilttr prepamtioii In (Summon u»e has tUc addition of sulpb&te of siuc«
554 POISONS: THEIR EFFECTS AND DETECTION. [§ 716.
copper), of each 8 grains ('SIS grm.) ; cuprio sulphate, 20 grains (1*3
grm.) ; q. s. of linseed meal and treacle.
(3) Eat and Fly Poisons, etc. — An arsenical paste sold for rats has
the following composition : —
Arsenious Acid, 5*0 per cent
Lampblack, *6 ,,
Wheat Flour, 46-3 „
Suet, 46-3
Oil of Aniseed, a small quantity.
Another rat poison is composed as follows : —
White Arsenic, 46*8 per cent
Carbonate of Baryta, . . . 46*8 ,,
Rose-pink,* 6*8 ,,
Oil of Aniseed, *2 , ,
Oil of Rhodium, '2 ,,
Various arsenical preparations are used to kill flies; the active
principle of the brown ^^ papier moure " is arsenious acid. A dark grey
powder, which used to be sold under the name of fly-powder, consisted
of metallic arsenic that had been exposed some time to the air.
Fly- water is a strong solution of arsenious acid of uncertain
strength, sweetened with sugar, treacle, or honey. Another fly-poison
consists of a mixture of arsenious acid, tersulphide of arsenic, treacle,
and honey.
(4) Quack and other Nostrums.— The analyst may meet with
several quack preparations for external use in cancer.' A celebrated
arsenical paste for this purpose is composed of : —
Arsenious Acid, 8 per cent
Cinnabar, 70 „
Dragon's Blood, 22 „
Freres Gome's Cancer Paste is composed of arsenious acid, 1 ;
charcoal, 1 ; red mercury sulphide, 4 ; water, q. s.
The tasteless " agtie drops " formerly used in malarious districts are
simply a solution of arsenite of potash.
Davidson's Cancer Bemedy consists, according to Dr. Paris, of equal
parts of arsenious acid and powdered hemlock.
In India, arsenic given as a medicine by native practitioners, or
administered as a poison, may be found coloured and impure, from
having been mixed either with cow's urine, or with the juice of leaves,
etc.t
Arsenious acid is used by dentists to destroy the nervous pulp of
decayed and painful teeth, about the twenty-fifth of a grain (2 5 mgrms.)
* Alum and carbonate of lead coloured with Brazil and peach woods,
t Chever, Me<L Jurispnidence/or India, p. 116.
§ /1 6.] "^^^ ARSKNia ^^^■^ 555
being placed in the Kavitj. A commoti formula m arsenbus acid, 2 ;
euJpbate of morphine, 1 ] cre^isote, q. s. to make a stiff pnste. There is
no record of any accident havipg resulted from thie practice hitherto ;
but 81 nee the dentist seldom weighs the arsenic^ it is aot altogether free
from daugen
(5) PigmeniBf etc. — King's yellow should be As^Sg, the trisulphide
of arsenic or orpiment. It m frequetitlj adulterated with 80 to 90 per
cent, of arseuious acid, aod in such a case is, of course, more poisonous.
King's yellow, if pure, yields to water nothing which gives any arsenical
reaction.
A blue pigment^ termed miVtero^ blv^ cooBistfl of about equal parts
of arseuite of copper and potash, and should contain 58*7 per cent, of
metallic arsenic ( = to 51 '084 Aa^O^H) and 15*6 of copper,
Scbweinfurt green (Byn. FhneraldHjrf^en)^ {G\xknj^j^\f^\x{Q^'^^0.^^ ih
a cupric arisen ite and acetate, and should contain 25 per cent, of copper
aod 58'4 per cent, of arsenions acid. In analysis, the copper in thii
compound is readily seimrated from the arsenic by first oitdising with
nitric acid, and then adding to the nitric add solution amraonia, until
the blue colour remains unchanged. At this point ammonium oxalate
is added in excesSi the solution is juat acidified by hydrochloric or nitric
acid, and, on standing, the copper separates completely (or almost so) as
oxalate, the arsenic remaining in solution.
Another method is to pass SH^ to saturation, collect the sulphides on
a filter, and, after washing and drying the mixed sulphides^ oxidise with
fuming nitric acid, evaporate to dryness, and again treat with nitric acid.
The r^idue is fused with soda and potasgic nitrate, the fused mass is
dissolved in water, acidulated with nitrio acid, and the copper is pre-
cipitated by potash; the solution is filtered, and in the filtrate the
araenio is precipitated as ammonio-magnesian arseniate or as tri-
sulphide.*
Scheele's green (CuHAsOjj) is a hydrocupric arsenite, and contains
52*8 per cenL of arseoious anhydride and 33"8 per cent, of copper.
(6) External Applicatioii of Arsenic for Sheep, etc. — Many of these
are simply solutions of arsenic, the solution being made by the farmer.
Most of the yellow sheep dipping compounds of commerce are made up
either ol impure carbonate of potash, or of soda ash, arsenic, soft soap,
and sulphur. The French hain de tersier is composed of : —
Araentous Add* , 1*00 kgnn,
FffTTOUB Sulphate^ 10 '00 ,,
Peroxide of Iron, «..,.. 0'40 „
Gentian Powder, . 0-^0 ,^
^ This is to be added to 100 kgrms. of water. Another common applica-
* P, Qaeci, Chim, CeMrhL. 1887, L528*
5S6 POISONS: their effects and detection. [§ 717.
tion consists of alum and areeuic (10 or 12 to 1), dissolved in two or
three hundred parts of water.
(7) Arsenical Soaps, etc. — Arsenic is used in preserving the skins of
animals. One of the compounds for this purpose, known under the name
of BScoeur^s arsenical soap, has the following composition : —
Camphor 8 '4 per cent
Arsenic 20*2 „
Carbonate of Potash 56*2 „
Lime,* 202 ,,
(8) Arsenical compounds used in pjrotechny :—
Parts.
Blue fires— (1) Realgar, 2
Charcoal 3
Potassic Chlorate, 5
Sulphur, 13
Nitrate of Baryta, 77
(2) Sulphur 40-9
Nitre, 36*8
Sulphide of Antimony, . .12*3
,, Arsenic, 5
Charcoal, 5
Green fires — Metallic Arsenic, 2
Charcoal 3
Chlorate of Potash 5
Sulphur 13
Nitrate of Baryta, 7
Light green fire — Charcoal, 1 '75
Sulphide of Arsenic, 1*76
Sulphur 10-60
Chlorate of Potash, .... 23*26
Nitrate of Baryta 62*50
White fire— (1) Arsenious Acid, '76
Charcoal 1*63
Sulphide of Antimony 12*27
Nitrate of Potash, 86*69
Sulphur 48*76
(2) Realgar 6*1
Sulphur, 21*2
Nitrate of Potash 72*7
§ 717. Statistics. — During the twelve years 1892-1903 there were
registered in England and Wales 242 deaths from arsenic ; of these 58
were suicidal deaths; 79 were registered during 1900-1901 as due to
* The dust from the preserved skins of animals has caused, at least, one case
of poisoning. Ann, (Tffyg, Pub. el tie Med.-Lig., 2 s^r., 1870, t. xzxiiL p. 314.
§7«8.7i9-]
ARSENIC.
SS7
araeQioal beer j tlie renmiuder were aeeitiental. The aj^e iind sex dis-
tribution of petijoiia dying from accidental or sivicidal arsenical poisoning
other than beer poisoning are detailed in the following table : —
DEATHS FROM ARSENIC DURING THE TWELVE YEARS 1892-1908.
AcaJ0ENT OB. KfiGLIOBNOK.
Agea, .
stales, .
Feaiales,
1-5
3
5
5-15
7
6
3
25-€e
23
42
> 6& and above
i
1
Total
43
57
Total.
8
l;i
9
70
5
105
Sit
ICTOl!,
Ages, .
MaleB,
Females r
*
15-26
i
a
25-65
a2
15
65 and abore
4
0
Total
40
IS
Total,
7
47
4
63
g 718, Law Eelative to the Sale of Arsenic. — By the 14th of Viet,
0. 12, every person selling arsenic ia hound to keep a written reconi of
every particular relative to each tranBaction, guch as the namei abode,
and calling of the purchaser, the purpose for which the poison is
required, and the qnautitj sold, etc. These particulars are to he signed
also by tlie purcliaaer. No person (sec, 2) is allowed to sell arsenic to
any one unknown to the aeller, unless in the presence of a witness whom
the seller is acquainted with. The arsenic sold (see. 3} is to be mi>ced
with soot or indigo hi the proportion of half an ounce of indigo to a
pound of arsenic. It, therefore, follows that the coloured substance
should not contain more than 70 per cent* of arsenioua acid. The Act
applies to all the colourless preparations of arsenic : but it ts not to
atfect chemists in making up prescriptions for medical men, or m
supplying medical men ; nor 18 it to affect the wholesale dealers in
supplying arsenic to retail shops, etc. The penalty for conviction is
£20, or less,*
§ TI9, Dose.^ — The smallest eingle dose of arsenic known to have
proved fattd to a human being is -IS grm, (2 J grains). Farriers and
grooms are iu the habit of giving aa mnoh as 1*3 grm. (20 grains) a day
to a horse, so that the poisonous dose for this animal must be very large.
The niaximnm dose for the honied cattle appears to be from *32 to
'38 grm, (5 to 6 grains); that for a dog is 16 mgrms. (| grain), and
even this may, in the smalt er kinds, cause illness*
* Coraxaercial arsemc is ofteo much, adulterated, especially with gypautDi chalky
eto. These are most readily d^teeted by subliming the jirsonic. The aublimed
ar^eitio itself may not be entircily pure, sometitne^ contaiaing arMUioal solpliide
and andjDQmons oxid«.
5SS
POISONS: THEIB EFFECTS AND DETECTION. [§720,72!-
Tbe following mnj be coiisidereEl as dawjerous doses of anieiiic: — *13
grni. (2 gmins) for an adult ; 1 '9 grin. (30 grains) for a horse ; "64 grm.
(10 graiDs) for h cow ; and 32 to 64 Digmis. (J to 1 grain) for a dog*
§ 720. Effects of Arsenious Acid on Plants.— If the root or etem
of a pliant ib hnmert»ed in a soliiLton of arsienioua acidi the hue of the
leaves noon alters in appearance, the green colour becomes of a whitish
or browniah hue, and the plant withers ; the effect being very similar to
that produced hv liot water. The tootic action may be traced from
below upwards^ and analysis will detect mhiute quantities of arsenic in
all portions of the plant.
[t has, however, been shown by Gorup-Besanez,* that if arsenious
acid be mixed with earth, and plants grown in such earth, they only take
up inhmtes^imal qnantitiea of arsenic. Hence, in cases of cattle poison-
ing, any defence based upon the alleged presence of arsenic in the pasture
will be more ingenious than just.
The influence of arsenical fumes as evolved from manufactories upon
slkrul>s and trees is in general insignificant* Pines and firs^ five to six
year 3 old, have been known to suffer from a disease in Mbich there is a
shedding of the leaves, the more tender herbage being at the same time
affected. Whatever dangers the practice of steeping corn intended for
seed in a solution of arsenious acid, as a preventive of "smnt,^* may
po8i^esS| it does not appear to influence deleteriously the growth of the
future plant.
Superph osph ate of ma n n re is f r eq u e n tl y rich i n arsen i c, I> r. Ed m und
Davy asserts that plants to which such manure is applied take up
arsenic in their tissues, and M. Andotiard has made a similar statement.
Tnson t has also undertaken some experiments, which confirm Andonard
and Davy's researches. The bearing of this with relation to the
detection of arsenic in the stomachs of the herbtvora needs no comment
g 72L Effects on Animal Life — Ani malcules. — A 1 1 infusoria and
forma of aniraalculedife hitherto observed perish rapidly if a minute
quantity of arsenious acid is dissolved in the water in which they exist.
Insects, — Tiie common arsenical fly-papers afford numerous oppor-
tunities for observing the action of arsenic on ordinary flies ; within a few
minutes (five to ten after taking the poison into their digestive organs)
they fall, apparently from paralyiis of the wings, and die. Spiders and
all insects into which the poison has been introduced exhibit a similar
sudden death. It is said that in the neighbourhood of arsenical manu-
factories thi^re is much destruction among bees and other forma of insect
life.
Annelids. — If arsenious acid is applied to the external surface of
' Anntd. d. Chemit u, PharmaeUi Bd. cxivii, H. 2* 24S.
i Coolej''s IHclunmr^^ Art. '* Arsenic ^*
§ 721.]
ABSBI^IC.
SS9
worms or leeches, the part which it touches perishes Hrst^ and h"fe 16
extinguished giiiccessLvely in the others. If a wound is made first, and
the arseuious acid then applied to it, the effects are only intensified and
hastened. There is always noticed an augmenlation of the excretions;
the vermicular movements are at first made more lively, they then
become languid, and death is very gradual.
Birds. — The symptoms with birds are somewhat different, and vaiy
according to the form in which the jwison is administered, viz., whether
as a vapour or in solution. In several experiments made by Eulenberg
on pigeons, the birds were secured under glass shades, and exposed to
the vapour of metallic arsenic vaporised by heat; It is scarcely neces-
sary to remark thjit in operating in this way, the poisoning w^as not
by metallic arsenic vapour, but by that of arsenions acid. One of these
experiments may be cited :■ — A pigeon was made to breathe an atmo-
f5phere charged with vapour from the volatilisation of metallic arsenic.
The bird was immediately r^tless ; in thirty minutes it vomited
repeatedly, and the nasal apertures were noticed to be moist ; after a
little while, the bird, still breathing the arsBuious acid atmosphere, was
mnch distressed, shook its head repeatedly, and yawned ; In fifty minutes
the reRpiration was lakuired, and in fifty-nine minutes there wtis much
vomiting. On removing the bird, after it had beeu exposed an hour to
the vapour (vl6 grm. of metallic arseulc having been evaporated in all),
it rapidly recovered.
Six days after, the pigeon was again exposed in the same way to the
vapour, but this time '56 grm. of metallic arsenic was volatiltaed. In
Bfteen minutes there was retching, followed by vomiting. On taking it
out after an hour it remained very quiet, ate nothing, and often puffed
itself out ; the breathing was normal, movements free, but it had
unusual thirst. On the second and third day the excretions were
frequent and 6uid ; the cardiac pulsations were slowed, and the bird was
disinclined to move. On the fourth day it con tinned in one place,
pufting itself out ; towards evening the respirations slowed, the beak
gaping at every inspiration. On attempting flight, the wings fluttered
and the bird fell on ita heatL After this it lay on its side, with slow,
lul^onred respiration, the heart-beats scarcely to he felt, and death took
phice without convulsions, and very quietly. On examining the organs
after d<*ath, the brain and spinal cord were very blooilless ; there were
ecchymosejs in the lungs ^ but little else characteristic. The experiment
quoted has a direct bearing upon the breathing of arsenical dust ; as, for
example, that which floats in the air of a room papered with an easily
detached arsenical pigment Other cxp^erimente on birds generally have
shown that the symptoms produced by arseuious acid in solution, or in
the solid form, in a dose insuJiioient to destroy life, are languor, loss of
56o
POISONS: THKIR KFFKCT3 AND DirTECTinN-
[§ 722.
appetite, and the voidance of large quantities of liquid excreta Itka
verdigris. Witli fatal doaes, the bird remaitia quiet ; there are fluid,
sometimes blood j, excretiotia ] Rpa&raodic movements of the pharynx,
anti-periatalttc contrnctioii of the oesophagus, vomitings general tretnb-
liug of the body, thirst, erection of the featherSj atid labotired respiratiota.
The bird becomes verj feeble, and the scene mostlj cloBea with
insensibility and convulsiona.
liatnnialB, such aa cats, dogs, etc., snflfer from symptoms fairly iden-
tical with thoae obReryed in man i but the nervous synxptoms (according
to P. Hugo) do not predominate, while with rabbits and guinea-pigSi
nervous syroptomB are more niarked and constant* There are vomiting,
purging, and often convulsions and paralyaia before death. It has been
noticed that the muscles after death ate in a state of great contraction.
The slow poiaoning of a dog, according to Lolliot,! produced an erythe-
matous eruption in the vicinity of the joints, ears, and other parts of the
body ; there were conjunctivitis, increased lachrymal secretion, and
photophobia ; the hair fell off.
§ 722. Effects of Arsenious Add on Man. — The symptoms produced
by arsenious acid vary according to the form of the poison — whether
solid, vaporous, or soluble— according to the condition of bodily health
of the person taking it, and according to the manner in which it ia intro-
duced into the animal economy ^ while they are also in no small degree
modified by individual peculiarities of organisation and by habit, as, for
instance, in the arsenic-eaters.
Arsenic-Eaters, — ^In all European conntries grooms and horse-dealers
are acquainted with the fact that a little arsenic given daily in the com
improves I he coat, increases, probably, the assimilation of the food, and
renders the horse plump and fat. On the Continent grooms have been
known to put a piece of arsenic, the size of a pea, in a little oatmeal,
make it into a hall, tie it up iti a linen rag, and attach it to the bit ; the
saliva dissolves, little by Uttle, the poison, while both the gentle irritation
and physiologiciil action excite a certain amount of salivation, and the
white foam at the mouth, and the champing of the horse, are thought
vastly to improve the appearance. Shot, which contains a small quantity
of arsenic, has been used for the same purpose, and from half a pound
to a pound of small shot has been given to horses. When a horse has
been for a long time dosed with arsenic, it seems necessary to ooutinue
the practice; if this is not done, the animal rapidly loses his condition.
The explanation probably is, that the arsenic stimulates the various cells
and glands of the intestinal tract to a superactioo^ the natural termina-
tion of which is an cnfeeblement of their secreting power— this especially
* Architff. w?pfr. Path, u. PhamiakQl, L^iptig, 1SS2*
t Jtude Phynml ifJr^^n/, Th^, Pmris, 1868.
S 725I
ABsamo.
561
ia the absence of tbe stimulua, Tummg from equine involuntaiy arsenic-
eaters, we find the stmnge custom of arsenic-eating vDluutarilj pursued bj
the nices of lower Austria and Styrla, especially by those dwelHttg on the
mountains separating Styria from Hungary. In India also (and eBpocially
in the Punjaub) the same practice prevails, and here it is often taken as
an aphrodisiac. The mountaineers imagine that it increases the respira-
tory power, n'>r is there wanting some evidence to show that this is
actually the fact, and medicinal doses of arsenic have been in use for
some time in cases of asthma and other diseases of the chest. The
arsenic-eaters begin with a very small dose, which is continued for several
weeks or months, until the system gets accustomed to it. The amount
is then slightly augmented until relatively large doses aro taken with
impunity* In one case ■* it appears that a countryman, in good health,
and sixty ymrs of age, took daily 4 grains of araenioua acid, a habit
which he had inherited from his father, and which he in turn bequeathed
to his son.
The existence of such a custom as arsenic-eating, in its literal sense,
has more than once been doubted, but all who have travelled over Styria
and other places where the habit prcvaih have convinced themselves
that the faot^ have not been overstated- For example, Dr, Maclagan, in
company with Dr, J. T, Rutter,t visited Styria in 1865, and having
carefully weighed 5 or 6 grains of arsenic, saw these doses actually
swallowed by two men. On collecting their urine, about two hours
afterwards, abundant quantitative evidence of its presence was found ;
hut in neither of the men were there the slightest symptoms of poisoning.
It is obvious that the existence of such a habit might seriously complicate
any inquiry into arsenical poisoning in these regions.
§ 723. Maimer of Introduction of Arsenic. — Arscnious acid eierts a
poisonous action, whether it is taken by the stomach, or introduced into
the system hy any other channel whatever* The differences in the
symptoms produced by external application (as through a wound), and by
swallowing arscnious acid in substance or in solution^ are not so marked
as might be expected. It w^as probably Hunter who first distinctly
recognised the fact that arBenic, eren when introduced outwardly by
applicAtion to an abraded surface, exerts & specific effect on the mucous
membrane of the stomach. Brodie J states, "Mr, Home informed me
that in an experiment made by Mr. Hunter himself, in which arsenic
was applied to a wound in a dog, the animal died in twenty-four hours,
and the stomach was found to be considerably inflamed* I repeated this
experiment several times, taking the precaution of always applying a
* TarJie\u tip. eii,
t Edin, Med. Jourtk, April 1S65 ; BriL and For. Mfd. CktK Jfmm.^ Oct IS 66.
t PhiL rniiw.,1812.
36
562 POISONS : THEIR EFFBCTS AND DETECTION. [§ 724.
bandage to prevent the animal licking the wound. The result was that
the inflammation of the stomach was commonly more violent and more
immediate than when the poison was administered internally, and that
it preceded in appearance the inflammation of the wound."
§ 724. Cases of Poisoning by the External Application of Arsenic.
— A mass-poisoning by the external use of arsenical violet powder to
infants occurred in England some years ago. Two deaths from this
cause were established by coroners' inquests.^ Dr. Tidy found the violet
powders used in the two cases to hkve the following composition : —
1. 2.
Per c«Dt. Per cent.
Anenious Acid, 38*5 38 '3
Starch (Potato), 54-8 65-4
Magnesia, etc 6*7 6'3t
Although the children were poisoned by absorption through the skin
(unless it is allowed that some may hd.ve found its way in the form of
arsenical dust into the throat, or, what is still more probable, that the
infants may from time to time have seized the puff-ball and sucked it),
the large quantity of "421 grm. (6*5 grains) of arsenious acid was
separated in the one case, and '194 grm. (3 grains) in the other. In
these cases arose the question which is sure to recur in legal inquiries into
poisoning by absorption, viz., whether the poison lying on the surface
and folds of the skin could not have been mixed during the post-mortem
examination with the organs of the body? In these particular cases
special care appears to have been taken, and the answer was satisfactory.
It is not amiss, however, to call attention to the extreme precaution
which such instances necessitate.
A woman, aged 51, had used a solution of arsenious acid to cure
• "Gleanings in Toxology," by 0. Meymott Tidy, li.B.— Lancet, Aug. 21,
1878.
t Two recipes were handed in at the coroner's inquest which pretty fairly represent
the composition of ordinary commercial violet powder : —
First QwUity, sold at 78. per gross.
Starch Powder 28 lbs.
Magnesia, 1} lb.
Orris-root, 1 lb.
Violet Perfume, 1 oz.
Essence of Roses 5 drops.
SecoTid QiuUity, sold at Qs. per gross.
Terra Alba (Sulphate of Lime), . . 14 lbs.
Potato starch, 211b8.
Magnesia, 3 lbs.
Orris-root, I4 lb.
Violet Perfume, 14 oz.
]SBsenoe of Roses, . 5 drops.
§ 724.]
ARSZKIC.
563
the iteh ; erysipelas of the body, however, followed, and she died after a
long iUneaa — one of the Bymptoms noted being trembling and paresis of
the Hmba,* In a ease recorded by Deegranges,! a young chambermaid
had applied to the un wounded scalp an arseoical ointment for the purpose
of destroying vermin. She also suffered from a severe erysipelas, and
the hair fell oC Quacks have frequently applied various arseoical pastes
to ulcers and cancerous breasts with a fatal result. Instances of this
abound ; in one, a charlatan applied to a chronic ulcer of the leg an
arsenical caustic ; the patient showed symptoms of violent poisoning, and
died on the sixth day* J In another, a lady suffering from some form of
tumour of the breast, applied to an unqualified practitioner, who made
from fifteen to twenty punctures with a lancet in the swelling, covered a
piece of bread with an arsenical compound, and applied the bread thus
prepared to the breast. Twelve hours afterwards symptoms of violent
gastric irritation commenced; and vomiting and a sauguinol en t diarrhoea
followed, with death on the fifth day. Arsenic was found in all the
organs, § 8uch examples might be multiplied. Arsenic has been in
more than one case introduced criminally into the va^na with a fatal
result II Foder^ e.g.t has recorded the case of a maidservant who
poisoned her mistress by intentionally administering several arsenical
enemata.^ Arsenious acid again has been respired in the form of vapour.
One of the best instances of this is recorded by Taylor, and was the sub-
ject of a trial at the York Lent Assizes, 1864. The prisoner placed some
burning pyrites at the doorway of a small room, in which there were
eight children, including an infant in the cradle. The other children
were removed speedily, but the infant was exposed to the vapour for an
hour; it suffered from vomiting and diarrhoea, and died in twenty -four
hours. There was slight inflammation of the stomach and intestines, the
brain and lungs were congested, and the lining membrane of the trachea
of a bright red colour. Arsenic was detected in the stomach, in the lungs,
and spleen. The pyrites contained arsenic^ and the fatal fumes were in
effect composed of sulphurous and arsenioua acids.
* BeUcic, MAl-Idg,, t. iv. p. Vli.
t Reeaeil de ia Sot;, de Af^L de ParU^ t vi p, 22, Ati. m ; also Tiirdieu, Mi^
M^. 'Legale itir VMmpoimmneinefU, Oba. jtxvii. p, iBJ,
t Mean, BiMiuth^qtt^ Med., U Ixxlv., IS2I, p» 401,
§ Tardieu, op* dt, Oba. ixix. ; Dr. Vernoia, Arm, ttlf^g. et de MM^'Ltg., t.
xxxvi*, lutser,, p. HI, 1849,
II Ansittulx, Ciiniqu£ ChifurgitSfUi, M&ngor {Acta SoeieL Jieg, Mafitientf liL
p. 178) gives the cas« of a man who poLsoned bia t!irec wives auccessively with
arteiilc — the last two by iatroducitig into the vAgiim ii iif)wd«?r oooiposued of flour And
uri^ntc. Another Himil&r tsssa is reliiM hy BriskGn* Mungot mado experiments
on m&rcs, showing that wbeti araenie is &|ipli^ to th« vugi^^^ d'titth may result
frum inflAinnuitiou,
S64
POISONS: THEIR EFFECTS AND DETKOTION. [§ 725, 726*
§ 725. Arseoic in Wall-Paperi.— It is now an accepted fact that
arseiiicjil eolourH ou waJl-papens cause illness. The symptoma are those
of chronic poisonings and present nothing distinctive from the aifectfi
produced from small doses of arsenic.
Kirschga^er^ has described the symptoms in detail of twentj^is
cases. That arEenic is aettially present in patients miSenng is often
susceptible of proof, by examining skilfully and carefully a considemble
volume (from one to two dayi' collectiou) of the urine; in most of
the cas^ thus ejta mined arsenic has been discovered. This poisoning
is produced J sometimes from the dust, tit othens from diethylarsine
(GjH5)*AsH, a gas produced by moulds t such as Mutor mueedo^
Asperffiiha ^lauats, and othera grt>wing in a medium in which arsenic
is present. Gosio cultivated tbo Mucor mucedo on slices of potato
arsenic free, in bulbs having a constriction in the neck ; in this con-
striction, four centimetres a«'ay from the slices of potato, was packed some
cotton wool impregnated with a weak solution of arsenic j in time the
mould crept up to and inv^ed the cotton wool. From this experiment
Gosio concluded that the mould could grow on the surface of the paper
turned to the wall, and that the mjcellium could grow through the
pores of paper and attack the arsenical colours in the wall side of
the paper. Diethylarsine is a gas with a strong alliaceous odour; it
precipitates a hydrochloric acid solution of sublimate, forming crystals
of diethylarsine -cbloro-mercurate, AsH(C3H J^HgCl^ ; the crystals
fuse at about 240°. It also gives a precipitate with mercuric nitrate,
As lI(C3Hg)-(N0^)^Hg Dthyl-ai^ine-raercuric nitrate.
The ga*! appears to be readily enough produced by the action
of the common moulds upon organic matter in the presence of small
amounts of arsenic; the moulds vary in this property: Mucor mucedQ
and Aspergillus glaucus react well ; on the contrary, Pemdllium ijlaufum^
Mucor raniosm^ and several others have either no action, or the action
is but alight. One mould, tiie PeniHUium hreHratd*'^ has quite a special
endf^wmcut in forming this peculiar arsenical compound ; so much so,
that Gosio has proposed its use as a reagent for arsenic, the garlic odour
being perceived when the fuugus is made to grow in solutions containing
organic matter and only trnees of arsenic,
g 726. Fonns of Arsetiical Poisoning.— There are at least four dis-
tinct rorms of arsenical poisouingj viz,, an acute, subacute, a nervous,
aud a chronie form.
Acnte Form. — All those casc^ in which the inflammatory symptoms
are severe from the commencement, and in which the snflerar dies within
■ FuiHitjahr./. ff$rkhi, Mtd., N. F., ix* m.
t Gosio, Arthivt^ Italiaines dc hiohgU^ 18&2.
It Abel aud P. Buttisiiborfj
1 727:\
AHSENIC,
565
tweuty-four bourn, may be called acute. The com men cement of the
symptoms iu these caaea ia always within the hour; they have been
knowu^ indeed, to occur within eight naiiiutea, but the most usual time
is from twenty minutes to half an hour. There ia au acrid feeling in
the throat, with nausea j vomiting soon sets in, the ejected mattora
being at first composed of the substances eaten ; later they may be
bilious or even bloody, or composed of a whitish liquid. Dianhcra
follows and accompanies the vomiting, the motions are aometimes like
those met with iu ordinar)' diarrhcoa and English cholera, and some-
times bloody, There is foldjiesM of tlie extremities, with great feeble-
ness, and the pulse ia small and difficult to feel Tlie face, at first very
pale, takes a bluish tint^ the temperature falls still lower; the patient
sinks in collapse, and death takes place in from five to twenty hours
after the taking of the poison,
There can scarcely be said to be m\^ clinical feature wliich dii^titi-
guishes the above description from that of cholera; and supposing that
cholera were epidemic, and no suspicious circumstance apparently
present y there can be little doubt that a most experienced physician
might mistake the cause of the malady, unless surrounding circum-
stances give some hint or clue to it. In the acute form diarrhcea may
be absent, and the patient die, as it were, from ** shock.'* This was
probably tl*e cause of death in a case related by Casper,* that of JuliuE
Bolle, poisoned by hia wife. He took an unknown quantity of atBenic
in solution at seven in the morning, and in about three-quarters of an
hour afterwards sudcred from pain and vomiting^ and died in little more
than three hours. There were no signs of inflammation in the stomach
and in tea tin es^ but from the contents of the stomach were sei>anited
'0132 grm, of arseniuus acid, and '00513 grm* from pieces of the liver,
spleen, kidneys, lung, and blood. The doae actually taken is supposed
nut to have been less than 388 grm. (6 grains).
g 727. The Subacute Form.— The subacute form is that which ii
most common ; it exhibila some variety of phenomena, and individual
cases vary much in the matter of time. Tlic commencement of
symptoms is, as in the mos^t acute form, usually within the hour, but
eEoeptiona to this rule occur. In tk case quoted by Taylor, t and re-
corded by M. Tonnelier, the poison did not cause any marked illness for
eight hours; it w^as found, on post-mortem exaumuitiou, that a cyst had
been formed in the stomach which sheathed the arsenic over, and iu
some degree explained this delay. Iu another case, again, ten hours
elapsed, and this is considered to be the maxtuutm period yet observed.
* Gftse 138 ill Ooqjor's ffmrntkuch,
+ Taylor'a Fnn^ij^ tind J^tM^iiev 0/ JuHsprudm^e, vol. i.
vaL L y* fi^
Fliijidiii,
566
POISONS: THEIR RFFECTS AND DETECTION.
[§ 7^7'
As with the acute formj there is a feeling of nausea, followed by vomit*
iDg, which continues although the stomach is quite empty ; at fit's t the
ejected matter ia a watery fluid, but later it may be streaked with
blood* The tongue ia thickly coated ; thure ia gretit thirst, but the
drinking of any liquid (even of ice-cold nater) increases the vomiting,
if early always pain is felt in the epigaatrium, spreading all ever the
abdomen, and extending to the loin (which is tense and tender on
presaure)* Deglutition is often painful, and i» accompanied by a sort
of spasmodic constriction of the pharyngeal muscles, Dtarrhcea follows
the voniitingi and has the same cbaractera as that previously described \
ooc&sionally, however, this feature is absent* In the case recorded hj
Marti neau,* a man, aged 25, was seized at 10 hM. anddenly with vomit-
ing, which persisted all tliat day and the next, during which time the
bowels were obstinately confined. On the second day a purgative was
administered, whereupon dtarThG>a set in, and continued iintit bis deaths
which occurred in about two day a and sixteen hoars from the com-
mencement of the symptoms. This case is also remarkable from the
absence of pain or tender noes of the abdomen.
In subacute cases the nrine has several times been suppresaedi and
it is generally scanty and red in colour. IiTegularity of the heart's
action and feebleness are tolerably constant phenomena. As the end
approaches, there is excessive muscular weakness, the face is pale» the
eyes hollow ; the mucous membranes first, and then the skin, take a
bluish tint; the skin itself is covered with perspiration, and there has
been noticed a peculiar odour, which has been Hkened to arsine (arseniu-
retted hydrogen). The respiration ia troubled, convulsive movements of
the limbs have been observed, and cramps in the calves of the legs \
death follows in a variable time — from twenty-four hours to several
days> In certain cases there is a curious remission after violent
symptoms, the patient rallies and seems to have recovered ; but the
appearance ia deceptive, for the symptoms recur, and death follows.
Recovery may also take place ptirtially from the primary eflPects, and
then inflammatory changes in the stomach, etc., set in, with fever and
the ordinary symptoms which are common \xi all internal inflammatioih
A single dose of arsenious acid may cause a prolonged and fatal
illnesSj one of the best known examples being that of the suicide of the
Due de Praslin, f who took, with suicidal intent, on Wednesday, August 1 8,
1847, a dose of arsenious acid. The exact time of the act could not be
ascertained, but the ftrst e fleets appeared at 10 p.m. ; there were the
usual signs of vomiting, followed on the next day by diarrhoea, fainting,
* Tardienj op. tH.^ Oba^ iik.
+ Tardi^u, " R<?lfltion MMi^o-Lc^gale de rAssoasinat de k Duohesee de Praslin,"
Ani^ d^Hyfj. Ptib. ci da MMico-lAg.^ lB47t t. xxxviii. [h {^90 ; abo op, cU.t Obi, xL
§ 728-1
AtlSKKIC.
0f
aud extreme feeblenesB of the piilae, On Friday there was a remtssioti
of tho syraptoms, but great coldnesa of the limbs, iatermitteiicy and
feebleuess of the hearths actiou, and depression. On Saturday there was
alight fever, but no paiti or teudeniess in the abdomen, vouiitmg:^ or
diairhcsa ; on this day no urine was passed. On the Sunday he com^
plained of a severe eonstnetjon of the throat, and deglutition was
extremely painful ; thirst was extreme, the tongue intensely red, as well
as the mucous membrane of the month and pharynx, and the ptitieut
bad a sensation of burning from the mouth to the anus. The abdomen
was painful and distended, the heat of the skin was pronounced, the
pulse frequent and irregular, — sometimes strong, at others feeble, — the
bowels had to be relieved bj injections, the urine was in very small
quantity ; during the night there was no eleep. Tho duke died at
4*35 A.M. on Tuesday the 24 th, the sixth day ; intelligence was retained
to the last. As the end iipproached, the respiration became embarrassed,
the body extremely cold, and the pulse very frequent.
^ 728. In the nervous form the ordinary vomiting and purging are
either entirely suppressed, or present in but feeble degree ; and under
this heading are classed the rare cases in which, in place of the ordinary
symptoms, atfections of the nervous system predominate. Naruotism,
paresis, deepening into [iaralysia^ delirium, and even acute mania, as well
as epileptiform convnlsious, have all been recorded. In short, the
lymptoms show so much variety, that an idea of the malady produced
in this very rare form can only be obtained by studying the clinical
history of cases which have presented this aspect. In a case recorded
by Guilbert,* a man, thirty- five years of age, Imd swallowed a solution
of arsenic, half of which was immediately rejected by vomiting. A
little while afterwards his respiration became laborious; the eyes were
bathed with tears, which were so acrid aa to inflame the eyelids and the
cheeks ; the museies of the face were from time to time convulsed ; he
perspired much, and the perspiration had a fcetid odour ; there was some
diarrhcea, the urine was suppressed, and from time to time he was
delirious. Afterwards the oonvukions became general, and the symptoms
continued with more or lass severity for five days. On the sixth a
copious miliary eruption broke out^ and the symptoms became less
severe. The eruption during fifteen days every now and again re>
appeared, and at the end of that time the patient was oonvatescent^
but weak, Bable to ophthalmia, and had a tmiversal trembling of the
limbs.
in one of Brodie'a t experiments on rabbitei 7 grains of arsenious
* jQurmd ds V&n d«r Momk, 1750, t ir. p. 3Sd ; Tardieu, op, ffU,, Oba. jdii.
p. 430.
t " The Actiou of Poisons,** FhU, Tmns^t 1812.
S68
l^ISONS: THEIR EFFECTS AND DETECTION. [§ 729, 73a
acid were inserts in a wound in the back ; the effect of which wae to
paralyee the hind legs« In other experiments on animals^ paralyBis of
the hind legs has been frequently noticed, but patulyeia certainly is
rare in man ; in the case, however, recorded by Barrier^* of the five
men who took by mistake a solution of ar^enioug aeid, one of them
was found stretched on the ground with the inferior extremitiea
paralysed.
In a case of **nia«B" poisoning reported by Dr. Coqueret^t three
persoug ate by mistake ati unknown quantity of araenious acid^ — two of
them only suffered slightly, but the third severely, vomiting occurring
almost immediately, and continuing with frequency nntil the end of the
fourth day. Two hours after g wallowing the poison, the patient took
the hydrated oxide of iron as an antidote. On the aijtth day there was
stupor and a semi -delirious state, with an eruption of a pustular
character compared to that of the small-pox. These symptonis con-
tinued more or less until the fifteenth day, when they diminished, and
ultimately the j>atieut recover*.^. In a caue related by Tardieu|, in
which a pirson died on the eleventh day from the eHects of the poison,
towards the end, as a specially marked symptom, there was noted
hypereesthesia of the inferior extremities, bo that the least touch was
painful
^ 729. Absence of Symptoms. ^In a few cases there have been a
remarkable aljeence of symptoms^ and this both in man and am mala.
Seven horses were fed with oats accidentally mixed with arseniate of
soda. The first succumbed three hours after taking the poison, without
hairing preseuted any symptom whatever; he fell suddenly^ and in a
short time expired,^ It is related by Orfila|| that a wonittn, aged 27,
expired in about twelve hours from a large dose of argenioos acid ; there
were the umml post-mortem appearances, but in life no sigu of pain^ no
vomitmg, and bub little thirst,
§ 730. Slow Poigoning.— Slow poisoning has been caused accidentaUy
by arsenical wall-paper, in the manufacture of arsenical pigments, by the
admixture of gmall quantities of arsenic with salt or other condimenta,
and repeated small doses have been aged for criminally producing a fatal
illness intended to simulate disease from natural canoes. The Illness
produced by amall intermittent doses may closely resemble in miniature,
ag it were, those prcxlnced by large amounts ; but^ on the other liand,
they may be different and Bcarcely to be desaribed otherwise than ag a
* joum. de MidtHne^ 1783( [i* 353 ; Tardieu, &p, ciL^ Obs. xiv. p. 431.
f Jimm. dt VonnaiitB, MM, Chirurg,^ 183&, p. 155; Tftrdieti, op* ciL^ 0\m, xv.
p. 432.
t Op, dL, Oli«, Jtvii p. 434.
% Bouley (Jeune), Ann. tfMyQ^ d de Midm-Lig,^ I S3 4, t xii. p. 393.
II TcmcL, ObB. iv. p. 314.
§ 7310
AESIKia
569
general condition of ill-health and Tnalaise. In auch cases there is loaa
of appetite, feebleness, and not nu frequently a slight yellowness of the
Bkin. A fairly constant effect seen, when a solution of arsetiious acid is
given contimionsly for a loug time, is an inflamtnation of the con-
jnnctivBB, as well as of the nasal miicouB membrane — the patient com-
plains of "always havin|j a cold." This inflammatory action also aflecta
the pharynx^ and may extend to the air-passages^ and even to the lung-
tissue. At the same time there is often seen an exanthem^ which has
reeeiTed a specific name — " eczema avfuenicale^^* Salivation is present, the
gums are sore, at times lacerated* In chronic poisoning by arsenic,
nerv'ous symptoms are almost constant, and exhibit great variety ; there
may be numbness, or the opposite oondition, hypersesthesia, in the ex-
tremities. In certain cases faintinir, paresis, paralysis, and sometimes
convulsions occur ; towards the end a sort of hectic fever super veneSf
and the patient dies of exhaustion.
|73L The May brick Oaae.'^Tho Maybiick cane mny he oouaidoiTed an example
of poisotiiiig extouding ov*jr a cuiistdL^mble j^ieriod laf time :• — Mr, Jameii Maybriek, a
Livorpnol coLttjfi- broker, ag<jd 49, married Florence Elizal>eth, an Atii^ricau ladj,
ftged 21 » They bad two cbildTen. The marriage jtrovtid An imbapjiy une. Some
two yeaiB halom his death in May 18S& thoy iiad occupiud two ^eparntf] rooms.
Seven wceka before the husliand'a drnthg Mrw. Majbrick went to London on & falsti
preteitt, mad lived for some dB^y^ tit an hot«l, ostensibly the wife of another imui.
Two day a after her retain^ Mr. and Mj-^ May brick atte tided the Grand Hational
m<!e meeting, and there a s^riens qnarrel arm^ between them res[)octing the m&n
with whom she had cohabited in Lundon ; tht<y returtied from the riit^, each
separately f and ahe slept aj>arL Next day un ap]>arent reconciliation trK)k pliic«
through the intervemtioTi of Dr. Fuller, Lbc' family uiedi^^l atteiidaiit.
On or about April 12-19tlii 1889, Mi^ Mi^y brick pn re hosed arsenical f]y-p&pera»
On April 13- 20th Mr, Haybriek vi9it43l Ltiiidwu, and caoaulted Dr» Fuller for dyai»|*flia,
who preacribed nnx voruka, acidn, and mild reniedi(^ (but no arsenic) ; in one bottle
of medicdue, oaicusilily made according to Dr« Fuller'^ preficription, araeoic waa
snbfkMiuently found.
Up to Saturday, April 27tli, BIr. Maybrlek was in Ms UMual benlth ; he was then
ulckf numbedj and in {mliii, and bad crMupia ; he told hia clerk be had been an hour
in the water-clofiet, but whether for diarrhoeia or constiputioii does not apixear ; he
ascribed the symptomM to an overdfjtse of Fuller's njedicine. About this dote %-
|fA}]>ers were found by the servants soaking io Mrs, Maybrick*s iMjdrooni in a ajM^ngt?-
Ijasin, carefully covered up* On the 20th she again purchased two do^tm tty-ptt|)eni
fmm another uhemiHt. On ApJil 2Sth Mr. M ay brick waa sick and ill; at 11 A,U,
Djv K, Humphreys was called m ; Mr. May brick complained of a |K>culiar sensation
about hm hearti and >^id he was in dread of paraljais. He attribute bis illne^ Ut
a etroiigcup cftra taken before hreak^t. Dei the fallowing day lie was better, and
on the 30tl] atill improving. On May 1»L and 2nd Mr, May brick went to his office
and lunchedi both dajij, off revalenta food, pre^iared at home and wanned at his office
in A new saucepau purcha^d for the occoj^ioo ; on one of these days the lauch was
foi^tten, 4nd wa» seM to Mr. May brick by his wife ; and on one of the two daya^
^ *'The Maybriek Trial and Araeuical Poisonifigt" by Thos. Stevonson, M.D*,
S70
POISONS: THKIR EFFECTS AND DBl'ECTIOX.
[§ 731-
it m not clear which^ Mr. Maybrick complained tLai Lib limch did not ttgr^ with
hiiUi aud lie attributed it ta inferior Bben^y put into hb Tood,
In a jug found at the oflice, and in which food had been takeu tliere, a trace of
the fond atill i'«maiued aft«r Mr* May brick ^ii death, and arsenic \^as found thereiii.
On Mt^y Srd the lastj fatal illness »et in. It m unoertiiin what food he had afl^r
breakfast ; he wt^ut to the ofiicti, and r^turtuKl home iHjtweon 5 and 6 ?.M. He had
been seen by Dr, HuTupJireys in the nioniing^ and appeared then not quite so wall ;
be found bim at midnight Buffering from what he thought was ievere sciatica ; the
jiatieut Baid be had been Kick from revalenta. On May 4th he waa continually sick,
nothing could be retained on the Mtomach, but the twiatic pain was gone ; on May 5tli
the Tomiting continued, tbe patient complained of the sensation of a hair sticking in
the throaty and of a filthy taste in the mouth. The throat und fauceii were only
slightly reddened, the tongue waa fun*^
On M&j 6th there was leas Tomiting;, but otherwiae the condition was the Batnei
and Fowler's aolution ordered^ but only a quantity equal to il^ grain waa actually
takeu.
May 7th the condition wats improv«5d, hut there wait no increase of jjower. Dr.
W, Cartsr was called in consultation. The vomiting waa passing away, and diarrbcBa
commenoing. The throat was red, dry^ and glazed - there were tnceasant attemptii
to cough up an imaginary hair. No cramps^ no |jain in tbe stomach or inti^tlnes,
tior conjunctivitis. On thiB day the f^mt direct evidence of diarrhoea h recorded, the
medical men actually seeing a loose motion « The result of the consultation was that
Mr. Maybnck must have taken somii initant in his food or drink.
On the 8tb a professional nurse took charge. During the Sth and 9th severe
tenesmus set in with diarrhoea, arjd blood was observed in the fieceR. Now arsenic
waa auapected, the urine was exanvined by Dr, Humphreys, and a rough analysis was
made of some Neaves' food which tbe patien t had been taking.
The patient di«d on tbe 10th, at 8.30 f.m.
The post-mortem apj>earance» were as follows t— '
The tongue was dark, tbe top of the gullet slightly red, but otherwise healthy,
save at the lower end, where the mucous momhrane was gelatinous^ and was dotted
over with black dota^ like frogs^ spawn.
There was a small shallow ulcer in the mucous membrane of the larynx at the back
rjf tbe ejiiglottiy, Tbe free margin of tbe epiglottis was rough and eroded i and on
the [losterior aspect of tlie cricoid cartilage there were two small red jra tehee. In the
stomaeb were from 5-5 nzs. of brown iali fluid. At the cardiac end there was a large
vermilion-red patch, interspersed bete and tbere with small dark ecchyinoses (spoken
of by Dr. Humphreys as a ilea'hitt4.»n appearance) ; to this followed a non-inflamed
sjiace, and near the pyloric orifice, and e:K tending 2 inches from it^ wa^ another red
inAamed portion of mucous membrane. In the small intestine tbe mucous membrane
was red and inBajDed^ fmm S inches below the pylorus to about 3 feet downwards.
About 18 or 20 feet lower down, iff., a little below the ileo-ejecal valve, the mucous
membrane was again inflamed to a le&a e?[t«nt over a sjiace of about two feet ; the
lower end of the rectum was also rod and ijiBamed, Ko arsenic was found in the
stomach or its contents, or in th<^ spleen » Arsenic was jiresent in the liver, in the
intestines, and in the kidneys. The quantity sejjarated altogether axnounted to over
0*1 grain. The Uver weigbefl 4S ozs., and fram 12 o£s* of the liver 0*07 6 grain of
arscuiCj roekoned as A^Oj, was separated.
The whole uouiae of the symptoms and the ptjst-mortem examination showed that
the deceased di&l fr^m an irritant ^joison ; and from the fact of a small quantity of
arsenic having been found in the body, there can be little doubt b\it that the poison
was arsenic. The symptoms were somewhat anomalous^ hut not more so than in
other recorded cases of uTidouht«d arsenical poisoning. The facts that tended to
oonneet the accused with the death were as follows i—On the night of either May
§ 73 1 A.]
ARSENIC.
57 f
Sth or thti lOtli Mi's. MiiybriL^k wb« olsaerved to i^move from th« table an opened
bottle of VftlentinR^a meat juice, and take it into an inner drossmg-room, and tl»5ii
replace it^ — the *et& being surreiititioua. In replrfcciug it, she was obaerved to take it
either from the iiocket of her dretising-gown or from nn inner poaket. The liniDg of
this i>ticket was (mud to be irapregrittted with AsjO^. The jidc© woa fouud to eontalzi
0*5 grain AsjQ^, and the liquid jfua of lower gmvity tUiiu commeiisiai Juice ; it had
probably, therefore, been diluted.
The following ib a liat of things coutaining araeaiio i—*
1. Mr^. Miiybrick*^ dressing gown.
2. J ^ apron.
3. A httiidkercljief wrapped aTound a bottle.
4. Packet of araenic *' for cats." (AraeQious aeid mixed with charooaUJ
Tumbler containing milk, with bawi kerchief ^laking in it ; at IviLsi
20 grain» of AsjO^t in the tumbler mixed with chareoal.
5. A portion of a handkerchief.
€. A bottle containing a strong eolutioD of arsetiious acid and several grain ej of
undissolved areenioim add.
7. A hottle containing from 15-20 gmliis of solid arsenic and a few dropB of
solution,
^. A laturated solution of arsetiious acid and eome solid arsenious acid.
0, Valentine^s meat juice*
iO. Prioe-s glycerin ; § grain in the whole bottle.
11, A bottle containing O'l grain of arsenious acid.
12* A bottle from Mr. May brick's office containing a few diojis of medicine pre-
scribed by Dr. Fuller (decidedly ar^senieal).
13. Jug from the office with remaiaft of food.
14. Sediment from trap of w.e. and Uvatory drain containing As^fl^.
Mrs, May brick waa convicted, but afterwards the sentence was commuted to
{.lenal servitude for life.
§731a, Poiiotuag hyAnezLio&l Beer.— The mass ijohioning by arsenical heer,
due in the fii'st |ilace to the use of a^Henic^al gliKxise^ which occurred in Lanoaahire
and the Midland counties* in 1890, gives excellent material for the study of the
effects of chronic ijoisoiuug by araenit^, the more pujietially jsinee the doses were small,
hut euntinued daily for montha \ It may be objected that the aymptonia and patho-
logical cbnnge^ cannot be ascribed entirely to the effects of araonici but are mixed up
and confu^ with those prodnoed by alcohol. This ia true with regard to a projiortion
of the caseSj hut the curious fact has been put on record that the [jeripheral neuritia
observed was confined to the beer drinkers, He^Lvy driiiker» of spirits in the aanie
locality and in the ^me clo^ of lite, so long as they did not drink beer, were
unaffected.
The chief feature of the outbreak waa peripheral neuritis A severe cose
recorded by l>n Kelynack and Mr. Kirby * tnaj be considered aa typieal of a large
nuniben
The i^atienl, a woman of 31}^ had beeu tn the habit of drinking at letaat
one pint of bMr daily^ and oocasionally two pinta; the boar waa found to contain
^^ grain of A&fl^ per pint For some time ihe had notiaed a watery di^harge from
the nose and eyes *, about Mix weeka after this sihe became aware of a brown din-
eoloratiou of the left side of the neek and left shoulder ; this subs^uently e^ttendvd
over the whole body \ the skin [leeled olf the forearm and hands In about twelve
we«ks she felt tenderntjss and pain in the solas of the feet, with Bensations of ** pin-
^nd ueedh^*" Walking liecamie luiiiiful * g^uttric symptiitms then developed; there
waa vomiting and some dkrrhcea ; tn about G| months ahe became too weak in leave
• Artmiiml Finmning in Beer Drinkers, London, l&Ol.
572
poisons: THKIR KFFBCTa AND DKTECTIOS.
[§73=
her b«i, atid bad hoaraenesa of voice* and troublesome cough ; the nftilsivere thickouod,
and there was considorable geneml brauny des^juamation*
Iq & good TOAtiy other canes with or without jtigmeiitAtion therti were Irerpetic
erythematous iiapular or vesicular eruiitiona. In aome there w&b quite au e^tra^
ordinary thickening of the cuUele of the haudii and feat Kervoua symptoms wer^
mi«tly ^ii'omiuentj and in bad c-asca complete jjaralysis rwcurred*
It waftp howevery aiiecially observExi that in the majority of the |iatient8 then;
was no Qonspicuoua ga«lro^iute»tiiuLl deningoment. Hence the only evidence of
araemml poiBoning was iieripheral ueiuitifi, with pigmentation or other affoctiona of
the skin.
During th© epidemic the urine of many of the patknte was examined ; in a few
oases only was amenie found. On the other liand, Ihc haii' and scales from the iikin
when ix^tnined yielded eridencs of arsenic,
§732, POBt-mortem Appearancee in AnimalB. — P. Hugo* has
made some resenrckes as to the pathological appearaitcea met with
in auimalB. His experiments were mode on seven dogB, eight
guinea-pigs, five rabbits, two pigeons, and five cats— all poisoned
by arseoions acid. According to Hugo, so far as these animals
were concerned, changes were more constant in the intestine than
in the stomach*
Stomach,— Changes in the mucous membrane were especially
noticed in the great curvature and towards the pylorns ; the pylorus
itself, and a part of tlie cardiac portion, remained unchanged. The
mucous membrane in dogs and cats was red, with a tinge of blue —
in many cases the redness was iu streaks, with injection of the
capillaries. The stomach of plant-eaters was less altered, and a
microscopical eKamiuattou of the mucous tiB^ues did not show any
fatty change.
The XntestineB. — In dogs and cats changes were evident; In rabbits
and guinea-pigs they were not so marked, but the intesthiea of the l&st
were extremely tender and brittle, very moist, and filled with a slimy,
serous, grey- white Buid ; nevertheless, the changes in all these animals
appear to be of essentially the same nature. The most striking effect is
the shedding of a pseudo-membrane ; in quite recent cases there is a
layer of from 1 to 1| mm, wide of a transparent, frog-spiiwn-like jelly
streaking the intestine. In later stages it becomes thicker, while
occasionally it resembles a diphtheritic exudation. The mucous
membrane itself is deep purple-red, showing up by the side of the
paeudo-membrane. With regard to the villi, the epithelial layer is
detached, and the capillary network filled with blood and enlarged.
The Liver.^ — Hugo met only CMicasionally with fatty degeneration of
the liver, but there was marked steatosis of the epithelium of the gall*
bladder of dogs, A fact not prominently noticed before^ is (at all events^
in dogs) a serous tmnsudatiou into the pleural sac and oedema of
' Archivf* ea^/«r, PaihoL u PAarrnaJbl,^ Leipzig^ 1882.
§ 7330
ilHSEKlC.
573
the lungs; the exudation may be oxeeBsivef so that more than 100 c,q.
of serous fluid can be ubtaiiied from the thorax ; there is also usually
much fluid in the pericardium^ In two of Hugo^s expenments there
was fluid in the cerebral ventricles ; aud in all there was iDcreaaed
mokture of ttie brain substance with itjjeetion of the capillary vessels,
especially of the pi a,
g 733. PoBt-mortem Appearances in Man-^A remarkable preserva-
tion of the body ia commonly, but not constantly, observed. When it
do€fi oocixr it may have great ijigniflcanee, particularly when the body is
placed under condition b in which it might be expected to decom[X)ge
rapidly. lu the celebmted Continental case of the apothecary Speiehert
(1876), Speichert's wife was exhumed eleven months after death. The
coffin stood partly in water, the corpse was mummitied. The organs
contained arsenic, the churchyard earth no ar^nic. H. Koch was
unable to explain the preservation of the body^ under those conditions,
in Quy other way than from the eflect of arsenic ; and this circumstance,
with others, was an important element which led to the conviction of
Speiehert*
When arseoious acid is swallowed in substance or solution, the moat
marked change is that in the mucous membrane of the stomach and
intestines ; and^ even when the poison has been absorbed by the skin
or taken in any other way, there may be a very pronounced inflammatory
action. On the other hand, this is occasionally absent. Orfila * relates
a case in which a man died in thirteen hours after having taken V2 grms.
of arsenious auid : — '* The mucous membrane of the stomach presented
in its whole extent no trace of inEammation^ no redness^ and no altem-
tiou of teiture,*' Many other similar crises are on record ; and, according
to Harvey's statistics, in 197 cases, 36 (about 18 "2 per centO presented
no lesiou of the stomach.
The usual changes produced by arsenious acid may be studied in
the museums of the Loudon hospitals. In Guy*s Hospital Muaeum
there are three preparations. In preparation 1798^^ is seen a large
stomach with the mucous membrane at certain points abraded, and at
the great curvature the whole coats are thinned ; it b also somewhat
congested. In preparation 1798*^* is a portion of coagulated lymph,
from the stomach of a lad, aged 14, who had taken aceideu tally a piece
of cheese charged with arsenious acid, prepared for the purj>06e of
destroying rats. He lived twenty-eiglit hours, and presented the
ordinary symptoms* The lymph has a membranous appearance, and
the rugfe of the stomach are impr^sed upon it. It m said when recent
to have presented numerous bright bloody spots, although there was no
visible breach of substance on the surface of the stomach. The mucous
• T0me i OU, v.
574
POISONS: THEIR EFFECTS AND DETECTION,
[§ 734-
mer.ibraae of the stomach is stated to have heen injected, and there was
also diffuae injection of the dtiodennm. Preparation 1798^ is the
stomach of a per^n who survived thirteen hours after taking a fatal
doae of arsenjons acid ; and in the same museum there m a wax model
of the appearances which the fresh propai'ation exhibited, showing a
large oval patch coated with mucus and tlie poison. The stomach was
intensely inflamed, the caecum injected. The rest of the intestine was
healthy.
In the museum of University College there are two preparations,
one * exhibiting intense swelling and congestion of the gastric mucous
membrane, which h of a perfectly vermilion colour. Another pre-
paration (No, 2868) shows the effect of a small dose of arsenic on the
stomach; there are spot® of arborescent estravasivtion, and slight con-
gestion of the summits of the rugse, but in other respects it is normal.
There m aliso a cast of Peyer's patches from the same case, sboiving
great prominence of the glauds, with some injection of the intestinal
mucous membrane-
In St Thomas* Hospital tht?ro is an interesting prej^aration (No. 8)
showing the gastrie mucous membrane dotted all over with minute
ulcers, none of which have an inflammatory zone-t The writers have
not, however, seen in any museum a preparation of the curious emphyse-
matons condition of the mucous membrane, which has more than once
been met with. For ejtample, in a case related by Tardieu^ J Schwann,
a labourer, died from the effects of arsenic in thirty-six hours. The
autopsy showed that the mucons menibrane of the stomach and small
intestine was covei^l with a pasty eoatiug, and was elevated in nearly
its whole extent by bullae filled with ga«, forming true emphysematous
swellings which encroached upon the diameter of the intestine* There
was neither redness nor ulceration, hut the mucous membrane was
softened.
The senior author saw, many years ago, at Barnard Castle, an
autopsy made on a gentleman who died from arsenic. In this cas^
the mucous membrane of the stomach presented a peculiar appear-
ance, being raised here and there by Httle blebs, and very slightly
reddened
g 734. The inflammatory and other changes rarely affect the gullet.
Brodte | never observed inflammation of the cesophagus aa an effect
of arsenic ; but, when arsenic is swallowed in the solid state, as in the
* This prepar&tioD at the time of viait hi^ no number.
t In A case related by OrfHn, t. i. Ob^ xv,, death ri^BuItfd from the outward
applicatioii of ursflnio ; the mucoua membrune of the stomach was natural in colour,
but tbere wer« four uleere, one of which was 50 centimotrea in diameter,
t Op, ciLj Oba. I p. 4eS. § Phil Trans,, 1812.
§ 7340
ARSKNia
575
suicide of SguflBaixl, gmphicaliy described by Oriila,* it may be afiected.
tn Soufflanl's Civse there was a vivid injection of the pharynx and
gullet
la many tnstauceSj when the argenic has been taken in the solid form,
the crystals with mucus and other matters adhere to the lining membrane.
One of the authors has seen in the stomach of a horsej poisoned by an ounce
of arsenic, an exquisite example of this, The inflammatory changes may
he recognised many months after death owing to the antiseptic properties
of arsenic ; nevertheless, great caution is necessary in giving an opinion,
for there is often a remarkable redness induced by putrefactive changes
in healthy stomachs, Casper, t on this point, very justly observes :— •* If
Orhla quotes a case from Lepe lie tier, in wljieh the inflammatory redness
of the mucous membrane of the stomach was to be recognised after nine
months* interment, and if Taylor cites two ciises in which it was observed
nineteen and twenty-one months after death respectively, this is in
contradiction of all that I, on my part, have seen in the very numerous
exhumed corpses examined by me in relation to the gradual progress
of putrefaction and of aaponificntion, and 1 cannot help here suspect-
ing a confusion with the putrefactive imbibition redness of the mucous
membrane/*
If examined microscopically, the liver and kidneys show no change
save a fatty degeueratioa and infiltration of the epithelial cells. In the
muscular substance of the hearty under the endocardium, there is >ilmoet
oonstautly noticed ecchymosis. In the most acute cases, in which a
cholera-like diarrhoea has exhausted the suflerer, the blood may be
thick en eel from toss of its aqueoui^ constituents, and the whole of the
organs will present that singularly dry appearance found in all cases In
which there has been a copious diainiug away of the body fluids. In
the narcotic form of arsenical poisoning, the vessels ol the brain have
been noted as congested, but this congestion is neither marked nor
pathognomonic. Among the mre pathological changes may be classed
glossitis, in which the whole tongue has swollen, and is found so large
as almost to Hll the mouth. This has been explained, in one case, aa
caused by solid arsenious acid having been left a little time in the mouth
before swallowing it. On the other hand, it has also been observed
when the poison has been absorbed from a cutaneous application. Wlieu
arsenic has been introduced into the vagina, the ordinary traces of
inflammatory action have been seen, and, even without direct contact,
an inflammation of the male and female sexual organs has been recorded,
extending so far as gangrene. As a rule, putrefaction is remarkably
retarded, and is especially slow in those organs which contain arsenic ;
so that, if the poiaon has been swallowed, the stomach will retain its
* T* i. p. 31ft, t Hmdhti^, vi>l. ii p, 420.
S76
FOISONB: THKTR KFFKCT8 AND DBTECTION.
[§ 735.
form, AU^, even to n, certaLu extent, its iiatuitkl appearauee, for au
indefinite period. In corpBes long buried of persons dying from arsenical
poisoning, the onliuary procesB af decay gives place to a sajKJniEcation,
and such bodieB present a striking eoutmst to others buried in the
same graveyard. This retardation of putrefaction is what might, a
priori, be expected , for arsenic has been long in use as a preservative of
orgunic tiBS[U6S.
§ 735, Physiological Action of Arsenic. — The older view with
regard to the e^ential action of arsenic was, without doubt ^ that the
effects were mainly locals and that death ensued from the corrosive
action on the stomach and other tissues — ^a view which is in its entirety
no longer accepted ; nevertheless, it is perfectly Inie that arsenic has a
corrosive local actioti ; it will mise blisters on tlie skin, will in dame the
tongue or mucous membranes with which it comes in contact; and, in
tliose rapid cases in which extensive lesions have been found in the
alimentary canal, it can hardly be denied that instaiices of death ivave
occurred more from the local than the constitutional action. In the vast
majority of cases, however, there is certainly insutficient local action to
account for death, and we must refer the lethal result to a more profound
and intimate ei^ect on the nervous centres. The curious fact that, when
arsenic is absorbed from a cutaneous surface or from a wound, the
mucouB membrane of the stomach inflames, is explained by the absorption
of the arsenic into the blood and its separation by the mucoua membrane^
in its passage exerting an irritant action. The dianbcea and hypersemia
of the interna) alidominal organs have been referred to a paralysis of
the apUiuchnic nerves, but Esser considers them due to an irritation of
the ganglia in the intestinal walls. Binz has advMiced a new and
original theory as to the action of arsenious acid j he considers that the
protoplasm of the ceils of many tissues possesses the power of oxidising
areteuious aeid to arsenic aciti, and this arsenic acid is again, by the same
agency, reduced to araenioua acid. In this way, by the alternate oxidation
^nd reduction of the arsenious acid, the cells are decomposed, and a
fatty degeneration takes place, Thus arsenic causes fatty changes in
the liver, kidney, and other cells by a process analogous to the action of
phosphorus. T. Araki* also considers tluit both ai"senic and phosphorus?
lessen oxidation, and points out that lactic acid appeart* in the urine
when either of these jKjisons are taken, such acid l>eing the result of
insufficient oxidation, A notable diminution of arterial pressure has
U^en observed. In an experiment by Hugo f 03 grm, of AsgOj was
injected intravenously, the normal arterial pressure being ITS mm*
Ten mitmtcB after injection the pressure sank to 47 mm, ; in sixteen
minutes it again rose to 127 mm. Accumulative action of eiBenic
• ^eU^phymoL Chm.., xvii, 311-330* t Op, cit
§ 736-7380
ARSENia
m
does not occur. Hebm has gJ veu, in akin diBeaseB, daring manj months
A total quantity of 12 grras. without evil result.
g 736. EliminAtion of Ai-aenic— Araeuic is separated especially by
the urine,* then through the bile, and by the akin and hair. The
eruption often observed on the skin has been referred to the local
action of small quantities of arscDic in thi^ way eliniinated. It
is found in the urine Brst after froui five to six houra, but the
elimination from a single dose is not tin Is bed till a period of from five
to eight days j it has often been lt>oked for twelve days after taking it,
but very seldom found. According to Vitali, the arsenic in the urine
is not free, but probably displaces phosphorus in phoapho -glyceric acid ;
possibly it may also replace phosphorus in lecithin.
% 737. Antidote and Treatment.— In any case in which there is
opportunity for immediate treatment, ferric hydrate should be adminis-
tered as an antidote. Ferric hydrate converts the soluble arBenious
acid into the iosoluble ferric arseniate, the ferric oxide being reduced
to ferrous oxide. It is necessary to use ferric hydrate recently
prepared, for if dried it changes into an osyhydrate, or even if
kept under water the same change occurs, ao that (according to
the eiperiments of Messrs, T» & H. Smith) after four months the
power of the moist mass is reduced to one-balf^ and after five
months to one-fourth.
It is obvious that ferric hydrate is not in the true sense of the word
an antidote^ for it will only act when it comes in contact with the
araenious acid ; and, when once the poison has been removed from the
stomach by absorption into the tissues^ the administration of the
hydrate is absolutely useless. Ferric hydrate may he readily prepared
by adding strong ammonia to the solution or tincture of ferric chloride,
found in every medical tnan*s surgery and in every cheniiat'a shop, care
being taken to add no caustic excess of ammonia : the liquid need not
be filtered, but should be at once administered. With regard to other
methods of medical treatment, they are simply those suggested by the
symptoms and well-known eflects of the poison. When absorbed, the
drinking of water in excess cannot but assist its elimination by the
kidneys.
I 738* Detectioii of Arsenic. — The analyst may have to identify
arsenic in substance, in solution, in aUoys, in walUpapers, in earth, and
in various animal, fatty, resinous, or other organic matters,
* An old «x^x<fiiue[it of OrJiU^jj Ilah mitm practical bearingij, und may be ettad
here. A dog was treated by *12 gnu, of arsiMUOUA acid, and supplied plentifully
with liquid to driuk ; bin urinei atittlysed from tiiiw* to time durirjg k-u daysi gave
alnitidatit evidrnces fyf arseuic. On killing the animal by haugiug on the tentli day,
no ftmente uotaM be detected in any of the organs of the body ; it Imd been, v» it
vrere^ waahed out
37
578 POISONS : thkr effects axd detbctiok. [§ 738.
Anenioiis Add in Substanoe. — The general chaimcten of anenions
acid have been already described, and are themselyes so marked as to
be unmiatakable. The following are the most ooDclnsive tests : —
(1) A small fragment placed in the subliming cell (p. 260), and
heated to about the temperature of 137'7* (286* F.), at once sablimes
in the form of an amorphous powder, if the upper glass disc is cool ;
but if heated (as it should be) to nearly the same temperature as the
lower, characteristic crystals are obtained, remarkable for their brilliancy
and permanency, and almost always distinct and separate. The pre-
▼ailing form is the regular octahedron, but the rhombic dodecahedron,
the rectangular prism, superimposed crystals, half crystals, deep
triangular plates like tetrahedra, and irregular and confused forms, all
occasionally occur.
(2) A beautiful and well-known test is that of Berzelius : — A small
hard-glass tube is taken, and the closed end drawn out to the size of a
knitting needle. Within the extreme point of this fine part is placed
the fragment (which may be no more than a milligramme) and a
splinter of charcoal, fine enough to enter freely the narrow part, as
shown in the figure. The portion of the tube containing the charcoal
(e) is first heated until it glows, and then the extreme end ; if arsenic
is present, a mirror-like coating is easily obtained in the broader
portion of the tube (d). That this coating is really arsenical can be
established by the behaviour of metallic crusts of arsenic towards
solvents (as given at p. 583). The portion of the tube containing the
crust may also be broken up, put in a very short, wide test-tube (the
mouth of which is occupied by a circle of thin microscopic glass) and
heated, when the arsenic will sublime on to the glass disc, partly as a
metal and partly as crystalline arsenious acid. With minute films of
metallic arsenic it is, however, better by means of a small pointed
flame to draw out the tube on both sides of the arsenical ring, and seal
it ; the sealed tube is then heated in a bath of ordinary solder to about
400* C. The oxygen of the enclosed air unites with the arsenic at
once ; and crystals are formed without any possibility of loss.
(3) Arsenious acid, itself inodorous, when heated on charcoal, after
mixing it with moist oxalate of potash, evolves a peculiar garlic-like
odour. To this test oxide of antimony adulterated with arsenic will
respond, if there is only a thousandth part present. Simply projecting
arsenious acid on either red-hot charcoal or iron produces the same
odour.
1 738.1
ARSENIC.
579
(4) A little bit of arsemous aoid, heated in a matrass with two or
three times its weight of acetate of potash, evolYes the misuppor table
odour of kakodyl,
Arsenites and ArsemateSj mt:xed with oxalate of 6oda and heated in
a matrass, afford distinct mirrors, especially the arsenites of the earths
and sih^er ; those of copper and iron are rather less distinct.
Sulphides of Arsenic are reduced by any of the processes described
on p. 598 ei seq.
In Solution. — An acid solution of arsenious acid gi^es, when treated
with Sllg^ a caiiarj-ycllow precipitate, aoluhle in ammonia, carbonate of
ammonia, and bisulphite of pjtash, and also a metallic sublimate when
heated in a tube with the reducing a^^euta in the manner described at
p, 599. By these properties the sulphide is distinguished and, indeed,
separated from antimony, tin, and cadmium-
The sulphides of tin and cadmium are certainly also jellow» but the
latter is quite insoluble in ammonia, while the former gives no metallic
sublimate when heated with reducing substrmces.
The sulphide of antimony, again, is orange, and quite insoluble in
potassic bisulphite, and scarcely dissolves in ammonia.
A small piece of sodium amalgam placed in a test-tube or Hask con-
taining an arsenic -holding liquid, or the liquid made alkaline with soda
or potash and a little bit of aluminium added, produces in a short time
arsine, which will blacken a piece of paper, soaked in nitrate of silver,
and inserted in the mouth of the flask. This is a convenient test for
arsenic. No an timoniu retted hydrogen {sHbim) is given off from an
alkaline solution and no SHj^
Gutzeit's taflt. — The principle of Gutaeit*a test is the production
of a yellow or orange stain, according to quantity, produced by
araeniuretted hydrogen. When passed through filter-paper impreg-
nated with mercuric chloride the teat is not affected by antinionTj
selenium, or tellurium, and is capable of detecting less than ^ J^ of a
mgrm. of As^Og.
The beat way to perform the test is to place from 50 to 100 c,c. of
the liquid to be tested in a small flask ; it is better for the liquid to be
free from organic matter, but not essentiaL In cases where the evolu-
tion of hydrogen causes frothing, the solution must be so altered in
physical characters by boiling with oxidising reagents that injurioua
frothing ceases. The solution is acidified by adding from 5-10 c.c, of
arsenic-free hydrochloric aoid and half a c,c, of a 15 per cent,
solution of cuprous chloride, and a rod of pure zinc inserted. The
gaa is passed through a small absorption cell containing lead acetate
solution^ ani' d over a short layer of dry cotton wool
and made & small disc of fllter-paper prBviously
S8o
poisons: THUS crrscTs and oETEcnoK,
[S 738.'
impregnated with a 5 per cenL SDltitiOQ of mercuric cUonde The
diac flhonld be capped on to tbe issuing tube, so that all tbe gaa
pBWtfTT tight throtigb tbe paper. It k well to pluugie the flask into
oM water so aa to keep the temperature down^ othennae tbe eirolu-
tioo of gal will be irregular.
Manth's Qngin^ Test for Araetuc consisted in eyolving naacent
hydrogen by due and sulphuric aj^id, and then adding the liquid to be
teatecL Tbe apparatua for Marab% test, in its amplest form^ coosiBta
of a flask proTided with a cork conveying two tubes, one a funnel reach-
ing nearly to the bottom of tbe flask ; the other, a delivery tubCf which
Is of some length, is provided with a chloride of calcium bulbi'^ and to*
wards tbe end is turned up at right angles, the end being narrowed. By
evolving hydrogeo from zinc and sulphuric acid, and then adding por.
tions of the liquid through the funnel, aneninretted hydrogen in a dry
state is driven along the leading tube^ can be ignited on its issue, and on
depressing a piece of cold i^>orcelain, a dark metallic spot of arsenic is
obtained, Or, if n.nj portion of the tube be made red-hot, the metal
18 deposited in the same way as a ring.
Purification of the Zinc, Sulphuric Acid and Hydroehlorio Add, —
(For the Margh-Berzelius apparatus and purification of materiatSf ns
recommended by the Joint Committee of tbe Society of Public Aoalysts
and tbe Society of Chemical Industry ^ see Foods, 5th edition, p, 437.)
Zinc (Hehner'a method as oiodified by Thorn et), — Commercially
pure zinc is melted in a crucible in a gas furnace, and when at or only
just above its melting-jioint sodium is mixed with it in the proportion of
about 1 grain to each pound of zinc. The crucible is then heated until
the dnc is completely fluid, and the dnc is poured into a second heated
crucible and back again into the first crucible to ensure thorough
melting'* The crucible, with the lid on, is then put back into the
furnace and heated to » dull red heat, when the furnace and crucible
lids are both removed, and the heating is continued for one hour, A
scum rises to tbe top and forms a crust on the surface. This crust,
when tbe crucible has cooled a little, is pierced at one side and the
molten mass is poured into a second heated crucible and skimmed if
necessary* The criicible is then heated to bright redness, any scum
removed, then allowed to cool and the isinc granulated just before the
* Otto rficoiumeudH the fir^t half of the drying tube connected with tha develop-
mi?nt flofik to bo filled witli caui$tic [wtosli, the latter hftlf with chloride of calcium
{Ansniiii«lung tier QiJlA), Drai^undorir approves of this, bat remarks thut it should
be uttad when nrsenic alone m Hcarcbed fori since caustic jiotash deoumpases atibine.
The potub fixpH SH^, and ^^roventa the forroation of chloride of iti^nlc ; on the other
hand, it MbHurb» some little AsH^
t L. T, TliorDfi, **The Purification of iSinc and HydrMhloric Acid fpoin Araenio,*'
^no/^at, April 1@00, p. 101.
§ ?38.]
ARSENIC.
S8i
aoHdifjing point b reached. Arsenic- free ziuc prepared in this luauiier,
and much of the uomiuerdal arseiiit^-free ssinc^ ia often '*insenaifcive/* /.«*,
it retains a certain amount of arBenic^ bo that qualitative results amj
be too low or traoes overlooked,
M* Blondlot,* several years ago, made the observation that if
ataunoua chloride be added to the coatenta of the Bask in the Marah-
Berzelius process, the whole of the arsenic \s given ott' even in the
presence of pure zinc and acid, and Chapinan and Lawt have receutiy
found that 1 to 3 grammes of cadmium i^iilphate, lead acetate, or
stannous chloride, completely overcome the ** insensitiveness ^' of the
pure tnaterial^. The same authors hiive shown thnt Buoh salts as
palladiiim chloride^ platiuum chloride, nickel sulphate, aud cobalt
sulphate cause, on the other hand, a retention of lar^e qiiftntitieB of
arsenic ; working also w^ith alloys of zinc with iron, nickel, cobalt^ copper,
silver, platinum, aodium, tin and eacltDium, they fouud that all of these^
witli the exception of tin and cadmium, caused retention of arsenic,
but in every ca^e the " insensitiveness " was removed by the addition of
2 grammes of cadmium sulphate, lead acetate, or stannous chloride,
except in the case of some metal alloys.
HydrocMorh Acid.- — Various methods have been proposetl for
freeing hydrochloric iicid from traces of arsenic. Of these we will only
give two of the most recent and convenient.
Ling and Rrnidyis Method 4 — ^Thia is Imsed upon the fact observed
by H. Cantoni and J. Chautenis, S that methyl arsenite is readily formed
and is very volatile, and that the Reiusch method as modified by Dr.
L, T. Thornell may be used for the purification of hydrochloric acid.
To 1500 cc. of commercial hydrochloric acid slightly above I'l sp» gr.
about 40 c.c. of redistilled commercial wood spirit are added. The
mixture is contained in a Wurtz flask of two litres capacity. About 5
to 10 grms, of arsenic-free granulated zinc are then added. The fli^k
is connected with a retiui condenser by an ordinary cork, in which is
fixed a glass rod supporting a coil of electmlytic copper foil, having
a surface of about 120 square inches. The side tube of the Wurt*
flaj^k having been plugged, the condenser is connected with an ex-
* Blondlot, " TmQBfMrmntiou du rAreeiiic eu kjdruits 3*jlid« \mt rUydrogvne
fabt^ut sou^ VinQiieaoe des com[>o9^ nitreux,^ J^ur, d& Ffntrm, ef de Chint.f 3*
^r , t. iliv. fh 486.
f A. C. Clmptiuiii and tf D. Ljiw, **Thp Reducing Actitm of Hydrogen,'"
Arnd^i Jun. 1S06, p. X
t Ai-thui^ R. Ling, and T. Reudle, *'Note oa the lleiuoviil of Ai-senic fmni
Hjrdruchlonc Aiud for uac m the Mitrsh^BerieULia Method/' Anaiifst^ Ft'K lUM^
IK 37.
§ Arck Se. PAy*, Nai, Otneve (4), xix. 864.
n Pro(k Chf^. Soc, 1&02, lis.
S82 POISONS : THEIR EFFECTS AND DETECTION. [§ 738.
liaust-pump, and the boiling oommenced. The acid is digeBted fur
about three hours, the copper being withdrawn and cleaned at least
once during that period. During the digestion a black tarry, fuming
liquid distils over, and the greater part of this is caught in a vessel
between the condenser and the pump. Another vessel containing water
is interposed to catch any hydrogen chloride which passes off.
Thame and Jefftri Method* — Redistilled hydrochloric acid is
diluted to a sp. gr. of a little under 1*1, and poured on to 2 to 3 grms.
of a copper-tin couple prepared as follows : —
Cuprous chloride is dissolved in excess of HCl, and a little granu-
lated tin added ; when the tin is dissolved, zinc dust is added, and the
copper and tin, which are precipitated as a gray spongy mass, washed
by decantation. The acid and couple are gradually heated, and boiled
gently for half an hour. The acid is then at once distilled from a flask
containing a small quantity of the couple and a little piece of lOO-mesh
copper gauze. The distilled acid is free from arsenic.
Sidphuric Add, — This acid may now be obtained free from arsenic,
but if it is found to be impure it may be freed from arsenic by diluting
with four volumes of water, adding a little sodium chloride, and distil-
ling. The first ^th of the distillate contains all the arsenic, and is
rejected.
The precautions to be observed in Marsh's or Marsh-Berzelius process
are : —
(1) Absolute freedom of the reagents used from arsenic, antimony,
and other impurities.
(2) The sulphuric acid or hydrochloric acid should be diluted
with from four to five times its weight of water, and if freshly prepared
should be cooled before use. Strong acid must not be employed.
(3) The fluid to be tested should be poured in little by little.
(4) Nitrous compounds^ nitric acid, chlorides, are all more or less
prejudicial.
(5) The gas should come off regularly in not too strong a stream,
nor out of too small an opening.
(6) The gas should pass through the red-hot tube at least half an
hour before adding the substance to be tested ; if there is then no
stain, the liquid to be tested is run in gradually and the test run for
at least one hour.
(7) A solution of cadmium sulphate should be added to the contents
of the flask, to counteract the " insensitiveness '' of the material.
The characteristics of the metallic stains which may occur either on
glass or porcelain in the use of Marsh's test, may be noted as under : —
♦ L. T. Thome and E. H. Jeffere, "The Purification of Zinc and Hydrochloric
Acid from Arsenic," Analyst^ April 1906, 102.
§ 738.]
ARSBNIO.
5S3
Mirror or Grubt of AtiaKNic Mirror or Crust op Antimony
Is deposited at a little disbanoe
from the Oame.
Ad arson ical stain is lo two
portiouB, the one brownish, the
other a glitter iug bkck.
Ou heatings it is rapidly vala-
tillaed as arseuious acid.
On transmission of a stream of
SH2, whilst immediately behind
the Btaio a gentle heat is applied,
the arsenic is changed to yellow
sulphide - * if dry CllC m now
transmitted, the arsenical sulphide
is unchanged.
Chloride of lime dissolves the
arsenic completely.
Protochloride of tiu baa no
action on metallic arsenic.
The arsenic stain^ dissolved in
aqna tegia^ or CIH and chloride
of potash, and then treated with
tartaric acid, ammouifti and mag-
nesia mixture, gives a precipitate
of ammonia magneaian arseniate*t
The mirror or crust of arsenic
as being composed of the pure
investigated the matter, and the
regnlts ; — -
There is no amorphous form of
Is deposited close to the Hame,
£).nd on both sides of it, and is
therefore notched.
The Htain is tolerably homo-
geneous, and usually has a tin-
like lustre.
Volatilisation very slow ; no
crygtalline sublimate obtainable.
The same process applied in
tbe case of antimony produces the
orange or black sulphide j and on
passing dry CIH, chloride of anti-
mony volatilises without the appli^
cation of heat.
Antimony not affected*
Dissolves slowly but completely
the antimony stain.
No precipitate with antimony.
is usually described and weighed
metal; but J. W. Hettgers has
following is an abstract of his
araenic, the variety generally thus
' It is deairable to dissolve a way the h^ sulphur often dapoattad with tho
Afsenic&l sulphide by biBulpliide of c&r1x^ii«
t Bcboiihein has proposed ozone a« an oxidiser of atsenicml stains. The sul^ianoe
cont&initig tba stain, together with a piece of moi^t phoaphomB, is placed under &
ahadoi and left there for eonie time ; the oxidisation product ib, of course^ coloured
yellofw by SH.^ if it is arsenious acid, orange if aiitimony. The vaponr of ioditie
eolouis metallic arsenie pale yellow, and later a brownish hue ; on exposure to the
air it loaeti it» colour. Iodine, on the other hand, givea with antimoiiy a Carmelite
brown, ohangiug to orange.
An arsenical nng may be also treated as follows ; — PFeeipitated Kino sulphide is
made into a poate with a little water, and introdn«ed Into the end of the tube ; the
same end ie then plunged into dilute sulphuric acid, and the ring h^ted, when tho
arsenical sulphide will be produced*
5U
POISONS: THEIR EFFECTS AND DETECTION.
[§ 738.
called being crystalline. Two modifications can he distinguished : the
one being a hexagonal silver- white variety possessed of metallic lustre,
specifically heavier and leas volatile than the second kind, which is
black in colour, crystallises apparently in the regular system, and
constitutes the true arsenic mirror. The former modification corre-
sponds to red hexagonal phosphorus (red phc^phorus having been
recently proved by the author to be oryatalline), and the latter to
yellow phosphorus, which crystallises in the regular system. Both
moditicationa of arsenic are perfectly opaque; depoaiti which are yellow
or brown, and more or less transparent, consist of the aul>o5tide and
hydride, As^O and AbH, The brown spot on porcelain produced by
contact with a flame of arseniuretted hydrogen is not a thin film of
As, but one ol the brown solid hydride AaH, formed by the decomposi-
tion of AsHg. This view is confirmed by the fact that arsenic sublimed
in an indifferent gas (e^g^t CO^) ia deposited in one or other of the
modifications described above, the brown transparent product being
obtained only in the presence of H or 0. Moreover, pure arsenic is
insoluble in all solvents., whereasi the ijlm on porcelain (AsH) is jsolnble
in many solvents, inclnding hydrocarbons of the benzene series {e.y,
xylene), warm methylene iodide, and hot caustic potash.
Hence quantitative res nits from weighing arsenical mirrors can
never be accurate, because the mirrors consist of mixtures of hydride
and suboxide.
Beinsch's Test, — A piece of bright copper foil, boiled in an acid
liquid containing either arsenic or antimonyj or both, becomes coated
with a dark deposit of antimony or arsenic, as the case may be, Th©
arsenical stain, according to Lippert^ is a true alloy, consisting of 1
aHienic to 5 copper,* Properly applied, the copper will withdraw every
trace of arsenic or antimony from a solution-
Copper gauze or copper foil is osidised iu the air by heating in au
open tube to a gentle 1^ heat. The film of black oxide is next dissolved
off by a few seconds' immersion in strong nitric acid, leaving a bright
chemical ly-cleau surface. The acid is removed from the copper by wash-
ing in a stream of water. A piece of copper thus prepared about 1 inch
X J inch is suspended by means of a thin platinum wire in from 50 to 100
c.c. of the liquid to be eiamincd, the liquid acidified by HCl and gently
boiled for twenty minutes. Operating on organic liquids, the copper
is usually darkened in colour, even if arsenic-free. Any black stain
may be caused by sulphur, by organic matter, by arsenic, or by antimony •
The copper is washed with alcohol and then by water ^ and, lastly, by
absolute alcohol, and dried at a very gentle heat. It is then dropped
into a small tube and gently heated to a temperature just below a red
* Joum. / praJtL CAewi., xiti* IftS*
§ 759. 740.1
ARSENIC.
sss
heat. If arsenic is present tbe metal sublimes fii the characteristic
crystals of arsenious acid.
Dr, John Clark {Joum. OhmtK Soc.^ 1893) has proposed dissolving off
the black film by potash and hydrogen peroxide ; the solution is boiled
and any uopper hydrate filtered od Should arsenic be present, it now
exists as pot^i^ic arsenate ; if anbimony be present, it exists as potassic
antimonate. If both arsenic and antimonj are preaentj the potassic salts
of both are formed. The arsenate may be decomposed and reduced by
terrous chloride and strong hydrochloric acid and distilled into water,
the arsenic being recognised in the distillate by sulphuretted hydrogen.
Any antimony left in the fiask is precipitated by SH^ ; shoutd a dark
black precipitate form, this means contamination by copper ; on treatment
with caustic soda and boiling, copper sulphide may be filtered off and
pure antimony sulphide obtained by acidifying the solution and again
treating with SH.^
§ 739. Arsenic in Glycerin. — Arsenic has been frequently fonnd in
commercial glycerin, the quantity varying from O'l to 1 mgrm. in 100 c.c*
The best method to detect the presence of arsenic in glycerin is as
follows :— A mixture of 5 e,c, of hydrochloric acid (1:7) and 1 grro. of
pure Kinc is placed in a long testrtubCg the month of which is covered
with a disc of filter-paper previously moistened with one or two drops of
mercuric chloride solution, and dried. If arsenic is present, a yellow
stain is produced upon tbe filter-paper within fifteen minutes, and it
subsequently becomes darker.*
§ 740. Arsenio in Organic Matters. — Orfila and the older school of
chemists took the greatest care^ in searching for arsenic, to destroy the
last trace of organic matter. Orfila*s practice was to chop up the sub-
stance and make it into a paste with 400 to 700 grms, of water ; to this
'010 grm> KHO in alcohol was addedi and '020 grm, of potassic nitrate*
The substances were heated up to from 80° to 90' for some time, untii
they were pretty well dissolved ; the organic matter was then burnt off
in a Hessian crucible heated to redness, on which small quantities of the
matters were placed at a time. Wlion the whole Imd thus been sub-
mitted to red heat, the melted mass wjis run into an almost red-hot
porcelain basin, and allowed to cooh Afterwards it was again heated
with concentrated sulphtiric acid, until all nitric and nitrous fumes were
dissipated^ on dissolving and filtering in water, the liquid was intro-
duced into a Marsh'S apparatus. Orfila never seems to have failed in
detecting arsenic by this process. For an organ tike the liver he con-
sidered that 1 00 grms. of potash and 86 of strong sulphuric acid were
necessary in order to destroy the organic matters.
• ''Arsenie la Glycerin," by Dr. U* B. H. Paul aad A. J. Cowaley, Pftitrm.
/ourjw, Feb. 24, 1894,
S86 POISONS : THEIR EFFECTS AND DETECTION. [§ 74O.
Distribution of Arsenic in the Body. — In searching for arsenic
in the fluids or tissues of the body, the analyst is generally at the
mercy of the pathologist, and sometimes the work of the chemist
leads to a negative result, solely from not having the proper organ
sent to him.
Brodie long ago stated that when arsenious acid had been given in
solution to any animal capable of vomiting, no arsenic could be detected
in the stomach ; this statement is too absolute, but in the majority of
cases true.
In all cases the chemist should have portions of the brain, spinal
cord, liver, kidneys, lungs, and muscular tissue, as well as the stomach
and its contents.
According to the experiments of Scolosuboflf,* arsenic is generally
greatest in the marrow, then in the brain, next in the liver, and least in
the muscles, the following being the proportion if muscle be taken as 1 : —
Muscles, 1
Liver, lO'S
Brain 36-6
Spinal Marrow 37*8
But Ludwig*s t experiments and conclusions are entirely opposed to
this, since both in acute and chronic cases he found as follows (per cent.
A82O3) :—
Brain -0002
Liver, '001
Kidney, '0004
Muscle -00025
So that he detected in the liver five times more than in the brain.
M. P. Hamberg has also confirmed the fact, that more is found in the
liver and kidneys than in the nervous tissues.
Chittenden I found in a body the following quantities of arsenic
estimated as arsenious acid : —
Grain.
Stomach and gullet, 0*158
Intestines 0*314
Liver 0*218
Kidney, 0'029
Lungs and Spleen, 0*172
Heart 0*112
Brain, 0*075
Diaphragm 0*010
The whole arsenic present was estimated as equal to 3*1 grains of
• Bull. Soc, Chim, (2), xxiv. p. 124.
t "Ueberdie VerhiJtung des Arsens im thierischen Organismus nach Einver-
leibung von arseniger Saure," Med, Jahrbuch, 1880.
t American Chemical Journal, v. 8.
§ 741-1
AHSBinC.
587
arsenious actd^ vk., 2*628 grains absorbed, and 0'472 unabsorbed ; of the
absorbed portion 8^3 per cent, was found in the liver,
Witb regard to the preliminary treatment of the stomach and fluids
submitted to the analyst, the careful noting of appearances, the decanta-
tiou, washing and examination* (microscopical and chemical) of anj
deposit, are precautions so obviously dictated by common sense, that
they need only be alluded to in passing. Of some considerable moment
is the question which may be put to the analyst in court, in reference
to the possible entrance of arsenic into the living body by food, by acci-
dental and, m to speak, subtle means. A. Gautier and Clausmann
believe that people take daily in their food only ^qqq mgrm, of arsenic,
therefore yearly 7 "66 mgrms. ; so that should y^u mgrm, of arsenic be
found in the corpse there is a fair presumption of poisoning. Other
sources of atsenic are the inhaliug of the fumes from the burnt ng of
arsenical candles,t and of emanations from papers (see p» 564), J as well
m the possible entrance of arsenic into the body after death from various
sources, such as arsenical earth, ko. g
§ 74L ImbiMtioii of Arsenic after Deatk— The arguments which
are likely to be used in favour of a corpse having become arsenical may
be gathered from a case related by Sonnenscbein ;— Certain bodies were
exhumed in two churchyards ; the evidence went to show that they had
been poisoned by arsenic, and this substance was actually found in the
bodieS} while at the same time it was discovered to exist also in traces in
the earth of the churchyardHP The theory for the defence was^ that
although the arsenic in the earth was in an insoluble state, yet that it
might combine with lime as an arsenite of lime ; this arsenite would
become soluble by the action of carbonic acid set free by vegetation, and
filter down to the corpse. SonnenHchein suspended a quantity of this
* Fhrm mm^ <»bai?rT&tionb of Fresetiiu& it would wmm necessary to test all gkas
remmin usod ; for it is difficult at present to purchuA aneiiio'free gliuss.
t 3ee a cam of poisoniug (aon-fat&l) of a lady by th« lue of arsenical candles, Med.
fifties mhd Qfiuiir^ vol. iii., 1876, p. 3^7.
X To solve this question, it has been at times oomidered ^ecesiaiy to analyw
an ojctraordinary number of things. In the "affaire DanvaP' {Jouni^ d*M)fffiine,
2e i^n, Ko. 108, July 1878), more than aiity different artiolesj oomprising druga,
drinks^ perfumes, bod-curtaioi, wall paper, and other mattenii were submitted to the
experts,
S The following important case is related by Sunnen^helii : —
Kicholaa Nobtil and his vdfe, Jerome, were borisd two metres from each other
in the churcbjrard at Spiiiah the earth of which notoriouslj t^ontained arserjic. A
soapimoEt of poisoning arose ► Tho bodies were ejthumedj and arsenie was found in
the Htomach and int^^atines of Nobel, but not the slightest trace iti the corpee of
tlie wife. The remains of the bodi^ were reinten^t *nd after sii months, on a
fresh suapjcton of poisoning arising, agaiu ejchumed. The corpse of the woman had
been put naked in the moist earth during a heavy shower, but this time aKi no
arsenic was detected in it
588
POISONS: THKIB EFFECTS AND DETECTION,
[§ 741.
earth in water, and passed CO, through it. for twelve hours ; on UlteriDg,
the liquid gave no evidence of araenie, A airailar result was obtamed
when an artificial mixture of I grm, of arsenioui acid and 1 pound of
earth were submitted to the same process.
The fact wDuld appear to stand thus : oxide of iron in ordinary earth
retalna arsenic, and requires treatment with a concentrated acid to dis-
solve it* U therefore follows that, if a defence of arsenical earth is
likely to be set up, and the analyst finds that by mere extraction of the
tissues by water he can detect arsenic, the defence is in all probability
unsound. The ejspert should, of course, deal with this question on its
meritSj and without prejudice. According to Eulenberg,* in arsenical
earth — if, after having been crushed and washed » it lies for soma titne
exposed to the disintegrating action of the air — soluble arsenical salts are
formed, which may find their way into brooks and Hupplies of drinking
water. We may infer that it is hardly probable (except under very
peculiiir circumf^tances) for a corpse to be contamiuated Internally with
an estimable quantity of arseiuc from the tmcts of arsenic met with in
a few churchyards.
It occasionally happens that an exhumation is ordered a very long
time after death, wiien no organs or parts (save the bones) are to be
distinguished, In the case of a man long dead, the widow confesgicg
that she had administered poisotj, the bones were analysed by Sonnen-
Bchein, and a small quantity of arsenic found, Goni^rbe and Orhla have
both asserted that arsenic is a normal constituent of the bun es~ a state-
ment which hna been repeatedly disproved. Sonnenschein relates :t —
^*l procured from a churchyard of this place (Berlin) the remnante of
the body of a person killed twenty -five years previouslyj and investigated
several others in a similar way, without finding the least trace of arsenic.
, Similar experiments in great numbers were repeated in my laboratory,
but in no case was arsenic recognised," The opinion of the expert
should he find arsenic in the boneSj must be formed from the amount
discovered, and other cironmstances.
A di 01 cult cuse on which to form an opinion is one recorded by
William P. Mason,* as follows: —
The dweoaed, u farmer, Imchetor, iLzt^-five yeara <^f Bge, and in good health, was
taken violently sick shortly after breakfast, with vomiting and distress in the
atoiiia<L'h, Althougli & iihyaiclan wjis summoned, the symptoTTis increased in aevarity^
and a lit tin after midnight death eiisuwl. TTie funeral took place threo days later.
Certain vtry damaging pieces uf ciicumHtantial evideune hftving bwu colleeled^ thi?
houaeln?eijer wa*i arrpstH on tin? charge €*( murder ^ it liaving bepn fsliown, among
otlier things, that on the day pr(*ceding the death she had purchased an ounce of
wMt« aTBeuic.
* Qm«rb$ Hifgime, p. 284. t SWcA^. CAewi,, p. 212,
X Chenu Kewst Feb. 23, tS04.
§741]
ABSRNIC.
589
Thirty* five days aftcf death (from Marcli 20 to AjirU 25) the body was exhumed,
nud found itt a alate uf remarkabk preserration, and frae from cadaveric snielL Thu
stomach f»res6iited erideuees of uiflaniiuatioo.
Portinna sent for analysis were tho tttomncli, portion of intt«stiii(*, portion of liv^er^
OHO kidtH*y, and the hearL Arsenic wan found in all these parts. White octahedral
crystals were found in the contents of the stomach, wliich on aepAration gave
arsenical reaction >
The {LHwuic found vtxsv —
Stomach and intestine,
Liver and kidney,
Heart, ,
0'237« gnn.
0^0032 „
0^0007 „
Total as metallic ai^'aenic,
0-2415
The amount of arsenic recovered and produced in coiu't was in quantily suffici^pt
to produce death. Some time *ifter the analytical report was made to the coronerj it
waa learned tliat ati embalming Quid, highly anenical in character, had been used
upon the body by the undertaker at the time of preparation for burial. No injection
of this emhalmini^ fluid was practiced, but cloths wrung out in the duid were laid
upon the face and che^t) and wc^rc kept constantly wet therewith during a period of
many hours. In all^ about two quarts of embalming fluid were so used. Its com-
poaition appeared to be a strongly acidised aolution of sodium arsenitc aod zinc sul-
phat<*. Only the arsenic and zinc were detBnained quantitatively, and they were
found to be ; zinc (metallic), 1*978 per ccqL, andaraeuic (motalUc), 1"365 percent, by
weight* An amount of this fluid measuring 15*7 cc, would thus contain a weight
of arsenic equal to that actually recovered from the body*
Extended medical tcatimony was otTered by the prosecution, tending to show that,
tinder the given ciix:nniiitaucea, no fluid of any kind could hav^e reached the stomach
through the nose or mouth after death— thus anticijtating what tho defence after-
wmrdt daimed, that the undertaker was reaponsible for the arsenic discovered in the
remains.
In order to gather further light upon the possibility of cadaveric imbibition of
entbalmiug fltiid through the unbroken skin, test was made for zinc in the heart and
stomach, and distinct traces of the metal were found in each iastance. That at
least a portion of the arsenic found in the body was due to post-mortem causes wa&
thus distinctly proven, A weighed ijortion {62 gmis.) of the stomach and contents was
then most carefully analysed i|uantitativfily for both dnc and arsenic, with the fol-
lowing rtssults : urseotc, O'OS'IS gruL, and zinc, Q'U079 grm. Bearing in mind the
relatire quantities of the two metals in the embalming fluid, it will be seen that the
arsenic found in the 52 grme, of the stomach was nearly twelve times larger than tt
should have been to have balanced the zinc which was also present This fact,
together with the discovery of crystals of white arsenic in the stomach, constituted
the cose for the prosecution, so far as the cliemical evidence was concerned.
The defence made an unsuccessful effort to show that the crystals of the tri-oiide
originated from the e[>ontaneous evaporation of the embalmiug fluid. The proseeu^
tion met this point by proving that such Huid had been abundantly experimented
ui>on by exposure to a very low temperature during an inteival of Heveml months,
and also by spontaneous evaporation with a view uf testtng that very question, and
tliftt tb^ results hod in every case been negative. Special importance was given thes
eiperimentSt because of the welbkfiown separation of octahedral crystals during the
spontaneous evuporaUon of a hydrochloric ftttd solution of the white oxide, it having
also appeared that, in the manufacture of the embalming fluid, the arsenic was used
«a white arsenic,
A very strong point waa flUally raised for the defence by the inability of the
59°
POISONS; THEIR EFFECTS AND DETKCTION.
[§ 742.
oipert on the side of the proaecution to state pomtiTely whether or not an «mb&Im-
mg Quid of the above composition would diffvise as a whole through de^ tissue, or
its seTeral part a would be imbibed at diffei'Oiit ratoB of speed, the line portion beeom-
ing ftmeted by album maid material and being therefore out^trijiped bj the araenic,
or ffi» mr&S^ The j prisoner waa ulttmately acquitted*
In a ease whrch occurred in the Western States of America, there
was good reatton for believing that arsenic had been introduced into the
corpse of a man after his deeeafle. With regard to the imbibition of
arsenic thua introduced, Orfik* says :— " I have often introduced into
the stomach (^is well as the rectum) of the corpses of men and dogs 3
to 8 grms* of arseuiotis acid, dissolved in from 400 to 500 grms, of
water, and have examined the different viscera at the end of eighty ten,
or twenty dajB. Constantly I have recognised the effects of cadaveric
imbibition. Sections of the liver or other organs which touch the
digestive canal, carefully cut and analysed, furnished arsenic, which
could not be obtained aenaibly (or not at all) from sections which had
not been in contact with this canaL If the corpse remained long on
the back after areenious acid had been introduced into the stomach, I
could obtain this metal from the left half of the diaphragm and from
the inferior lobe of the left lung, whilst I did not obtain it from other
portions of the diaphragm nor from the right lung," Dr, Roece has
also made some eaperimcnta on the imbibition of arsenic after death.
He injected solutions of arsenious acid into the stomach of various
warm-blooded animals, and found at variou^i periods arsenic, not alone
in the intestitial canal, btit also in the spleen, liver, and kidneys,
§742. Analysia of Wall-Baper for Arsenic. ^The separutfon of
arsenic from paper admits of great variety of manipulation. A q^niok
special method isasfollowa: — The paper ja saturated with chlorate of
potash solution, dried, set on fire in a suitable plate, and instantly
covered with a bell-glass. The ash i% collected, pulverised, and ex-
hausted with cold water, which haa previously thoroughly cleansed the
plate and bell-glaa8 ; the arsenic in combination with the potash is dis-
solved, whilst oxides of chromium, copper, aluminium, tin, and lead
remain in the insoluble portion.!
Fresenius and Hintz | have elaborated a method for the examination
of wall-papers^ fabrics, yams, and similar substances, whicli, provided
the reagents are pure, is accurate and easy. Twenty-five grms* of the
substance are placed in a half-litre distilling flask or retort, and 250 c,c*
of HCl, specific gravity I '1 9, added; after digestion for an hour, 5 c*c,
of a saturated solution of ferrous chloride are added, and the liquid
• 0;*. ea,. tl p. 809.
t Kapferschkeger ; Etw Uni'om'uUe dei M>iM, 1876.
X Mfit»anai, Chem,i i.xvu. 17^182^
I 743-1
ARSKMIC.
S9t
slowly distilled until frothing stops anj further diatillation, A further
quantity of 100 c.c. HCl is then added, and distilled over. The re-
ceiver, in each case, contains water^ and must be kept cooU The united
diatillates are diluted to 800 c.c. and saturated with SIL^. The areenious
sulphide is collected on an asbestos filter. After partial washing, it is
heated with bromine in HCl of ri9 specific gravity, and the solution
again distilled with ferrous chloride. The distillatej on now being
treated with SH^, gives arsenious sulphide free from organic matter.
§ 743, Estimation of Arsemc— Most of the methodts for the quanti-
tative determiDation of arsenic are also excellent tests for its presence.
It may be regarded, indeed, aa an axiom in legal chemistry, that the
precise amount of every substance detected, if it can be weighed or
estimated by any process whatever^ should be accurately stated. In-
definite expressions, such as "a small quantity was found," "traces were
detected," etc, are most objectionable. The more perfect of the methods
of evolving arsine are now quantitative, because the arsenical ring can
be compared with standard rings produced under as nearly as possible
the same experimental conditions. Pure araine, passed into nitrate
of silver solution, decomposes it in such a manner that^ if either
the silver deposited or the free acid is estimated, the quaniity of
arsenic can from such data be deduced. A very convenient method,
applicable in many cases, is to throw out the silver by hydrochloric
acid, alkalise the filtrate by bicarbonate of soda, and titrate with iodine
solution. The latter is made by dissolving eiactly 12 '7 grms. of pure
dry iodine by the aid of 18 grms, of potasaic iodide in one litre of water,
observing that the solution must take place in the cold, without the
application of heat. The principle of the titration is, that ai^enious
acid, in the presence of water and free alkali, is converted into arsenic
acid —
As^Oij + 41 + 2N%0 = AsjjOfi + 4NaL
The end of the reaction Is known Tiy adding a little starch-paste to
the solution ; as soon as a blue colour appears, the process is finished.
Another convenient way by which (in very dilute solutions of
ai'senlous acid) the arsenic may be determined, is a colorimetric method,
which depends on the fact that sulphuretted hydrogen, when arsenious
acid is present in small quantity, produces no precipitate at iirst^ but a
yellow colour, proportionate to the amount of ai'senic present. The
silver solution containing arsenious acid is free<i from silver by hydro-
chloric acid ; a measured quantity of saturated SH^ water is added to a
fractional and, if necessary, diluted portion, lu a N easier cylinder or
colorimtjtric apparatus, and the colour produced exactly imitated, by
the aid of a dilute solution of arzsenious acid, added Eroni a burette to a
592
POISONS: THEIR KPPEOTS AND DETKCTION.
[§744.
similar quantity of SHg water in another cylinder, the fluid being
acidified with HCl.
§ 744. Electrolytic Methods.— The method used in the Govern-
ment laboratory, as arranged by J. E. Thorpe,* requires the following
apparatus : —
A glass vessel of the shape shown iu the figure is open at the bottom,
and at the top fitted with a ground glass stopper. Through this stopper
is passed the stem of the tap fuimel ; it also carries the gas exit tube
on which there is a bulb. This tube is connected by means of a ground
glass joint with a drying tube. Through the glass cap is fused a stout
platinum wire for making the connection outside with the current and
within the vessel to the electrode.
The inner electrode forming the cathode is a cone of sheet platinum
provided with several perforations. It is suspended from a hook made
Thorpe's Apparatus.
on the end of the wire passing through the glass stopper, and is adjusted
so that when the stopper is inserted in the vessel the lower edge of the
electrode is one millimetre above the bottom of the vessel ; it is then
securely attached to the wire by closing the hook. The porous vessel
is two or three times larger in diameter than the cylindrical portion of
the glass vessel. The glass vessel rests by its bulged-out shoulder on
the edge of the porous vessel, and is thus kept off the bottom.
The porous vessel is of unglazed highly-siliceous ware. The cell for
the anode consists of a stout glass vessel, upon the flat bottom of which
the porous vessel supporting the bulged glass vessel stands. The
anode consists of a band of platinum 2 cm. broad, passing loosely
round the porous cell and connected with the current by means of a
stout platinum wire. The apparatus, lastly, is put iu a large dish con-
taining cold water, for, in action, the temperature should not exceed
♦ J(mm, Chem. Soc. Trans, ^ 1903, 974.
§744.]
ARSENIC*
593
50* C. The d tying tube is prepared by iasertiiig, first, cotton-woolj and
tbea gmnukted calcium chloride for about 5 cm. ; another loose plug
of cotton -woo I follows, then a roll of dried lead acetate paper. To the
end of the drying tube i& lixedj hy means of rubber, a hard Jena glasa
tube, outfiide diameter 5 mm., inside 3'5 mm. ; a portion of this tube, 2 cm,
in length, 5 cm. from the end of the tube, is drawn out to a length of
7-8 cm., having at a distance of 1 cm. from the shoulder of the tube an
external diameter of 2 mm., a sbi© to be maintained as nearly as possible
througbont the length of the constricted part.
The tube is drawn out, cut off near the end of the drawn-out portion,
and the last cm. turned up at right angles.
A piece of phitinum gauze 2 cm. square is wrapped round the bard
glaae tube at the point where it ia to be heated by a BuuBeii fiame. A
special small burner is recommended with slotted coue to receive the
tube. The current giving the best results ia one of five amptres and
seven volts ; this may he obtained in plncea where there is a oontinuous
supply of electricity from the mains by interposing suitable resistances,
sucii, for inatauce, m a rheostat of incandescent lamps.
The authorE have used for some time a boron battery of four cells,
the exciting liquid being a sulphuric acid s^alution of potassic bichromate ;
the amperage and voltage are regulated by a sliding resistance.
The method of working is as follows ; — After thoroughly cleansing
and connecting up, 30 c.c. of dilute sulphuric acid (I : T) are poured
into the auode cell and 20 c,c. into the cathode cell by means of
the stoppered bottle, the stem of which must be kept full of liquid >
The current is allowed to pass for about ten minutes to expel air,
aud then the burner is lighted so as to heat the hard glass tube, and
the current passed for another fifteen minutes; if by the end of this
time no brown ring is seen, the testing liqmds are presumed to be
pure. Two c.c. of amy! alcohol are tun into the inner cell by means
of the tap funnel, and followed by the solution to be tested. The
solution, if quantitative results are to he obtained, should be con-
centrated down BO as not to he more than from 30 to 50 c.c.
Obviously, no air must be admitted, and the stem must remain lull
of liquid, the last portions of the liquid being rinsed into the flask by
distilled water.
The final operation is to preserve any ring formed in an atmosphere
of hydrogen, which is aocompliahed very simply as follows;— The
stopper of the funnel is opened, aud a small pointed flame directed
against the narrow tube at a point 3 cm. from the deposit between
the deposit aud turiiedup end of the ttjbe, and drawn off; the electric
current is now interrupted, and the tube, still full of hydrogen, heated
and drawn off near the shoulder.
38
594
F0180MS: THEIR EFFICTS AND DETECTION.
[§ 745-
Hy. Julius Salomon Sand and John Edward Hackford* have
modified the apparatus by replacing the platinum electrodes by
those of lead, and maintain that lead cathodes give better reanlta than
platinum. A, C, Chapman and H. D. Law have also esc penmen ted
with various cathodee, and l>ave obtained good results with lead, tin,
and cadmium, t
§ 745. Gautier J has also devised a process by which the most
minute quantity of arsenic can be separated ; the process is based on
the fact that iron oxide in preetpitatiug from a solution carries down
with it any arsenic. Gautier uses a solution of ferrous sulphate, freed
from every trace of arsenic^ as follows : —
100 grms, of ferrous sulphate are dissolved in H HtreH of water^ and
after the addition of 25 grms. of pure sulphuric acid heated with SH^
any precipitate is tiltered off; and the solution oxidised with 28 grms.
of arsenic- free nitric acid. The iron is now precipitated by ammonia,
the precipitate filtered, washed, and dissolved tu the cold by means of
dilate sulphuric acid. Granulated ainc is added, and the solution heated
to boiling under diminished pressure for two days. The solution ia
again oxidised with nitric acid, and again precipitated} washed, etc., and
finally dissolved in dilute sulphuric acid.
After destruction of organic matters in the way before indictited, to
the final sol nt ion in water so small a quantity of the iron solution is
added that, after tsuch addition, there is no reaction with ferridcyanide ;
the precipitate which forms contains no arsenic, and ia filtered ofti The
filtrate is now precipitated with 5 c.c, of the iron soJution^ and boiled.
Ammonia is added to neutral reaction. The resulting precipitate is
dissolved in a mixture of nitric and sulphuric acids, the nitric acid
expelled by boiling, and the innal sulphuric acid tested for arsenic in the
modified Marsh apparatus already described.
The apparatus recommended by Gautier has been modified somewhat
by Gabriel Bertrand, and as, in essential principles, it is the same as
Gautier 's apparatus slightly improved, it will suffice to describe here
only Eertrand*8 process.
The apparatus consists of a flask of 90 c.c. capacity, in which the
reduction of the arsenical compound is effected by Einc and sulphuric
acid. The Hask is fuinished with a long tube and cylindrical funnel, £,
to which is fixed by means of a cork the bulb tube, A, furnished with &
stop-cock. The gas passes through the tubcj L^ 30 c.c. long, charged
with highly dried cotton wool ; to this tube succeeds C, made of diffi-
cultly fusible glass — the internal diameter is 1 mm«, and the walls
2 mm. thick. The tube is surrounded by asbestos, and heated by a
• Jofim. ahem. S&€. Trans,, lUOl, 1018. f Analyai, IfiOS. 12,
t Compt* E«7\d,t oxxxvii. ifiS.
§ 746]
ARSENIC.
S9S
**ramp" of gas for the length of 10 c.c. ] 3 c.c. from the heated pnrt a
small stream of cold water, dropping on a piece of filter* paper wrapped
around the tube, oools the iasuiug gas, which fin ally buhbles through
T^ater at V,
The method of procedure with this apparatus is as follows : — 10-30
grms. of granulated zmc are introduced into a flask^ with 30 c.c. of
water and a few drops of a solution of platinum chloride. As soon as
the stinc is platinised, which is denoted by the bright surfaces becoming
of a dull grey black, the water is poured away, and, after washing the
Kinc with a little diatilled water, the aiinc is transferred to the flask, F,
and the apparatua connected up* The air is now diBplaced by a current
of dry carbonic acid gas, and 10 e.c, of sulpliuric acid (I of acid to 4 of
water) added ; a brisk effervescence follows, and the carbonic acid gas
Gabriel Bertmiid*» A ^[laratus.
is expelled from the apparatus by the hydrogen ; 10 cm* of the
capillary thick-walled tiube is now brought to a dull red heat, and the
cooling arrangement adiuated. After ten to fifteen minutes the evolution
of gas has become somewhat alow, and the solution to he tested for
arsenic is introduced by means of the bulb funnel, little by little, into
the flask. The bulb is washed out at first with 20 c,c, of dilute
sulphuric acid (10 per cent), and theti with 10 e,c. of the 1 to 4 acid,
taking care that the acid only falls into the Jipparatus drop by drop.
The most anitable evolution of gas is found to he from 4 to 5 ox. per
minute : a guess of the quantity evolved may be made by counting the
linbbles of gas escaping through the final water in Y,
g 746. Precipitation as Tersulphide. ~ The advantages of the
processeji described ut^ great when dealing with minute quantities,
but the old method of precipitatiou with hydric sulphide SU^ ia
59fi
POISOKS: THKIR KFFacra AlTD DITTBCTIOK.
[S74&
hmt for qiiAQtities of srsenie which admit of heiog direetly weighed.
H this he used^ it is well in mott cases to pass sulphurous
anhydride through the liqaid uotll it smelb strongly of the gas, fof
by thtB meatiB any arsenic a^id present h reduced ; the sulphurous
anhydnde is quickly got rid of by a current of carbonic anhydride,
and then the liquid ia eatumted with hydric sulphide. In the ordinary
way, much time ia often wasted in saturating the liquid with this gas*
Those, however, who have large laboratories, and dmly employ hydric
sulphide, possess (or should possess) a water saturated with the gas
under pressure ; such a liquid, added in equal Tolume to an arsenical
solution, is able to convert the whole of the arsenic into sulphide in a
very few minutes. Tbose who do not possess this hydric sulphide water
can saturate in an hour the liquid to be tested^ by passing the gas in
under pressure. A convenient method is to evolve SH^ from sulphide
of antimony and CIH ; the gaa passes first into a wash-bottle, and then
into a strong Eask containing the solution under trial. This flask is
furnished with a safety-valve, proportioned to the strength of the
apparatus ; the two tubes dipping into tbe wash-l>ottle and the last flask
are provided with Bunsen's valves, which only allow the gas to pasB
in one direction. The hydric sulphide is then driven over by heat^
and when sufficient gas has in tbia way passed into the liquid, the
tlame ia withdrawn, and the apparatus allo^^ed to stand for some
hours, the valves preventing any backward iiow of the liquid or gas.
When the precipitate has settled to the bottom, the supernatant fluid
is carefully passed through a filter, and the precipitate washed by
decantation in the flask, without transference to the Alter, if it can
be avoided.
Tbe impure sulphide is washed with water, then with alcohol, then
with carbon disulphide, then, after having got rid of the latter, again
with alcohol, and En ally with water. It is then dissolved in ammonia,
the ammonia solution filtered, and the filtrate evaporated to dryness
on a sand-tmth at a somewhat high temperature; in this way it m
freed from eulphur and, to a great extent, from organic matter. After
weighing, it may be purified or identiticd by some of the following
methods : —
(a) Solutloti in Ammonm and Estimation by lodiQe,*— The filter
is pierced, the sidphide washed into a flssk by ammonia water (which
need not be concentrated), and dissolved by warming, filtered from any
insoluble matter, and estimated by iodine and starch.
(h) Oxidation of the Sulphide and Precipitation aa Ammonia
Magnesian Arseniate. — The tarsulphide is dissolved in ammonia
(uoi omitting' the filter-paper, which should be soaked in this
* ?. Ulmmpiou and H. Fellett, MiUL Soc. Chim. (2), xxvj. |rp. &41-&ii.
I 746,1 AR91N1C. 597
reagent), the aolution tiltereil, and evaporated to dryness* Tlie dry
residue is now ojtidieed hy fu mi ug tiitric acid, tuking care to proteet
the dish with a large watch-glass {or other cover) during the
first violent action ; the dish is then heated in the watcrlmth until
all the stdphnr has disappeared, and only a small bulk of the liquid
remains ; it is then diluted and precipitated hy " magnesia mixture/* *
The fluid must stand for several hours, and^ if the arsamo is to be
determined as the usual ammoniacal salt, it tnuat be passed through
a weighed iiiter, and washed with a little amoioniacal water (1 : 3).
The solubility of the precipitate is consiJerable, and for every 16 cc.
of the filtrate (not the washings) I mgnn, must be allowed. The
precipitate, dried at 100", 2(NH4MgAsOJH20t represents 39*47 per
cent, metallic arsenic.
The solubility of the magnesium an^eniate itself, and the general dis-
like which chemists have to weighing in such hygroscopic material as a
ftlber, are, perhaps, the main reasons for the Viiriatiou of tliia old method,
which has lately come into notice* Rose proposed some time ago the cou-
version of the double salt into the pyro-arseniate^a method condemned
by FreseniuB and Patnell, but eitamined and pronounced a practicable
and accurate process by Remol, Rammelsberg, Thorpe, Fuller, Wittstein,
Emereon, Macivor, Wotxl, and Brauner. The modification of Bofie's
process, recommended by Wood,t and still further improved by Brauuer^
m&y be accepted*
The precipitation is effected by magnesia miiture, with the addition
of half its bulk of alcohol. The solution is allowed to stand for several
hours, until it is possible to decant the clear liquid from the precipitate ;
the latter is now dissolved in CIH, re precipitated as before^ thrown on a
small filter, and washed with a mixture of one volume of ammonia, two
volumes of alcohol, and three of water.
The precipitate is now dried, and transferred as completely as
possible from the filter into a small porcelain crucible, included in
a larger one ruade of platinum, moistened with nitric acid, covered
and heated at Brst gently, lastly to a bright reduess ; the filter is
then treated similarly, and the crucible with its contents weighed.
Pyro-nrseniate of magnesia (MgaAsjOy) contains 48 '29 per cent, of
metal lie arsenic.
* Mftgneaift Mix tare : —
Sulph£it« of magneBis, .,«»..« ^ I
Chiaiiile of Ammomiuu, ...««..!
Bolution of amnioniiip ...,..., 4
Water, , B
tHfisolve ; then allow to stand hr seror*l days ; finally fitter, ond keep for use.
t ^fliMkr. far antU. Chem,^ vd. xiv, p, M%,
t i^u^i VQ. pp. 57, C8.
598
POIBONS : THEIB EFFECTS ASTD DKTECTION,
r§ 746.
(e) Gonversiou of the Trieulphide of Arseiiic into Lbe Arsenomo-
lybdate of Ammonia.— T lie purilied sulphide 1% oiLidimd by nitric acid ;
the acid solution m rendered alkaline by ammonia, and then precipitated
bj a molybdenum aolutlon, made as follows: — 100 grms. of moljbdtc
acid are disaolved in 150 c,c. of ordinary ammonia and 80 of water ; this
solution m poured drop by drop into 500 C-c. of pure nitric acid and 300 c.c,
of water ; it ia allowed to settle, and, if necessary, filtered. The niolybdic
solution must be mixed in exceas with the liquid under treatment, the
temperature raised to 70'' or SO'', and nitric acid added in excess until
a yellow coloration appears ; the liquid is then passed tbrougb a tared
(liter, and dried at 100^, It contains 5 1 per cent, of arsenic acid
[3*3 As].*
(fZ) Conversion of the Sulphide into Metallic Arsenia — If there
should be any doubt as to the nature of the precipitated substances, the
very best way of resolving this doubt is to reduce the sulphide to metal ;
the easiest method of proving thiu is to dissolve in potash and obtain
arshie by the action of aluminium ; or if it is desired to byoItb arsine
from an acid solution with zinc in the usual way, then by dissolving
a slight excess of due oxide iu potash or soda, and dissolving in tbis the
arsenic sulphide ; the zinc combines with all the sulphur, and converts
the fiulpharsenite into arsenite; the sine sulphide is filtered off, and the
filtrate acidified and introduced into Marsh's apparatus* The original
process of Fresenins was to mix the sulphide with carbonate of soda
and cyanide of potassium, and place the mixture in the wide part of a
tube of hard Gerniau glass, drawn out at one end to a capillary fineness.
Carbonic anhydride, properly dried, was passed through the tube> and
the portion containing the mixture heated to redness ; in this way the
arsenical sulphide was reduced, and the metal condensed in the capil-
lary portion, where the smallest quantity could be recognised* A more
elaborate and accurate process, based on the same principles, has been
advocated by Mohr,t
A convenient quantity of carbonate of soda is added to the sulphide,
and the whole mixed with a very little water and gently warmed. The
yellow precipitate is very soon dissolved, and then the whole is
evaporated carefully, until it is in a granularf somewhat moist, adhesive
state. It is now transferred to a glass tube, open at top and bottom,
hut the top widened into a funnel ; this tube is firmly held perpend icu*
larly on a glass plate, and the prepared sulphide hammered into a
compact cylinder by the aid of a glass rod, which just fits the tube«
The cylinder is now dried over a flame until no more moisture is to
be detected, and then transferred into a glass tube 4 or 5 inches k
" Ohtrnpiou and PeUet, Buii. Soe, €him.t Jan. 7, 1&77*
t Mohr'a Toxi&}l(^ief p» 67*
§ 746.]
ARSEKia
S99
and with one eud drawn to a \mn% (the weight of thm tube should be
fiffit accurately taken )« The tube is connected with the folio wiog
aenea: — (1) A chloride of calcium tube; (3) a small bottle containing
nitrate of silver solution ; {3} a hydrogen-genera ting bottle containing
ziac and sulphuric acid. Tbe hydrogen goes through the argentic
nitrate solution, leaving behind any sulphur and araenic it may contain ;
it ia then dried by chloride of calcium, and streams in a pure dry state
over tbe cylinder of prepared sulphide (no error with regard to impurities
in the gas is likely to occur; but in rigid inquiries it is advisable to
heat a portion of the tube, previous to the insertion of the cylinder, for
Bome time^ in order to prove the absence of any external arsenical
source); when it ia certain that pure hydrogen, unmixed with air, la
being evolved, the portion of the tube in which the cylinder rests is
heated slowly to rednesSi and the metallic arsenic sublimes at a little
distance from the source of heat liOas is ioevi table if the tube is too
short, or the stream of hydrogen too powerful.
The tube, after the operation, is divided j the portion soiled by the
soda thoroughly cleansed, and then both parte weighed ; the difference
between tbe weight of tbe empty tube and the tube + arsenic gives the
metallic araenic. This is the process as recommended by Mohr ; it may,
however, be pointed out that the glass tube itaelf loses weight when any
portion of it is kept red-hot for some little time ; and, therefore, unless
the crust is required in the original tube, it is better to divide it^
carefully weigh the arsenical portion, remove the crust, and then
re* weigh. The method is not perfectly accurate, The mirror is
not pure metallic arsenic, and if the white alkaline residue be
examined^ arsenic will be detected in it, the reason being that the
arsenical sulphide generally contains pentasulphide of arsenic as well as
free sulphur. Now the pentasulphide does not give up metallic arsenic
when treated as before detailed ; nor, indeed, does the trisulphide, if
mixed with much sulphur^ yield an arsenical crust. It is, therefore, of
great moment to free the precipitate aa much as possible from sulphur,
before nttempting the reduction*
The development of a reducing gas from a special and somewhat
complicated apparatus is not absolutely necessary* The whole process
of reduction, from beginning to end, may take place in a single tube by
any of the following processes :^-{l) The sulphide is mixed with oxalate
of soda (a salt which contains no water of crystallisation), and the dry
mixture is transferred to a suitable tube, sealed at one end. An
arsenical mirror ia readily obtained, and, if the heat is continued long
enough, no arsenic remains behind — an excellent and easy method, in
which the reducing gas is carbonic oxide, in an atmosphere of carbonic
* iride* (2) The sulphide ia oxidised by aqua regiUf and the solution
6oo
POISONS : THEIR EFFECTS AKD DETEGTION. [§ 747, 748,
eTflporated to complete diyneRs. This residue is then dissolTed in a fevr
drop« of water, with the addition of some largish grains of good wood
charcoal (which absorb most of the solutioti)i and the whole carefully
dried* The mass is now transferred to a tube closed at one end, a little
charcoal added m the form of an upper layer, and heat applied, first to
this ujjper layer, so as to replace the air with CO^^ aod then to bring
the whole tube gradually to redness from above downwards. In this
case also the whole of the aiBenic Btiblimes as a metallic mirron
There are various other modifieationSf but the above are trustworthy,
and quite sufficient.
2. ANTIMONY,
g 747. Metallic Antimony.— Atomic weighty 120*3 (K. Schneider).
120*14 (Cook); specific gravity, 6*715; fusing-point about 621'
(1150* F.)* In the course of analysisj metallic antimony may be seen
as a black pom'der thrown down from solutions ; aa a film deposited on
copper or platinum ; and, lastly, as a ring on the inside of a tube from
the docom position of stibine* At a bright red-heat it is volatilised
slowly, even when hydrogen is passed over it ; chlorine, bromine, and
iodine combine with it directly. It may be boiled in concentrated
CIH without solution ; but a>qiia regta^ sulphides of potassium and
sodium, readily dissolve it. The distinction between thin films of this
metal and arsenic on copper and glass are pointed out at pp. 583
and 584, It is chiefly used in the arts for purposes of alloy, and enters
to a amall extent into the composition of fireworks (mile pp. 556
and 604).
§ 748, Antimonions Sulphide, ^Sulphide of antimony = 336 ; com-
position in 100 parts, Sb 7176, S 28*24. The commercial article, known
uoder the name of black antimony, is the native sulphide, freed from
flilioeoua matter by fusion, and afterwards pulverised. It is a crystalline
metallic-looking powder, of a steel-grey colour, and is often much con-
taminated with iron, lead, copper, and arseuiCi
The amorphous sulphide (as obtaiued by saturating a solution of
tartar emetic with SH^) is an orange-red powder^ soluble in potash and
in ammonic, sodic, and potasaic sulphides; and dissolving also in
hydrochloric acid with evolution of SH^. It is insoluble in water and
very dilute ncid, scarcely dissolves in carbonate of ammonia, and is
quite insoluble in potass ic bisulphite. If iguited gently in a stream of
carbonic acid gm, the weight remains constant To render it anhydrous,
n heat of 200* is required.
Several lamentable accidents have happened through mistaking the
sulphide of antimony for oxide of manganese, and using it with potassic
chlorate for the production of oxygen. The addition of a drop of
§ 749. 75oJ
ANTIMONY.
60!
hydrochloric acid, It is scarcely necessary to say^ will di&tiuguisli
between the two*
Antimony is freqnently estimated oa sulphide. An amorphous
tersnlphide of mercury, oootaining a small admixture of antimonions
oxide and sulphide of potassiam, i« known under the name of Kennetf
mineral^ and has been employed in the vulcaniaing ol imiia-rubber*
Prepared iu this way, the latter may be used for various purposes, and
thus become a source of danger. It behoves the analyst, there tore, iu
searching for antimony, to take special care not to use any india-rubber
fittings which might contain the preparation.
A pentcmilphide of antimtmy (from the decomposition of Sehleppe's
ialt [Na^Sb^S^ + 9K^0], when heated wttb an acid) is used in calico-
printing.
§ 740, Tartarated Antimony, Tartrate of Potash and Antimony,
or Tartar Emetic, is, in a medico-legal sense, the most important of
the antimonial salts. Its formula is KSbC^H^O^HaOi and 100 ptirts,
theoretically, should contain 35 '2 per cent, of metallic antimony. The
B,P, gives a method of estimation of tartar emetic not free from error,
and Professor Dunstan has proposed the following : — Bissolve 0*3 grra.
of tartar emetic in SO o.o. of water, add to this 10 e.c. of a 5 per cent^
solution of sodium bicarbonate, and imm^iately titrate with a decinonual
solution of iodine, using starch as an indicator. One c-c. of — iodine —
0*0166 grm. tartar emetic ; therefore, if pure, the quantity used by
0'3 grm, should be 18 e.c. Tartar emetic occurs in commerce in
colourless, transparant, rhombic, octahedral crystals, slightly efflorescing
in dry ain
A crystal, placed in the subliming cell (p. 260), decrepitates at 193*3*
(380" F.), sublimes at '248-8' (480' R) very slowly and scantily, and
chara at a still higher temperature, 287 "7'' (SSO"" F*), On evaporating a
few drops of a solution of tartar emetic, and examining the residue by-
the microscope, the crystals are cither tetrahedra, cubes, or branched
figures. 100 parts of cold water dissolve 5 of tartar emetic, whilst the
same quantity of boiling water dissolves ten times as much, viz., 50,
The watery solution decomposes readily with the format ion of alg®; it
gives uo precipitate with ferrocyanide of potassium, chloride of barium,
or nitrate of silver^ unless concentrated*
§ 700, Metantimonic Acid^ so familiar to the practical chemist from
its insoluble sodium salt, is technically applied in the painting of glass,
poroelain, and enamels ; and in an impure condition, as antimony ash, to
the glazing of earthenware
6o2
POISONS : THKIB EFFKCl^S AND DETECTION.
L§75i.
g 75L Pharmaceutical, Veterinary, and Quack Freparatioiis
of Antimony.*
(1) Phannacetitical Prepaxations : —
Oxide of Antimony {Sb^Oj) is a white powder, fusible at a low red
heatj and aoltible without effervesceuce in hydrochloric iicid, the solution
responding to the ordinary tests for antimony. Arsenic may be present
in it aa an impurity. Carbonate of lime appears alao to have been fonnd
in the oxide of commercei
Antrmonial Powder is composed of one part of oxide of antimony
and two parts of phosphate of liaie; in other words, it ought to give
33*3 per cent, of SKO^,
Tartar Emetic itself baa been already deaoribed* The preparations
used in medicine are —
The Wine of Antimony (Yiuum antimoniale), which is a solution
of tartar emoLic in sherry wine, and should contain two grains of the salt
in each ounce of the wine (045 grm. in 100 c.c.).
Antimcmy Ointment ( Unguent um antimonii tartar ati) is a mechani-
cal mixture of tartar emetic and lard, or simple ointment ; t strength, 20
per cent* There is no recorded case of conviction for the aduiteration of
tartar emetic ; cream of tartar is the only probable addition. In such a
case the mixture is less soluble than tartar emetic itself, and on adding
a small quantity of carbonate of soda to a boiling solution of the suspected
salt, the precipitated oxide at first thrown down becomes redissolvod.
Solution of GMoride of Antimony is a solution of the terchloride in
hydrochloric acid ; it is a heavy lii^uid of a yellowish-red colour, power*
fully escharotic ; its specific gravity is 147; on dilution with water, the
whitish-yellow oxychlorido of antimony is precipitated. One driicbm
(3 "549 c.c.) mixed with four ounces (112 c.c.) of a solution of tartaric
acid ('25 : 4) gives a precipitate with SH^, which weighs al least 22
grains (1425 grm.). This liquid is used on very rare occasions as an
outward application by medical men ; farriers sometimes employ it in
the foot-rot of sheep.
Ptuiied Black Antimony (Antunoniiun nigrum purificatinn) is the
purified native sulphide 51x283 ; it should be absolutely free from arsenic.
Sulphurated Antimony (Antimonium sulphnratum) is a mixture of
sulphide of antimony, Sl>^Saj with a small and variable amount of oxide,
SbgOg. The B.P. states that 60 grains (3-888 grms.) dissolved in CIH,
and poured into water, should give a white precipitate of oxy chloride of
* The lii^tory t>f Antimony eis \l drug is ounou!^. Ita use w^fl pixthibited irt Frauiw
in I6^(tj because it was considered poisojiDUs, one Beeiiier being *ctUttlly expelled from
but fatiuhy for tranwgi'esaiug the Iaw on this jK^int. The edict was repealed in 1650 ;
the in IM& tbcre was & fresh enaciment, confining ita use to the doctors of the faotUty.
t Simple ointment is earn posed of white wax 2, lard 3, (tlnioTid oil 3 parts.
I 7510
ANTIMONY.
603
antimony, which (pmperly washed and dried) welghi about 53 grains
{3*444 grrus*). TUe ottlctnal compound pill of aubchloride of mercury
{Piiuia hydrargyri suhcMoridi composiia) coc tains 1 grain ('0648 grm.)
of sulphurated antimony in every 5 grains (^324 grtn.), i.e. 20 per ceut,
(2) Patent and ftuack Fills:—
Br, J. Jolm«oii^fl FillB.^Froni the rarmula each pill itliould catit^in i —
Gratni. Orra.
Compound Extract of Colocyn til, ♦ . . 2*5 = '162
Calomel, '62 = ^039
Tftrtar Emetie, ..,..,. "04 = '002
Oil of Caasia, ..,,,.. 12 = '007
3*28 = '210
The oil Qfcusaia oan b« eitmcbed by petroleum ether ; tlie oalomel sublimed aud
identiljed by the metlioda given in thti article on '* Mercury"; the antimoeiy do-
posited in the ai«tJ*llic hUU on pktijiiuu or tin ; and the colocynth extracted by
dtBdolving in water, acidifying, and shaking up with chloroform. On evu{jorating
the chloroform the residue i^hould taste extremely bitter ; diaaolved in sulphuric acid
it changes to & red colour^ and diBHolved in Frohde'a reagent to a cherry-red> It
should alsK) hare the oidinary reoctiona of a gluco^tde.
Uitohell's PilU <}oDtuin in each pill i —
GrmtnA. Onn.
AloM, 1-1= 070
Ehtibarb^ ........ 1*6 = -103
Oilomd, . -16 = 010
Tartftr Em«tie, 'OS - "003
2*ei = *]86
The mineral subetances in Ihinare easy of detection by the methods already gi^eai ;
the aloes by the formation of chrysammic acid, and the rhubarb by its mioroscopical
olmracters*
Diion^e Pilli probably contain the following in each pill % —
Comjwund Extract of Colocynth,
Bhubarbf . , » . .
Tartar £mjetiGv
2'0 = '1296
1-0 = *0e48
*06 = '0038
3*06 = '1082
(3) AnMmoiiial Medicines, chiefly Veterinary : ♦—
Liver of Antimony is a [jreparatii/n t'onnmly much used by farriers.
It \» A
* There bus long prevailed an idea (the tn^th of whiqh iadonbtful) that antimony
given to animalB improvee their condition ; thu^if thi> Bn^tfchp, Brii.^ £th ed., arL
** Antimony ^*;—^* A horse that h* lean and scrubby, iind not to be fiitted by any
meanflj wUl become fat on taking a dose of antimony every murning for two montba
together, A hoar fed for brawn^ and having an ounce of autlmony given him every
morning, will become fat a fortnight sooner thtin utbera put into the sty at the uame
time, and fed in the same manner, hut without the antimony." Probably the writer
means by the term anH'^noHy the hn^ure suJpliide, To thifl may be added the un-
doubted iact^ that in Bnmirwick the breeders of fat geeae add ti small ijuantity of
antimotjious osdde to tha food, aa a tiiiditioual outitom.
604 POISONS : THBIR EFFECTS AND DETECTION. [§ 752.
mixture of antimonions oxide, sulphide of potassium, carbonate of potassium, and
undecomposed trisulphide of antimony (and may also contain sulphate of potassium),
all in very undetermined proportions. When deprived of the soluble potash salts,
it becomes the washed saffron of antimony of the old pharmacists. A receipt for a
grease-ball, in a modem veterinary work, gives, with liver of antimony, cream of
tartar and guaiacum as ingredients.
Hind's Sweating-ball is composed of 60 grains (3*888 grms. ) of tartar emetic and
an equal portion of assafcetida, made up into a ball with liquorice-powder and syrup.
The assafcetida will be readily detected by the odour, and the antimony by the
methods already recommended.
Ethiops of Antimony, veiy rarely used now, is the mechanical mixture of the
sulphides of antimony and mercury — proportions, 3 of the former to 2 of the latter.
The Flowers of Antimony is an impure oxysulphide of antimony, with variable
proportions of trioxide and undecomposed trisulphide.
Diaphoretic Antimony (calcined antimony) is simply antimoniate of potash.
Glass of Antimony is a mixture of sulphide and oxide of antimony, contaminated
with a small quantity of silica and iron.
A quack pill, by name, Ward's Bed Pill, is said to contain glass of antimony and
dragon's blood.
Antimonial Oomponnds used in Pyroteohny :~
Blue Fire :—
Antimonious sulphide, 1
Sulphur, 2
Nitre, 6
This composition is used for the blue or Bengal signal-light at sea. Bisulphide
of carbon and water are solvents which will easily separate the powder into its three
constituents.
Crimson Fire : —
Potassic Chlorate, 17-25
Alder or Willow Charcoal, 4* 6
Sulphur, 18-
Nitrate of Strontia, 55 *
Antimonious Sulphide 5* 5
The spectroscope will readily detect strontia and potassium, and the analysis
presents no difficulty. In addition to these a very great number of other pyro-
technical preparations contain antimony.
§ 752. Alloys. — Antimony is much used in alloys. The ancient PoctUa emeUea,
or everlasting emetic cups, were made of antimony, and with wine standing in them
for a day or two they acquired emetic properties. The principal antimonial alloys
are Britannia and type metal, the composition of which is as follows : —
Tin, Copper. Antimony,
per cent. per cent. per cent.
Britannia Metal, Best, . . . 92*0 1*8 6*2
Common, . .92 1 2*0 5*9
For Castings, . 92*9 1*8 5*8
For Lamps, . . 94*0 1*3 4*7
Tea Lead, Antimony, Block Tin,
per cent. per cent. per cent
TypeMetel, . . . M^) ^'^ ^0 5
xypemewi, * * * \ (2) 70 25 5
Metal for Stereotype, .84*2 18*5 2*8
There is also antimony in brass, concave mirrors, bell-metal, etc.
§ 753-7S5']
ANTrWONY.
605
% 7BB. Pigments.— 0&:s^elk and Kapl^ ydlnw Ate pniid|mlly oomposod of th^
autUxionUtie of lead.
AnMmony YeUow is a mixture of antimoniate of le^d with basic chloride of
lea4
g 754. Dose*— A medicinal doso of a soluble antimouial salt should
Dot eiceed 97^^ mgrms, (IJ graio). With cirgum stances favouring ita
action, a dose of 129^6 mgrma, (2 grains) has proved fatal;* but this
IB qaite exceptional, and few medical men would consider so small a
quantity dangerous for a healthy adult, especially since most posological
tables prescribe tartar emetic as an emetic in doses from 64"8 to 194*4
mgnna. (1 to 3 grains). The a mall est dose which has killed a child
appears to be 48*5 mgrms, ( j grain), t The dose of tartar emetic for
horses and cattle is very large, as much as 5*B33 grms, (90 grains)
being often given to a horse in his gruel three times a day. 3*8 grms.
(60 grmins) are considered a full, but not au excessive, dose for cattle ;
'38 grm. (6 gnuns) is used as an emetic for pigs, and half this quantity
for dogs.
§ 755. Effects of Tartar Emetic and of Antimony Oxide on AnimalB.
— Large do^es of tartar emetic txct on the warm-blooded animals as on
man; whether the poison is taken by the mouth, or injected subcu-
taneously, all animals able to vomit ^ do so. The heart's action, at
first quickened, is afterwards slowed, weakened, and lastly paralysed.
This action is noticed in cold as well as in warm blooded animals. It is
to be ascribed to a direct action on the heart; for if the brain and
spinal cord of the frag be destroyed — or even if a solution of the salt be
applied direct to the frog^s heart separated from the body— the eflPect is
the same. The weak action of the heart, of courset causes the blood-
pressure to diminishj and the heart stops in diastole. The voluntary
♦ TVylor, Qufi ff&ip. E^porU, Oct. 1857. + Op. cit.
t I*^ Hermann {L^hrbit^h dcr cj^perimnUdUn Tf^icoltyrfU) remarkfl that the
voniitiiig must be confide rod as a reflex action from the itiQam.tiiati>ry eioitemDtit of
the digeativo apijaratus, eBpecially of the stomacii. It is witnessed if the j>oiflon ii
administered Bubcsutaneounly ctr injected into the bmliL tnd&ed, it Ih enUhlished
that (at least, St) fiir 4a the mmscleH are concenitid) the eo-ordinnte moveQienta
producing vomiting are caused by excitement of the medulla oblongata, Glannnaai
and pthorB found that aft«r section between the ft rat and third vertebiis of dogi», and
Bubsequent admin istmti on of tartar emetic^ no vomiting took plaee ; and Grimm's
reaearches aeeni to show tiiat the sm pec ted f^l^^^e«fl£^f ia identical with the
reipintoxy centre, so that the vomitiDg nu»yemetit is only an abnonual respiratory
movement, L» Hermann^ however, oonaiders the theory that when tartar emetic
\h introduce^d into the TesMls tha vomii-e^nJtr^ is directly elicited ^ erroneous » for(l)
in introducing it by the vaiiui mtiah UrgCT doie* are required to exeite vomiting than
by the itonxach ; and {%\ aft<»r subcutaneous injection of the salt, antimony is found
ia th« flrat vomit* Hb eiplauation, therefore, is that antimony is excreted by the
intestinal tract, and in ttia |)assage excites this acrtion, Majendie*s well -known
experiment — desmonstrnting that, after e3cttr|)ation nf the stomoeh, vomiting move-
munta were noticed— ia not 4K»naiderBd opposed to this view.
6o6
POISONS: THEIB BFFECT8 AND DETECTION.
[§ 756-
musclea of the body are also weakened ; the breathing is affected, partly
from til© action on the musclea. The temperature of the body is
depressed (according to ¥. A, Falck^s researches) from 4 '4* to 6'2°»
The effect of anmll doses giveu repeatedly to an i mala baa been
several times investigated. Dr, Kevin* experimented upon eleven
rabbits^ giviug them tartar emetic four times a day in doses of 32*4
mgi^ms. (^ grain )j 64 'S mgrms. (1 gTain)^ and 129*6 mgrms. {2 grains).
Five died, the first after four, the last after seventeen days; three
were killed after one, three, and four days respectively, two after an
interval of fourteen days, aud one thirty -one days after taking the last
dose. There waa no vomiting ; diarrho&a was present in about half the
number ; one of the rabbits, being with young, aborted. The chief
symptoms were general dnlneas, loss of appetile, and in a few days
great emaciation. Four of the five that died were convulsed before
death ; and several of the animals exhibited ulcera of the mucous
membrane of the mouth, in places with which the powder had come in
contact. Caillol and Livon have also studied the action of small doses
of the white oxide of antimony given in milk to cats. A cat took in
this way in 109 days '626 grm. The animal passed gradually into a
cachectic state, diarrhoea supervened, and it died miserably thin and
exhausted.
§ 756- Effects of Tartar Emetic on Maat — ^The analogy between
the symptoms produced by arsenic and antimony is striking, and in
some acute cases of poisoning by tartar emetic there is but little (if
any) clinical difference- If the dose of tartar emetic is very large,
there may be complete absence of vomiting, or only a single evacuation
of the stomach. Thus^ in a case mentioned by Taylor, in which a
veterinary surgeon swallowed by mistake 13 grms. (200 grains) of
tartar emetic, vomiting after fifteen minutes could only be induced by
tickling the throat. So, again, in the case reported by Mr. Freer,
a man^ aged 23, took 7*77 grms. (130 grains) of tartar emetic
by mistake for Epsom salts; he vomited only once; half an hour
after taking the poison be had violent pain in the stomach and
abdomen, and spasmodic contraction of the abdomen and armsj
• Lev^r, Med. Chit. Joum^^ No. 1.
t AutimoTiy occasion ally finds its way into articles <rf food through obscure
channels. Dr. Pag^ has recorded the fact of antimouial lo^ngiea having h^en sold
openly hy an itinerant vendor of confectioneTy, Efich loz^jnge contained nearly a
quartet of a grain ('16 mgrra.), and they cansed well -marked Byiuptoms of jHnsoning
in the case of & servant and two children. How the antimuny got in was unknown*
In this cose it appears to have existed not as tartar emetic, but as an insoluble uxid*^
for it would not dialyae in aqueouH solution. — '* On a remarkable instanoe of PoIeod*
ing by means of Lozenges contalnitig Antimony,*' by David P&g&, M.D., Medical
OMcer of Healthy LaneH, vol i, IB? 9, p. 6^9.
§ 7S7-1
ANTIMONY,
607
the fingers were firmly contracted, the muBcles quite rigid, and
there was iiiToluotary aqueous purging. After nit hours^ during
which he waa treated with green tea, brandy, and decoction of oak-
barkf he began to recover, but suffered for many nights from profuse
perspL rations.
With more moderate and jet large doses, nausea and vomiting are
very prominent symptoms, and are seldom delajed more than half ati
hour. The regular course of symptoms may therefore be summed up
thus :^A metallic taste in the mouth ; repeated vomitings, which are
sometimes bloody ; great faintneas and depression ; pains in the abdomen
and stomach ; and diarrhcea, which njay be involuntary. If the case is
to terminate fatally, the urine is siippreased, the temperature faUs, the
face becomes cyauotici delirium and convulsions supervene, and death
occurs iu from two to six days* Antimouy, like arsenic, often produces
a pustular eruption, SoHtary cases deviate more or less from the
course described — t,e. severe cramps affecting all the musclea,
hBemorrbage from the stomach, kidney, or bowel^ and death from collapse
in a few hours, have all been noticed. In a case recorded by Mr,
Morleyi* a surgeon's daughter, aged 18, took by mistake an unknown
quantity of antimonial wine ; she soon felt sleepy and powerlessj and
suffered from the usual symptoms in combination with tetanic spasms
of the legs. She afterwards had enteritis for three weeks, and on
recovery her hair fell off. Orlila relates a curious case of intense spasm
of the gullet from a large dose of tartar emetic,
§757. Chronic Antimonial Poisoning, — The cases of Palmer and
J, P, Cook, M, Mullen, Freeman^ Winslow, Pritchardp the remarkable
Bravo case, and the Chapman case have given the subject of chronic
antimonial poisoning a considerable prominence^ In the trials referred
to, it wiia showu that medical men might easily mistake the effects of
doses of antimony given at intervals for the action of disease — the
symptoms being great nausea, followed by vomiting, chronic diarrhoea^
alternating with constipation, small frequent pulse, loss of voice, great
muscular weakness, depression, with coldness of the skin and a clammy
peropiratiou. In the case of Mrs Prit€hard,f her face was flushed, and
her manner so excited as to give an ordinary observer the ideii that she
bad been drinking ; and with the usual symptoms of vomiting and
purging, she suffered from cramps in the hands. Dr* P rite hard tried to
make it appear that she was sufiering from typhoid fever, which the
symptoms iu a few respects oii!y resembled.
According to Eulealwrg, workmen, exposed for a long period to the
vapour of the oxide of antimouy, suffer pain in the bladder and a born*
f min. Mid. Jmtn., ISftB.
6o8
POISONS: THEIB EFFKCTS AND DKTECTION
[§ 758.
ing eensatioQ in the urethm^ and cotitinued inhaJatiou even leads to
impotence and wasting of the testicles.*
§ 75 B. Tbe Ctiapman CBse. — tSeverino EloswBti aitoit George Ohapman
was a Russian Pole who had been apprenticed to a surgeon in Warsaw,
and had obtained the degree of "Faldsohen" Coming to England be
acted aa a barber'B assistant, and married a Lucci Padergei in October
1889, This woman left him after a short time. He then took the
name of Chapman and lived with a woman, Mrs. Isabella Spint^ who
passed as ^frs. Chapman, The couple went to live at Hastings, where
Chapman became more or less intimate with a chemist, from whom ho
obtained about an ounce of tartar emetic. Leaving Hastings, be next
appears as the landloi-d of the " Prince of Wales " pnblic-honse, Bartholo-
mew Square, Finaburj, l^Irs, Chapman now became ill, the chief symp-
tom being frequent vomitings Chapman ascribing her illnesR to excessive
drinking. On Christmas Day, 1897, Mrs. Chapaian was extremely ill,
and her husband gave her freqnent doses of brandy, after each of which
the sickness increased. She died about midday. His neit victim was
Elizabeth Taylor, who tiist appeared as barmaid, and was then per-
suaded to go through some form of marriage with Chapman in the
spring of 1 899. In Marob they moved into the " Monument " public
house in Sonthwark^ where the woman became ill^ the symptonis being
the same as before. Dr. Stoker, who was called in on lat January^
ascribed the illness to some obscure stomach disease, this opinion being
cou firmed by two medical colleagues who were summoned. The case
ended fatally on 13th February.
In August, Maud Marsh appears as barmaid, and in October the
parents of this girl were deceived by a tale of a sudden marriage with
Chapman. The " Monument " public house shortly after this being burnt
iJown, the couple moved to the '* Crown, ^' wherCj owing to the attraction
of a new barmaid. Chapman's affection for Maud Marsh seems to have
waned, with the result that in July 1902 Maud began to feel unwelb
She had brandy administered to her by Chapman which always brought
on violent sickness. On 2Sth July she went to Guy*s Hospital as an
in-patient for three weeks, where she was treated for inflammation of the
stomaeh and discharged cured. On returning to tVie ** Crown " she at once
became ill again, and in the l>eginning of Octotier Dr* Stoker was again
callefl in, and, later, Dr. Orapell. On 22nd October Maud Mar^h died,
and Dr. Stoker refused to give a certificate of death before holding a
post-mortem examination,
Dr, Stoker's prelimiuiiry examination revealed much inflammation
* In the first oiieraticin^^ of iinishing printent* tyjtes, the workmen luhsle »
Tiieta.llic dii<)t, which gives nne to elfeet« samilftr to load colic ; and probably in this
oaite the lead is more Mtive thaa the ansoci&ted antimony.
I 759-]
ANTIMOKY.
609
of the stomaohf but no sigua of organic disease. He sent some portion
of the mcera to Mr, Bodraer, Public AiialyBt for Berraondsej, who found
in it arsenic in small quantity and a considerable quantity of antimony^
Chapman waa jiovf arrested, and hia room at the ** Crown *' searched,
where the police found soTeral medical works and some powders which,
upon analjsiSf proved to be tartar emetic«
A further post- mortem examination wag made ou the body of Maud
Marsh by Dr. Freyberger, pathologist to tlie London County Council,
and the organs submitted to Dr. SteveuBon for analyeis. The result of
these inyestigations left no doubt as to the cfiuse of death, Dr Stevenson
Knding from 25 to 30 grains of tartar emetic in the stom&oh alone.
In the meanwhile the bodies of Bessie Taylor and Isabella Spiot were
eiihumed, and found to be in an astonishing state of preservation,
eapeotally remarkable in the case of the latter who had been buried five
yearSp Dr, Stevenson found 1'37 grains of antimony in the organs of
Isabella Spint, and no less than 29' 12 grains in those of Bessie Taylor.
Chapman was found guilty, and hanged on 7 th April 1903,
§ 759. FoBt-mortem Appearances. ^^The effect of large doses of
tartar emetic is mainly concentrated upon the gastro-intesttnal mucous
membrane. There is an example in the museum of University College
Hospital of the changes which resulted from the administration of tartar
emetic in the treatment of pneumonia. These are ascribed in the cata-
logue^ in part to the local action of the medicine, and in part to the
eitreme prostration of the patient. In the preparation (No. 1052) the
mucous membrane over the fore border of the epiglottis and adjacent
part of the pharynx has been deatrf>yed by sloughing ; the ulceration
extends into the upper part of the oesophagus. About an inch below its
commencement, the nuieous membrane has been entirely removed by
sloughing and nlcenition^ the circular muscular fibres being exposed.
Above the upper limit of this ulcer, the mucous membrane presents
several oval, elongated, and ulcerated areasj occupied by strips of mucous
membrane which have sloughed* In other places, irregular portions of
the mucous membrane, of a dull ashen-grey colour, have undergone
sloughing; the edges of the sloughing portion are of colours varying
from brown to black*
It is seldom that so much change is seen in the gullet and pharynx
as this museum preparation exhibits ; but redness, swelling, and the
general signs of inflammation are seldom absent from the stomach and
sonie parts of the intestines. Ou the lining membrane of the mouth,
ulcers and pustules have been observed.
In Dr. Nevin's experiments on the chronic poisoning of rabbita
ulready rcferreil to, the post-mortem appearances consisted in congestion
of the liver in all the rabbits ; in nearly all there was vivid rednesa of
6io
POISONS: THEIR EFFECTS AND DKTECTJON. [§ 760-762,
the atomac^h ; in two casaa there wti8 ulceration ; in some, cartQagmoua
hardnesB of the pjlonis, while in others the amall intestines presented
patches of inflanimation. In two of the rabbits the solitary glands
throughout the intastines were prominent, yellow in colourj and loaded
with autiraony. The oolon and rectum were healthy, the kidneys
congested ^ the lungs were in most congested^ in some actually infiamedf
or hepatised and gorged with blood. Bloody extravasations in the cheat
and abdomen were frequent.
Salkowsky,* in feeding animals daily with antimony, found invariably
in the oourse of fonrteeu to nineteen days fatty degeneration of the
liver, and sometimes of the kidney and heart. In the experiment of
Caillol and Livon also all the organs were pale, the liver had undergone
fatty degeneration, and the lung had its alveoli filled with large
degenerated cells, consisting almost entirely of fat. The mesenteric
glands also formed large caseous masses, yellowish-white in colour,
which, under the microscope, were seen to be composed of fatty cells, so
that there ia a complete analogy between the action of arsenic and
antimony on the body tissues.
g 760. Elimination of Antimony.— Autimony is mainly eliminated
by the urine. In 1S40, Orfila showed to the Aead^mie de MMecine
metallic antimony, which he had extracted from a patient who had
taken '1 2 grm, of tartar emetic in twenty-four hours, He also obtained
antimony from an old woman, aged 80, who twelve hours before had
taken "6 grm, (d^ grains) — a large dose, which had neither produced
vomiting nor purging. In Dr, Nevin's experimenta on rabbits, antimony
was discovered in the urine after the twelfth dose, and even in the urine
of an animal twenty-one days after the administration of the i)oiaon had
been suspended. According to Pouchet^f experiments on dogs and
rabbits^ antimony in chronic poiaotiing accumulates in the digestive
tract and is found in only small quautitiea in the organs of the body.
g 761. Antidotes for Tartar Emetic. ^ — Any infusion containing
tannin or allied astringent principles, such ns decoctionB of tea, oak-bark ^
etc., may be given with advantage in cases of recent poisoning by tartar
emetic, for any of the salt which has been expelled by vomiting may in
this way be decomposed and rendereii harmless. The treatment of acute
poisoning which has proved most successful, has been the encouraging
of vomiting by tickling the fauces, giving strong green tea and stimu-
lants. {See Appendix.)
§ 762, Efifectft of Chloride or Butter of Antimony.— Only a few
caaee of poisoning by butter of antimony are on record : ita action,
* Yirchonf^n Arch. f. p&iL AmU., Bd. xiv,; also, OeniralhlaU /» Med. fFismt.,
No. 23, 1865,
f Oompt. h'enii\, 1901,
§ 763.]
AKTIMONY,
6ti
generally apeakiugf on the dssues is like that of an »ciii, but there liuM
been cooeiderable variety iti the symptoms. Five cmses are recorded
by Taylor; three of tlie number recovered after taking reajjectively
doses of 77 grms, (2 draehmB) and 15^^ grms. (4 draebms), ^i^d twa
died after taking from 56*6 to 1 1 3 grms. {2 to 4 ouiiees). In one of
these eases the symptoms were more like those of a narcotic pobon^ in
the other fatal case there was abundant vomiting with purging. The
autopsy in the first case showed a black appearance from the mouth to
the jejunum, as if the parts had been charred, atid extensive destruction
of the mucous membrane. In the other case there were similar changes
in the stomach and the upper part of the jutestiuea, but neither the lips
nor the lower end of the gullet were eroded. In a case recorded by
Mr. Barrington Cooke,* a farmer's wife, aged 40, of unsound mind,
managed to elude the watchfulness of her friends, and swallowed an
unknown quantity of antimuny chloride about L30 p,m. Shortly after-
wards she vomited several tinies, and had diarrhcea ; at 3,30 a medical
man found her lying on her back insensible^ and very livid In the face
and neck. She was retchitig, and emitting from her mouth a frothy
mucous fluid, mixed vfllh ejected matter of a grumous colour; the
breathing was laboured and spasmodic ; the pulse could not be felt, and
the body was cold and clammy* Sho expired at 3,30, about one hour
and a half from the commencemeut of symptoms, and probably within
two hours from the taking of the poison. The autopsy showed no corru-
gation of the tongue or inner surface of the liuing membrane of the
mouthy and no appearance of the action of a corrosive upon the lips,
fauces, or mucous membrane of the o^sophiigus. The whole of the
mucons membrane of the stomach was intensely eong«^»ted, of a dark and
almost black colour; the rest of the viscera were healthy. Chemical
analysis separated aiitimony equivalent to nearly a grm. {15 grains) of
the chloride^ with a small quantity of arsenic, from the contents of the
stomach.
§763. Detection of Antimony m Ot^anic Matters* — In acute
poif^oning by tartar emetic it is not impossible to find a mere trace only
in the stomach, the greater part having been expelled by vomiting,
which nearly always occurs early, so tliat the most certain method is,
where possible, to analyse the ejected matters. If it should be suspected
that a living person is being slowly poisoned by antimony, it mtist be
remembered that the poiifon is excreted by the kidneys, and the urine
should afford some indication. The readiest way to teat is to collect a
considerable quantity of the nrine (if necessary, two or three days^
excretion), and test. In any case, whether the analyst operates on nn
organic solid or liquid, the organic matter is destroyed by one or other of
* Imnoeit May 19, 1833.
6l2 POISONS: THEIB KFFSCTS AXD DKTICTION. [§ 763.
the processes detailed at pp. 52-55 : the acid solution ultimatelj obtained
is then concentrated and saturated with sulphuretted hydrogen. It is
important that the liquid should only just be acid ; for Lang and Carson
have shown that antimony sulphide is soluble in HCl of sp. gr. I'lG,
and that it is generally much more soluble than arsenic sulphide. Any
precipitate of whatever colour is filtered off, washed, and digested with
ammonium sulphide.
The sulphides soluble in ammonium sulphide* are as follows : —
Ooloiir of Sulphide.
Anenic yellow.
Antimony onnge.
Stannous salts brown.
Stannic salts dirty yellow.
Gennaniom white.
Selenimn orange.
Tellnrimn black.
Gold brownish black.
Platinum brownish black.
Iridium brownish black.
In a toxicological research, only arsenic or antimony or tin are
likely to be present, although, if platinum utensils have been used, we
have known the sulphides to be darkened by a small proportion of
platinum sulphide.
The sulphide or sulphides may now be separated and identified in
various ways.
(a) Dry Method. — The sulphides are dried and intimately mixed
with dry potassium cyanide and sodic carbonate, and submitted to the
reducing flame of the blowpipe on charcoal; an onion-like odour
indicates arsenic, a white coating slowly volatilising — antimony, and
ultimately tin, if present, may be obtained as small globules.
The dry process is, however, more applicable for the quantities met
with in mineral analysis than for toxicological research.
(b) Wet Processes.— The sulphides are treated with concentrated
hydrochloric acid and heated to about 70°. Antimony and tin sulphides
pass into solution ; arsenic sulphide, if present^ remains, and may be
dissolved by ammonia and ammonium carbonate.
The solution of possible antimony and tin sulphides is placed in
a platinum dish, and a small strip of zinc foil immersed therein.
Antimony immediately causes a dark stain; on removing the zinc
thus stained, and well washing, the zinc is treated with hot nitric
* Ammonium sulphide slightly dissolves copper sulphide, and since the liver
always contains copper, it is useful in researches in that organ to rather use sodium
sulphide which will not dissolve copper sulphide. Gold, platinum, and iridium
sulphides are very insoluble by themselves, but when in presence of the arsenic group
of sulphides are somewhat soluble.
S 763]
AWTIMOffT.
613
acid. The nitric Rcld aolution will respond to the special tests for
antimoujr (e.tj, it maj be tested with the cffisium eompouud salt).
The strip of zinc freed from the antimony deposit may be replaced
in the original liquid ; if tin is present, tin in a metallic form will be
depoaited.
Hyposulphite Method of SeparatioiL — This e^ccellent method of
obtaining a separation of the three sulphides has been already described
(see page 56),
Tartanc Acid Method. — ^The sulphide or sulphides are treated
with 15 ex. of nitric acid, and the mixture evaporated to drjnesa.
The residue is dissolved in 100 c,c* of warm water. The arsenic acid
dissolves, and may be precipitated by magnesia mixture ; antimony
and tin J if present, remain as insoluble oxides on treatment with
tartaric acid solution for an hour — antimony oxide diesolres, tin oxide
is left. The tartrate of antimony aolution may be now feebly saturated
with hydrie sulpinde, adding a little HO ; the sulphide collected Is
i5on verted into oiide by nitric acid and weighed as tetroxide/
It will, however, be advisable to reserve a small portion of the
tartaric acid solution for a conhrmatory teat^ such as the formation
of antimony ciBsium iodide.
Sodium Peroxide Method.— The sulphides are diluted and heated
with a little ^vater in a porcelain ba.«iiu, and caustic soda, in not too
great excess, added until no more of the precipitate seems to dissolve.
Three or four drops of ammonium sulphide solution are then added, and
the liquid boiled until free from odour of ammonia. The solution is
now dihited with warm water and filtered.
The hltrate contains the arsenic group, and, possibly, mercury. After
further dilution the ti Urate is boiled, and sodium peroxide gradually
added until there is a permanent eifervesceuce of oxygen ; any mercury
will go down as sulphide and can be hltei-ed off— the filtrate contains
only sodium arsenate, antimoniate, and stannate.
Should tin be present » this is separated by adding ammonium chloride
in the proportion of three times the bulk of the sodium peroxidei and
boiling ; the tin separates as a white getatiuous precipitate.
The filtrate is now first acidified v^ith hydrocMaric acid and warmed
until oxygen oeas^ to be evolved, it is then cooled and treated with
a rapid current of BH^* Antimony, if present, is ai once precipitated
us an orange or golden-yellow sulphide ; this is filtered ofT and confirmed.
To the flit rate, which ought to smell feebly of SHg, a few drops of
sodium thiosulphate is added and the solution warmed until a pre-
cipitate begins to separate. The solution is then treated with SH^,
If the precipitate is white, it consists merely of sulphur; if bright yellow,
* Wnu B. Lttug, C. M. Gai^ou, AudJ. C. Miickiiitoah— Sac. Ckem. lud., 1902*
6i4
POISONS : Ttrem effects and detkgtion. [§ 763A, 764.
it coutaiofl arsenioos sulphide, which must \m c^nHrmed in the usual
manner.*
Autimony compounds dissolved in HCl (1 -A) or dilute H^SOi (I : 10)
and treated with a solution of potassium iodide and caesium chloride
(1 of KI to 3 of C«C1 in 10 c.c, water), give the insoluble antimony
csBsium iodide in yellow or garnet^red hexagonal lamellie. This will
detect a thouBandth of a milligmmme of antimony in presence of 500
times its weight of arsenic, t Marah'a test (already described) may, if
antimony be present^ reveal its presence by the character of the stain ;
practical chemists would not, however, in a special search for antimony
use Marah'fi test, but proceed in the manner already detailed. Tha
characters of stibine are as follows : —
§ T63a. Stibine (antimony bydridej an timoniu retted hydrc^en),
SbHg. — Molecular w^cight, 125. The gas contains 97*6 per cent. Sb,
2 '4 per cent- H. The gas, by cooling with liquid air, has recently l>een
obtained in a pure state. The solidified gas melts at - 88° to a colour-
lass liquid J the boiling-point at normal pressure is — 17*. } The liquid
has a sp. gr. of 2'36 at ^25*, and 3%34 at -50\
At ordinary temperatures 1 volume of water dissolves 15 volumes
oF the gas ; 1 volume of alcohol dissolires alao the same volume ; at 0"
1 volume of carbon disulphide dissolves no less than 250 volumes of the
gas.
The dry gas is fairly stable, but the moist gas is unstable. In
presence of air or oxygen at ordinary temperatures it decomposes into
antimony, water, and a little hydrogen.g The gas passed into a solu-
tiou of mercury and potassium iodides HgU + KI (Hgl «KI, with w> 2)
gives a brown-black precipitate of SbHg^l^ ; arsine acts similarly, and
phosphtne gi^es, under the same circumstances, a yellow crystalline
solid.|| When the gas is pissed over sulphur, stibine is decomixwsed
according to the equation 28bH3 4- 6S = Sh^S^ + 38H^„ and the sulphur
assumes a deep orange tint The reaction takes place very slowly in
ordinary daylight, rapidly in sunshine* Given bright sunshine, tbis
reaction may be utilised as a test. The antimony sulphide may be
freed from aulphur by digestion in CSj. The distinctions between the
ataius depcKiited by heating arsine or stibine have been already described.
Stibine, like arsine, is intensely poiaonous ; mice die in a few seconds if
exposed to air containing 1 per cent, of stibine.
§764. ftoantitative Estimatioii.— The quantitative estimation of
antimony is bes^t tuade by Home volumetric process — e.^. the sulphide can
* JsiQti Walker, Jmirn. C.S., Trant.^ 1903.
t Georges Denige*, Compt Revd., ISOl.
t Stock and Doht, Ser., 1902. § Stock *nd Guttmau, Ber.^ 1901.
Jl Pftul Lemoult, CtimpL EeHd,^ 1904.
§ 765-77a]
CADIUDH.
6is
be dissolved m HCl, some tartrate of soda added, and then carbonate of
soda to weak alkaline reaction. The strength of the solution of tartariaed
antimony thus obtained can now be estimated by a deci normal solution
of iodine, the end reaction being indicated by the previous addition of a
little starch solntioni or by a solution of permanganate of potaah, either
of which should be standardised by the aid of a solution of tartar emetic
of known strength.
S. CADMIUM.
g 765, Cftdmium, Cd = 112 ; spedfio gmvity, S'6 to 8*59 ; fumng- point, 227 'S'
(442* F.) ; boiling'^Kiint, 800'' (1530^ F.).— Cadruiun] in analysis is seldom sepAmted
&s ft metal, but is oetimabed either ils o^tde or sulphidi?.
g 7fl6. Cadmium Oxidf^ CdO = 12S — (^dmiumj B7^5 pereeut, ; oxygen, 12'5 per
cant.— 'ift a ysUowiiih or reddUt^ brown powder, non-voliktile even i^t « wliito heat;
iunoliible in wAter, but disfjolving in ncids. Ignited (»q charcoal, it \s redaoed to
motal, whjcb volatiliscB^ and is then deposited ugain aa oxide, givikig to the ohanioiil
11 distinct coat of an otanga*yeUow colour in very thin lajera ; in thicker layers,
brown.
S 767. CadtilinM Sulphide, CJS=:144— Cd, 77*7 per ceot- \ 8, 2*2 3 per cent—
knoTK^n as a nun era! termed Green ockito. When j!i^]>ared in the wet way, it is a
lemon -yeUow powder, which oantiot be ignited in hydrogen witbout loss, and is
insoluble in water, dilnte acids, olkaliei^ alkaline sulphides, sulphate of soda, and
cyanide of [Kitaasium. The solution must not contain too mucb hydrochloric acid,
for the sulphide h raadily soluble with fle^sirfttion of sulphur in concentrated hydro-
chloric Acidi It may be dried in the ordinary way at 100" without suffering any
docom{>oaition*
g 76S. Medieinal FrefMirationa. — The Iodide qf Cadmium (Cdig) occurs In whita,
flat, micacieoun cry^tab, meltiug at about 'iU**&'' (419 '9' F.)» and at a dull rod heat
giving off violet yijiour. In aolutioti, the shU gives the reactians of iodine and
ci^dmium< The uintnient uf iodide of cadmium {UwfuetUufn eathaii ioduii) pontajnis
tlie iodide in the proportion of 6^ graitia to the oumcc^, or 14 i>er cent,
Cadminm Snlphate is oMainal in the Belgian, Fortiiguefl<5, and French pharma-
copceiaH.
g 7i30. Cadmium in the Arta, etc, —Cadmium is need in vano^ie alloys. The
sulpyde is found a« a colouring ingredient in certain toikt »o<ips, and It is mu@h
valued by artists as a pigmetiU The iodide of cadmium is employed in photography,
and an amalgam of metaUic cadmium to some eitent in dentistry.
§ 770. Fat*l Doae of Cadmium. — Although no deaths from the use of oadmium
appear to have as yet oLH^urrcd* its U^ m photography, etc., may kad to accidents^
There can be no quesdou about the ^Kiisonous action uf cadmium, for Marm^,* in
his experiiueDts on it with animalA, observed giddiness, voinitiogp syncope, difficulty
in respiration, loss of consoiousness, and crampA. The amount neoe^ssaty to destroy
Hfe can only bo gathered from the OTpeninoiila on animals. A strong bound di^
after the injection of 'O^j grm. { '462 grain) subcutaneously of a salt of cadmium '■>
rabbits are fjoisoned if from IS'-t to 38*8 mgrms. (*3 to ^0 grain) arc introduced into
the stomach. A walefy solution of *5 gnu. (7*6 grains) of the bromide administered
to a pigeon caused instant death, without convulsion ; the samo dose of the chloride
killed a second pigjeon in six minutes ; '25 grra. (3 '86 grains) of sulphide of cadmium
administered to a pigeon excited vomiting, and, after two hours, diarrhcisa — it died
In eight days. Another pigeon died from a similar doee in fourteen days, and
* Z^iUthr.f, rtilvmeU* Mtd,^ vol. zxix. p. 1, ldd7,
6l6 POISOK8: THEIR EFFECTS AND DETECTION. [§771,772,
cadntium, on analyais, was separated from the Mver, From the aboTQ cases it would
seem probable thut 4 grms. (61 *7 grains) would l>e a daiigeroua dose of a soluble salt
of ciMlmium for an odiilt, and that in a ea&R of chronic poisoning it would most
probably be found in the liver,
§ 771. aoparation and Detection of Cadmium, — If cadmium b« in solution, and
the solution in not too acid, on the addition of SH^ tbere ia precipitated a yellow
sulphide, which is distinguished fronj antimony and arsenical sulphidee by Iti in-
solubility in ammonia and alkaline aulphides. Should all three sulphides be on the
filter (an oct^urrence which will seldom, p^rhapH never, happen)^ the sulphide of arsenic
can be diasotred out by ammania, the antimony by sulphide of aodiumi leaving the
sulphide of cadmium as the residne.*
The further tests of the sulphide are : —
(1) II dissolves in dilute nitric acid to a colour! ass fluidj with separation of
sulphur,
(2) The solution, filtered and fri^ml from oxceHS of nitric acid by evaporation, gives
with a solution of ammonic car^Htnate a white precipitate of carbonate of cadnaiiun
iniioluble in excess, Thia dijitinguishes it from zinc, which gives a similar white
precif)itate, but iw aolublo in the estceas of the precipitant
(3) The carbonate thus obtained, heated on platinum foil, is changed into the
brown-red non-volatile oxide.
(4) The oxide behaves on charcoal as already detailed.
(5) A metallic portion can be obtained by metting the oxide with cyanide of
potassium ; it is between sine and tiu iu brilliancy, and msiEeB a mark on paper like
lead, but not so readily. There are many other teats, hut the above are conclusive.
If cadmium in any ca§e be Jtpecially searched for in the organs or tissues, the latter
should be boiled with nitric acid* The acid solution is filtered, saturated with
eauatic potash, evaporated to dryness, and ignited ; the residue ia dissolved in dilute
hydrochloric acid, and treated after filtration with BH^ Qidmium may also be
eatimated volumetrically by digesting the sulphide in a att»ppered flaak with ferric
chloride and hydrochloric acid ; the resulting ferrous comi>onnd is titrated with
pennMiganate, each cc. of a d,n. nolution of ].>ermHnganate= '0056 grm, of cadmium.
I L— PRECIPITATE BY HYDRIC SULPHIDE IN HYDRO-
CHLORIC ACID SOLUTION ^BLACK,
Lead— Copper— Bismuth— Silver— Mercury,
L LEAD,
I 772, Lead, Pb== 207.— Lead is a well-knowu bluish-white, soft
metal — fusing- point, 325* ; Bpecific gravity, 11 SS.
Oxides of Lead.— The two oiides of lead oecesaary to notice here
briedy are — litharge and minium.
Litharge or Oxide of Lead, PbO = 223 — apecifio gravity, 9 2 to 9'5 ;
Ph 92*82 per cent, 0 7*18 — ib either in cryatallitie scalei, a fuaed mafis,
or a powder, varying in colour (aoiiording tu its mode of preparation)
from yellow to reddiah-yeUow or orange. When prepared below the
* It ij3 uaneoessary to ataie th^t ab^nea of aulphur is proaupposed.
§ 773-77^ 1
LEiLD.
617
temperature of fusion it is called " masaieot/' It may he fused without
alteration in weight ; in a state of fusion it diaaolTes giUcic acid and
silicates of the earths. It must not be fused in platinum vessels.
Minium, or Eed Le&d, *2PbO, PbOj— spaeifie gravity^ 9 '08— is a
iiompound of protoxide of lead with the dioxide. It is of a brilliant red
colour, much used in the arts^ and especially m the preparation of
dint-glass,
§ 773, Sulphide of Lead, PbS= 239— Pb, 86 61 per cent ; S, 13 39
per cent— occurring in the usual way^ is a black precipitate insoluble
in water, dilute acids, alkalies, potassium cyanide^ and alkaline sul-
phides. It dissolves in strong nitric acid with separation of sulphur,
and in strong hydrochloric acid >vith evolution of SH^. Fuming nitric
acid does not separate sulphur, but converts the sulphide into
sulphate,
§ 774, Sulphate of Lead, PbSO^ = 303— specific gravity, 6 '3; PbO,
73*61 per cent. ; SQ^, 26'39 per cent, — when produced artificially, is a
heavy white powder, of slight solubility in water, 22,800 parts of cold
water dissolving only one of lead sulphate ; and if the water contains
sulphuric acid, no less than 36,500 parts of water are required. Alkaline
acetates^ the acetate, tartrate, and citrate of ammonia dissolve the sul-
phate without change ; sodic bypotiulphite dissolves lead sulphate,
changing it partly into sulphite. The sulphate can be readily changed
into the carbonate of lead by boiling it with solutions of the alkaline
carbonates. The sulphate of lead, fused with cyanide of potassium,
yields metallic lead; it may be also reduced on charcoal, fuid alone
it may be fused without decomposition, provided reducing gases are
excluded.
§775, Acetate of Lead, Sugar of Lead, Fh{a^U^0^\mH^ = ^7^t
ia found iu commerce iu white, spongy masses cooiposed of acicular
crystals. It may, however, be obtained in flat, four-aided prisms.
It has a sweet metallic taste, is soluble iu water, and responds to the
usual tests for lead. The F,B. directs that 38 grains dissolved In
water require, for complete precipit^rioti, 200 grain measures of the
volumetric solution of oxalic acid, corresponding to 22*3 grains of
oxide of lead,
§776. Chloride of Lead, PbCl^ = 278— specific gravity, 5 8; Pb,
7448 per cent. ; CI, 25*52 per cent, — is in the form of brilliant crystalline
needles. It is very insoluble iu cold water containing hydrochloric or
nitric acids* According to Bischof, 1635 parts of water containing nitric
acid dissolve one part only of chloride of lead. It is insoluble in absolute
alcohol, and sparingly in alcohol of 70 to SO per cent- It fuses below
red heat without losing weight; at higher temperatures it may be
decomposed.
6iS
poisons: their kffects and detection.
[§ 777
Carbonate of Lead, — Tbe commercial carbonate of lead (according
to the exlituiBtive researchea of Wigaer and Harland *) m composed of a
mixture of neutral carbonate of lead and hjdrate of lead, tbe beat
mixture being 25 per cent* of hydrate, corref^ponding to an actual
percentage of 12 '3 per cent, carbonic acid. The nearer the mixture
approitaiateg to thia compoaition the better the paint ; whilst samples
containing as much as 1633 per cent., or as little as 10-39 per cent., of
CO^ are practically useless.
§ 777. PreparationB of Lead used m Hedicme) tbe Arts, etc.
(1) Pharumceutical;—
Lead Plaster (Emplastmm pliunbi) h simply a lead soap, in which
the lead h combined with oleic and margaric acids, and contains some
mechanically inclnded glycerin.
Lead Iodide, PbJ2J i* contained in the Empl(Mifnm plumbi iodidi
to the extent of 10 per i^eiit., and in the Unguefdum plumbi iodidi to
the extent of about 12^5 per cent.
Acetate of Lead is contained in a ptU, a suppository, and an oint^
ment. The pill {Pilnla plumM cum ifpio) contains 75 per cent, of lead
acetate, and 12'5 per cent, of opium, the rest confection of rosea The
suppository {Suppomioria plumbi composita) contains 20 per cent, of
acetate of lead, and 6*6 per cent, of opium, mixed with oil of tbeobmma.
Tbe ointment (Umjfifmium plumbi aretatu) contains 20'6 per cent* of
lead acetate, mixed with ben^oated lard.
The solution of subacetate of lead (Uquor phwtfji mfjOfetaiu) is the
subacetate, Pb(C<,Hjj02)2rbO, dissolved in water; it contains nearly 27
per cent, of subacetate,
A dilute solution of the stronger, under the uanie of Liquor
plitmhi mitbaeetidi^ tUiuiiu^ and commonly called Goulard water, is
prepared by mixing 1 part (by volume) of the solution and 1 part of
spirit, and 78 parts of distilled wnter; the strength is equal to 1*'25
per cent
There is an ointment, called the Oomfiound OintmefU of mihacetate of
leadf which contains the subacetate in about the proportion of 2 per
cent, of the oxide, the other eonstituerita being camphor, i*bite wax, and
almond 01 L
Caxbonate of Lead*— The ointment ( Ungueiilum plumbi earbonaiis)
should contain about 12 5 per cent, of the carbonate, and tbe rest simple
ointnvent.
(2) Qa&ok KoBtrumi, etc, : —
The quack medicixies eamjKi^ed o( le&d are not very namerQUs,
liebcrt^s Ooimetiqae Inf&illiUe h s&id to bar a for its buis nitmte of lei^d.
* "On the Composition of Commercial Samples of White Lead," by G.
WignmiiiidR, H. Hikriatid.— J nalffst, IS77, j*. 208.
W.
§ 777:\
LEAD.
619
One of ** All Ahmed^B TT^&flureB of the Doaeti,'^ vk., the antiseptic niAkgma^
is a pl&£tt«r mode up uf leaJ plaster 37 '5 |>or c«iit, frankmcen^ 25 |jer cetit| naiad
oil 25 per cent*j beeswast 12 "5 per cent.
Ii«wIa' Silver Or earn crmtfiitis white pr«cipitate and a salt of lead.
0<»tiiard*s Balsam is niade by trita rating acetate of lead with hot oil of
turpentine.
Thtsre are varioua oltitmfstita in iiiie tn^de up of lithnrget Some herbalists iu the
country (from caaes that have come under the writers' own knowledge) apply to
canccrouii ulciers^ etc., a liniment of linseed and other oommon oib mixed with
lithjirge and acetate of lead.
Acetate uf lead may aleio be found aa a cnnstitueut of various eye- waters.
(3) FreparatioaB of Lead used izr the Arta, etc. ;^
Ledoyen'fl Diimfeoiing Fluid has for its basi^ uitrate of lead.
In various hair-dyea tke following are all used: — Litharge^ lime, and starch ;
lime and carbomite of kad ; lime and acetate of lewd ; litharge, Hme, and
potaasic bicarbotiate. The diitection of le^ad in the hair thus treated is ex-
trvmely easy ; it may be dissolved out by dilute nitric acid.
Lead Figments. — Tiie principal pigments of lead are white, yellow, and red.
White Hgmenti :—
White Lead, Flake White Ceruse, Mineral WMt«, are ho many dilferent iiamea
for the carbonate of lead alre^^ly described,
Ntwcastle White is white lead made with molassea vinegar.
Nottingham White,— White lead made with alegar (sour ale )^ often, however,
replaced by jiermanent white, *',*, sulphate of baryta.
Miiuature Faintera' White, White Frecipitate of Lead, \% simply lead
anl|)bate,
FattlBon's White is an wychloride of lead, PbOl^PhO,
Teliow Figmetita :—
Ohrotne Ydllow may be a fairly pure chromate of lead, or It may be mixed with
sulphates of lead, barium, and calcium. The pigment known aa '^ Cologne yellow '^
consists of ^5 i^artd of lead ehrnmate, 15 of lead sulpliate^ and 60 of calcic bulpliate.
The easiest method of aualyeing chrome yellow is to extract with Wiling hydro-
chlnrio iMnd in the presence of a Ice hot, which dissolves the chromium ae cbloridu,
and leavets uudissnlved chloride of titad, sulphate of lead, and other substances in-
soluble in CIH. Every grain of chromate of lead should yield 0'24 gram of oxide of
chromium, and 0 4 grain of chloride of leaiL
Turner's Yellow, OasseUa YeUow, Faient Yellow, ia ati ojcy chloride of lead
(?bCir^7Pb03 extremely fusible,
Dttt<3h Ftnk sometimes contains white lead*
Bed Pigments : —
Chrome Bed Ib a bichromate of lead,
Eed Lead or Minium is tbe red oxide of lesd.
Orange Bed is an oxide prepared by calcining the carbonate.
The chief preparations of lead which may be met with in the arts, in addition to
the oxidea and the mrbonate, are —
The Nitrate of Lead, muL-h used in calico- printings
The Fyroiignite of Lesd^ which is an impure acetate used iu dyeing ', and
The Sulphate of Lead is a by-product in the preparation of acetate of aluminium
for dyeing,
Tbe alloys eontainiug lead are extremely numerous ; but, according to the ex-
periments of Enapp/ the amall quantitj of lead in thoM uaed for houaehold purposes
has no hygienie importance.
Um^, F^!}f(^ch. jQitm.^ vd. ecii. pp. 4l6-i53.
620
POrsOHS: THEIR IFFUCTS ANti DITKGTION, [§ 778, 779.
§ 778. Statietics of Lead-PoiBOning.— During the ten years ending
December 1 ^03, 926 persons died from the effecU of lead ; 754 males
and 165 females were registered as having died fronn accidental lead-
poisoning — 6 males and 1 female used lead salts as a means of snicide
^but no case of murder was recorded*
§ 779. Lead as a Poison. ^All the eomt^onnds of lead are uaid to be
poisonous ; but this statement cannot be regarded as entirely correct,
for the Bulpbocyanide has been proved by experiment not to be so,*
and the sulphide is also probably inactive. In the treatment of cases
of lead poisoning, the ilowera of snip bur given in tern ally appear to be
successful t
Lead *po ISO nlng^ either in its obscure form {producing uric itcid in
the blood, and, as a conseqaence^ indigestion and other evils), or in the
acute form (as lead colic and variona nervona afiTections), h most frequent
among those who are habitually exposed to the influence of the metal in
its different preparations, viz., wnrkers of lead, house-paii iters, artist*;,
gliders^ workurs of arsenic, svorkers of gold, calico-priuters. colourists,
type - founderd, type - setters, shot - fonnders, potters, faience makers,
braisiers, and many others. i lu white-lead factories so large a number
of the employees suffer from poisoning that it has excited more than
once the attention of the Govemttient§
* EuIenWg^ Gewcrbe iiyijkm, y. 712. t Mobr's Tojicolo^,y, 78p
Z The litteutiou whish the iiae of leofl iu the urts hiis always e^ocilad Is e^idetit
fpfjm the fact that oti^ of the oldest works on Tmde Hjgiene {by StQckhauBen) ia
entitled, Bs lithanjyrii funi^ im^iu morbijuio tptsqv^ mfitaliic& /rtqumtiiori ffiorbo
vulgodkia hUttttikatu^ G&sUr, 1556.
§ A depiLi'tmiitttAl c^miniittee, appointed to mquire into the white lead afid
ullted industries, in u report presented to the Home Secretary stated ;--
*^ 8. («) It ia knewn tlmt if lead (in any fonn)j oven in ivhat tody b*? calU'd
int^nft^tmal quantities, gains entraac^^ into the Bystf<m for » lengthened ].»enQd4 by
such channels aa the stomach, by swallowing lead duat in the salivi^, or through the
medium of fowl and drink ; by the respiratory orgaiiH^ as by the inhnlatiny of dust ;
ui through the Sjkin ; there is developed a aeries of wynifptoms, the most frequent of
which ia colie. If early all the individuala engaged in factoriea where lead or its
ooiiipounda are nisidiiulatcd loi>k pak, and it is this bloodkaeness and the preitencG
of a blue line along the margin of the ^mB^ close to the teeth^ that herald the other
symptoms of plumbism. {h) A form of paralysis known aa wristdrop or lead -palsy
ocoasionally affects tho hands of the operatives. There is^ ill addition, a form of
acute lead-poisoning, most frequently met with in young girls from IS to 24 yeara of
age, which is suddenly develoj^ed and is extremely fatal. In it the i^rst complaint is
headache J followed Mooner or later by convulsions and nnconsoiouauesa. Death often
terminates such a case within three days. In aome cases of recovery fVoni oonvuldoiia
total bliuduess riimaina,
*'9, Therfl has been conaid^rahle doubt as lo the channels by wbioli the poison
enters the system. The coiumittee have taken much evidence on this aubjeot, and
have arrived at the coDclujaioD (a) that curbunate of lead may be absorbed through the
poR^s of the skiUp and that the chance of this is much increased during peraplratton
and whero there jb any friction bstweeu the skin and the clothing ; {b) that minitte
|7;9.]
LEAD.
62 1
Lead, again ^ has been found by the analyst in most of the ordinary
foods I such as flour, bread, beer, cider, winea, b pints, tea, vinegur, sugar,
coDFectionery, etc., as well as in numerous drugs, especially those manu-
factured by the aid of sulphuric acid (the latter nearly always containing
lead), and those salts or chemical products which (like citric and tartaric
acids) are cryatalHsed in leaden pans. Hence it follows that in almost
everything eaten or drunk the analyst, as a matter of routincj tests for
lead. The channels through which it may enter into the system are,
however, so perfectly familiar to practical chemists, that a few unmual
instances of lead -poisoning only need he quoted here.
A cabman suffered from lead colic, traced to his taking the 6rst glass
of beer every morning at a certain public-house ; the beer standing in the
pipes all night, as proved by analysts^ was strongly impregnated with
lead,*
The employment of red lead for repairing the joints of steam-pipes
has before now caused poisonous symptoms from volatilisation of lead.f
The use of old painted wood in a baker's oven, and subsequent adherence
of the oxide of lead to the outside of the loaves, has caused the illness
of sixty-sir people. J
Seven persons became affected with lead-poisoning through horse-hair
coloured with lead.J^
The manufacture of American overland cloth creates a whitehead dimt,
which has caused serious symptoms among the workmen {Dr. G?, Johnmm),
The cleaning of pewter pots,|| the handling of vulcanised rubber, If the
wrapping up of various fomls in tinfoil,** and the fingering of lead
counters covered with brine by Bshmongera, have all caused accidents in
men.
The lead in glass, though in the form of an insoluble silicate, is said
to have been dissolved by vinegar and other acid fluids to a dangerous
extent. This, however, is hardly well established. tt
The various glazes used in the pottery manufacture are largely com-
posed of lead compounds^ — litharge, white and red leads being used ;
some of the glaaies are fused with siliceous materials (fritted), but few
portions of le»d %ft Gftrrl^d by the haada, uad«r ftnd round th« anilj, etc., on to tlje
foodf and so into thfi stoiumch ; (r) but th^t the mxmt uaual mattner i» by th« In hala-
tion of lead dust. Some of thia becomes dissolved in the alkaline a^cretioiiK ofthe
mouth, and is swallowed by the saHva, thus finding its wny to thp atoniach* Other
partieles of dmit are oarried to the lungs^ where thej are reodored soluble and absorbed
hy the blood,**— i8ejiw< of Chisf Insjieeior 0/ Fadoruit for 1S&3.
• Chmn. Hiv^i^ f Eulenbefg, op. ct%^ p, 708.
t jinnaUfi (VtlyrfUi^^ 1877, SOT* § Hitzig, Studien Uher Blciiicrgijliing,
\[ Med. Gu^iU, ilviij. 1047* ^1 Ph^trm. Joitrn., 1870, p. 436,
•* Tmylor, FriiK Med, JurUpnui.t L
+t Bm AtrtU. lHi4:fitgmzht, /. Bakm^ Jahrg.p 18«S&; Buehn^r's Rtp, Phann.^
Bd. xix, {K 1 ; Mtd, CffHirhl,, Jahrg., 1S69, p. iO.
622
POISONS: THEIR BPFKCTS AKD DETECTION.
[§ 780.
of thes^ silicatea are abaolutely insoluble in aoids ; hence acid vegetable
juices, especially if heated, are liable to dissolTe out the lead from a
lead-glazed earthenware vessel. Dr. Campbell (Lancelf 188G) has re-
corded a series of cases of poisoning from home-made wioe fermented in
lead -glazed earthenware pans. Thorpe * haa investigated the composi-
tion of most of the lead silicates used as glaxes^ and has sho^n that the
primary factor governing solubility or otherwise in complex lead silicate
is the relation between the basic oxides and the acidic oxides. The
percentage weight of each oxide is divided by its molecular weight ; the
quotient represent the relative number of that oxide present in a
definite weight of the silicate — adding all the quotients for the acidic
oxides gives the total number of acidic molecules, and similarly for
No. of acidic molecules
the basic molecules the ratio =
So long as this
14^0. of basic molecules
ratio is higher than or approximately equal to 2, the solubility of the
lead Thorpe found to be small, being for the most part below 2 per
cent. ; but when the ratio falls below 2, the quantity of lead dissolved
(in hydrochloric acid) begins rapidly to increase.
g 780. EflFecta of Lead Compounds on Animals. — ^Oriila and the
older school of toxicologists made a number of experiments on the action
of sugar of lead and other compounds, but they are of little value for
el acid a ting the physiological or toxic action of lead, because they were, for
the most part, made under un natural conditiona, the gullet being ligatured
to avoid expulsion of the salt by vomiting, Haniack, in order to avoid
the local and corrosive ejects of sugar of lead, used an organic compound,
viz., plumbic trie thy 1 acetate, which has no local action. Frogs exhibited
symptoms after subcutaneous doses of from 3 to 3 mgrma., rabbits after
40 mgrms. ; there was increased peristaltic action of the intestines, with
spasmodic contraction risiug to colic, very often diarrhoea, and death
followed through heart paralysis. Dogs given the ethyl compound
exhibited nervous symptoms like chorea, Gussemof haa also made
experiments on animals as to the effects of lead, using lead phosphate,
and giving from 1 '3 grm. to a rabbit and a dog daily. Rosenstein t and
Keubel^ used somll doses of acetate, the latter giving dogs daily from *2
to "5 grm. The results arrived at by Gusserno were, mainly, that the
animals became emaciated, shivered, and had some piiralysis of the hinder
extremities ; while Rosenstein observed towards the end epileptiform con-
vulsions, anvl Heubel alone saw, in a few of his cases, colic. A consider*
able number of cattle have been poisoned from time to time with lead, and
• Joum. Ckem. Soe., ?>««*., 190L
t Yirichow*a AreMvf. imth. Anai. , voL iii, p. 44S»
X l^id- , vol. itixiz. pp, 1 and 74,
I Palhogmtse u. Sym^im dcr chronischm SUv^itgiftnny^ Berlin, IfiTl.
§ 78i0
LIAB.
623
one instanoa of this fell under the eeuior aiithor^e obfiervation. A pasture
had been manured with refuse frons a pUimber^s yard, and pieces of paint
were in this way strewn about the field in every direction ; a herd of
fifteen young cattle were placed in the fields and in two or three days
they allj without exception, began rapidly to lose condition, and to show
peculiar symptoms — diarrhoea, loss of appetite ; in two, blindness, the
retina presenting an appearance not unlike that seen in Bright's disease ;
in three, a sort of delirium. Four died, and showed on post>mortem
examination granular conditions of the kidneys, which was the most
striking change observable. In the fatal cases, paralysis of the hind
extremities, coma, and convulsions preceded death. In another case^
seven cows and a bull died from eating lead paint ; the symptoms were
loss of appetite, obstinate constipation, suspension of rumination, dry
mnffle, quick breathing, and coma. In other cases a marked symptom
has been paralysis. Cattle t have also several! times beeu poisoned from
eating grass which has been splashed by the spray from bullets, as in
pastures in the vicinity of rifle butts ; here we must allow that the
intestinal juices have dissolved the metal, and transformed it into
compounds capable of being taken into the system,
§ 7Sl. Effects of Lead Oompoiinds on Man —Acute Poisoning. —
Acute poisoning by preparations of lead is not common, and, when it
does occur, is seldom fatal. With regard to the common acetate, it
would seem that a large single dose is less likely to destroy life than
smaller quantities given iu divided doses for a considerable perio<:1. The
symptom a produced by a considerable dose of sugar of lead usually
commence within a few minutes ; tliere is immediately a metallic
taste, with burning, and a sensation of great dryness in the mouth
and throat ; vomiting, which occurs usually within Jirteen minutes, is
in very rare cases delayed from one to two hours. The retching and
vomiting are verj obstinate, and continue for a loug time ; the matters
thrown up are sometimes streaked with blood ; there is pain in the
ablomen of a colicky eharaoter — a pain relieved by preasnre* The
bowels are, as a rule, constipated, but occiisionally relaxed. The stools
at a later date are black from the presence of lead sulphide* The
urine^ as a rule, is diminished. The breath hiis a foul odour, and the
tongue is coated; the skin is dt7, and the pulse small and frequent
The full development of the toxic action is completed by the appcanmce
of various nervous phenomena — headache, shouting pains in the limbs,
cramps in the legs, and local numbness. All the symptoms enumerated
are not present iu each case ; the most constant are the vomiting and
the colic If the sufferer is to die, death ooours about the second or
* Sm a paper by Profeesor Tumq, Fftcrtnof^an, vd. JCXxviiL^ IMl,
+ IHd^ i also Taylor, op* eiL
624
POISOKS: THEIR EFFECTS AND DETICTIDN.
[§78l'
third day. If the patient fecovers, convalescence may be much
retarded, aa shown in the caae of two gii'le,^ who had each swallowed
an ounce of lead acetate by mistake, and who su0ered even after the
lapae of a year from pain aud tendeniesa in the stotnacli and sickness.
There are ** masa-poiaonings " by acetate of lead on record, which
afford considerable insight into the varying action of this salt on
difTerent individuals, A case (e.g.) occurred at Stourbridge in 18405t
in which no less tVian 500 people were ixiisoned by thirty pounds of
lead acetate being accidentally mixed with eighty aacks of flour at a
mUler's. The symptoms commenced after a few days — conatrictiou of
the throaty cramping and twisting pains round the umbilicus, rigidity
of the abdominal muscles, dragging paina at the loins, cramps and
paralysis of the lower extremities. There was obstinate constipation ;
the urine was scanty and of a deep red colour, aud the secretions
were generally arrested ; the pulse was slow and feeble ; the countenance
depressed, often livid ; and the gums showed the usual blue line. The
temperature of the skin was low. In only a few cases was there
sickness, and in these it soon ceased- It is curious that not one of
the 600 cases proved fatal, although some of the victims were extremely
ill, and their condition alarming. It was specially observed that^ after
apparent convalescence, the symptoms, without any obvious cause,
suddenly returned, and this even in a more aggravated form. Remit-
tance of this kind is of medico-legal import ; it might, for example be
wrongly inferred that a fresh dose had been taken. In the 500 cases
there were no Inflammatory symptoms; complete recovery took some
time. On examining the bread, the poison was found so unequally
distributed that no idea could be formed as to the iictual amount taken.
There is also recorded I an outbreak of lead-poifioning among 150
men of the 7th Infantry at Tione, in the Southern TyroL One case
proved fatal, forty-five required treatment in hospital. The syaiptoms
were pallor, a blue line in the gtims, metallic taste in the mouth, a
peculiar odour of the breath, a loaded tongue with a bluish tint*
obstinate constipation with loss of appetite ; whilst all complained, in
addition, of dragging of the limbs and of the musclea of the chest, and
difficulty of breathing. In the severer caaes there were tetanic spasma,
musenlar tremors, and antiE^thesia of the fingers and toes. The pulse
and temperature were normal, save in a few cases in which there were
fever and sweats at night, hi none wag there eolie, but the constipation
was obstioate. In two of the worst cases there was strangury. Acute
cases occur occasionally from poisoning by the earbonaie of lead. Dr.
* JVof, Med. Joumnlt 1846,
t Recorded bj Mn Buicka, Lancet^ May 5, IS 49, p. 47&
t KuDigaclimiedi OMirathL AUg./Ur Gmundheiigpfie^t^ 2 Jabrg., Heft 1,
§ 7^20
LS^D.
625
Snow recorded an instance (in 1844) of a child who had aaten a piece
as big as a marble, ground up with oiL For three days the child
suffered from pain in the abdomen and vomitings and died ninety hours
after taking the poison. In another case, in which a young man took
from 19 to 20 grnis. of lead carbonate in mistake for chalk aa a remedy
for heartburn^ the symptoms of vomiting, pain in the stomach, etc.,
oomnienced after a few houra; but, under treatment with magnesic
sulphate, he recovered.
The Cbromate of Lead is still more poisonous (see art. " Chromiiun").
§782. Chrome foisomng by Lead. - Chronic poisoning by le-ad—
often cauaed by strange and unsuspected channelsi more frequently an
incident, nay, almost a necessity, of certain trades, and occasionally
induced by a cunning criminal for the purpose of simulating natural
disease — is of great toxicological and hygienic importance. In the
white-lead trade it is, as might be expected, most frequently witnessed ;
but also in all occupations which involye the daily use of lead in
almost any shape. The chief signs of chronic poisoning are those of
general ill health ; the digestion is disturbed, the appetite lessened, the
bowels obstinately con^ned, the skin assumes a peculiar yellowish hue,
and sometimes the suiferer is jaundiced. The gums show a black streak
from two to three lines in breadth, which microscopical examination
and chemical tests alike show to be composed oF sulphide of lead ;
occasionally the teeth turn black.^ The pulse Is slow, and all secretions
are diminished. Pregnant women have a tendency to abort. There
are also special symptoms, one of the most prominent of which is
often lead colic.
In 142 cases of lead -poisoning, treated between 1852 and 1862 at
the Jacob's Hospital, Leipzig^ forty- four patients (or about 31 per cent,)
suftered from colic. Arthralgia — that is, pains in the joints — is also
very common ; it seldom occurs alone, but in combination with other
symptoms. Thus, in seventy-five cases of lead -arthralgia treated at
Jacob's Hospital, in only seven were pain in the joints without other
(M>mpli<^tions^ fifty -six being accompanied by colic, five by paralysis,
and Bflven by other affections of the nervous system. The total
percentage of cases of lead -poisonings In which arthralgia occurs, varies
from 32 to 57 per cent.
Paralysis, in mme form or other, Tanqueril t found in 5 to 8 per cent
of the cases, and noticed that it occurred as earlj as the third day after
* The black line soou develops ; If aisatxa bos seen it in a dog, exposed to ihe
inEuenc« of 1«»d, la so short ■ period as thrc« days (B^tfrma mid,^ 1889, Nob. 248-
257, 1),
t Tanqueril dea Planohos, Tr^US dtjt Maltnti&t de Fltmth, Paris, 1S59.
Tsnqneril^s xnonogmpli m & clfrsaic&l work full of in formation «
626
POISONS: THKIR EFFECTS ANI> DETKCTION.
[§ 783.
workiBg in lead. The muBcles affected are usually those of the upper
extremitj, then the legs, and still more mreljr the mui^ulea of the trunk.
It ia onlj exceptioQaUj that the paralysis extends over uii entire limb ;
it more usually affects a muscular group, or even a single muscle. Its
common seat is the extenaora of the hand and fingers ; hence the eipres-
sion ** dropped- wrist," for the hands droop, and occasionally the triceps
and the deltoid are afteeted. The paralysis is usually syui me tribal on
lK>th sides. Although the exteu&orB are affected most^ the flexors nearly
always participate, and a careful investigation will show that they are
weakened. If the paralysis continues, there is a wasting and degenera-
tion of the muscle ; but this is seen in paralysis from any cause. The
muscular affection may cause deformities in the hands, shoulders, etc*
AniBstheaja of portions of the skin is generally present in a greater or
less degree, A complete analgesia affecting the whole body has beeo
noticed to Eiuch an extent that thei'e was absolute insensibility to burna
or punctures ; but it is uauaUy confined to the right half of the body,
and is especially intense in the right band and wrist.
% 783. The older writers recognised the toxic effect of lead on the
nervous system. Thus Dioacorides speaks of delirium produced by lead,
Aretaeus of epilepsy, and Paul of ^Egina refers to it as a factor of
epilepsy and convulsions. But in 1830^ Tanqueril first definitely de-
scribed the production of a mental disease, which he called ** lead
encephalopathy.^^ This he divided into four forms — (1) a delirious
form ; (2) a comatose ; (3) a convulsive; and (4) a combined form, com*
prining the delirious, convulsive, and comatose. Dr. Henry K'ayner,*
and a few other Knglish alienists, have directed! their attention to this
quegtton ; and, according to Dr, Rayner's researclies, the number of male
patients admitted into Hanwell Asylum, engaged in trades such as
plumbing, painting, and the like, is larger in proportion to the number
admitted from other trades than it should be, compared with the projior-
tion of the various trades in the cotmty of Middlesex, as ascertained
from the census. Putting aside coarae lead- poisoning which may ooca-*
sionally produce acute mania, the insanity produced by prolonged minute
lead intoxications possesses some pecuHiir features. It develops slowlj,
and in nearly all cases there are illusions of the senses, of hearing, taste,
or smell, und especially of sight* Thus, in one of Dr, Hay ner*a caaes
the patient saw round him " wind*bags blo^ii out to look like men,"
apparitions which made remarks to him and generally worried him.
Besides this form, there is also another which closely resembles general
paralysis, and, in the absence of the history^ might be mistaken for it,
* Set! ail important paper, '* Insaoity from Leacl-PoisaDing," by Drs, H, R&yiier,
Rob©rts<iB^ Savage, and Atkma, Joitni, ^f Mental Sd^ncs^ vol. xivi. p. 222; also a
im]iev by Dr. BartoD, AUgemeins Z^itschrift fiir FsydiialrU, Bd, xx^vij, H» 4, p« 9,
§ TU]
LlilD.
^^^" 627
§ 784, The degenerative influence on the organ of sight is shown in
aix of Dr. Eoberttion s patieuts, whose insauity wa^ ascribed to lead —
four of the six were either totally or partially blind,
The amaurosis has beeu known to come on anddenly, and after a
very brief exposure to lead^-e.^* a man, thirty-four years of age, after
working for three days in a white-lead factory, was seized with intense
ciliary neuralgia, had pains in his limbs and symptoms of lead-poisoning,
and the right eye became aoiaurotic.'^ This form of impairment or loss
of vision isdii^erent from the Retijnfu alhummuricaif which may also be
produced as a secondary effect of the poison ; the kidneys in such o&ses
being profoundly atlected. The kind of diseased kidtiey produced by
lead is tbe granular contracted kidney.
Eulenberg speaks of the sexual functions being weakened, leading
to more or leas impotence,
Lewy,J in 1186 patients suffering from lead- poisoning, has found
caries or necrosis in tweuty4wo Ciiees, or about 1 '8 per cent* ; hfteen
were carious affections of the upper jaw, four of the fore-arm, two of tbe
thigli, and one of the rib and sternum. Epilepsy and epileptiform con-
vulsions occur in a few cases ; it is very possible that the epilepsy may
be a result of the urtemio poisoning induced by diseased kidneys*
Five eases of fatal poisoniiig ocoiirred between 1884-6 among the
employees of a certain white*load factory in the east of London. The
cases presented the following commou characters. They were all adult
waoienj aged from 18 to 33, and they had worked at the factory for
short periods^ from three to twelve months, Tliey all exhibited mild
symptoms of plumbism, such as a blue line round the gums, and more or
less ill-defined indisposition ; psfa) ysea were absent. They were all in
their usual state of health within a few hours or days preceding death.
Death was unexpected, mostly sudden. In four cases it was preceded
by epileptic hts and coma; but in the fifth case uo couvulsioiis were
noted, although they may have occurred in the night.
The senior atithor§ had an opportunity of investigating by chemical
means the distribution of learl in the fourth and tifth cases in the liver,
kidney, and brain.
In the fourth case, from 403 grms, of liver 24*26 mgrms, of lead
sulphate were separated. Tbe right kidney {weighing 81 grms.) yicldetl
5*42 mgrms. of lead sulphate. The brain was dehydrated with alcohol,
• SmnelBolin, Monmi^hL J\ Aiu*niheifl% vol xi. j», 246, ISTS. See tiA^ « cas<i f*f
lead nmaura^ii, dpacril>eri by Mr* W. Holder, P/mrm. J&atiKi €H?t. H, 1976.
t Ran, Arch. / Ophi/iaL^ vol i (2)t p* 206, ISSS, mud SchmitUs Jahr hitch,
Bet cxxxiii. (I. 116 \ Bd. cxliii. p. 57.
t BU BiTufjikrank fl. Bki(trtmlrrt Wieii, 1873, 8. 10.
§ ** Tbe DislribnIioL td" Leu*! in the Brii^iria of two L^d Fiwtory Oporfttiv«i/*
628 POISONS : THSIB KFFBCT8 AND DBTECTION. [§ 785.
and then treated with ether, hot alcohol, and chloroform until an
albuminoid residue renudned; lead was extracted from each of these
portions, viz., the alcohol used for dehydration, the ethereal and chloro-
form extracts, and the albuminoid residue, as follows : —
. of
Sulphate.
Soluble in cold alcohol, 1*11
Soluble in ether and chlorofonn and hot alcohol, . 25*47
Albominoid reddue, 776
84*84
In the fifth case, the brain was examined more in detail, and the lead
present estimated in the following solutions and substances : —
1. Alcohol used for dehydration. This may be called " the watery
extract," for, after the brain has remained in strong alcohol for some
weeks, the result is that the alcohol contains much water and substances
extracted with water.
2. White matter — (a) from cerebrum ; (b) from cerebellum.
3. Kephalin — (a) from cerebrum ; (b) from cerebellum.
4. Ether extract, kephalin-free— (a) from cerebrum ; (b) from cere-
bellum.
5. Substances soluble in cold alcohol — (a) from cerebrum ; (b) from
cerebellum.
6. The albuminoid residue^ — (a) from cerebrum ; (b) from cerebellum.
The general results were as follows : —
Cerebnim, CerebeUnm,
400*8 gnns. 1M*2 grmt.
Mgrmi. of PbS04. Mgrnu. of PbS04 .
White matter fireed from kephalin by ether, . .0*0 6*0
Kephalin 1*5 6'0
Ether extract, kephalin-free, .... 0*0 0*0
Substances solnble in cold alcohol, . . . O'O 0*0
Albuminoid residue, 40*0 6*0
41*6 17*0
The aqueous extract contained 1 *5 mgrm. of lead sulphate. In neither
of the cases did the pathologist ascertain the total weight of the brain,
but, presuming that the weight was an average weight, and that the lead
in the remainder of the brain was similarly distributed, the amount of
lead calculated as sulphate would amount to 117 mgrms. From these
results it appears to the authors probable that lead forms a substitution
compound with some of the organic brain matters. This view would
explain the absence of changes apparent to the eye found in so many of
the fatal cases of lead encephalopathy.
§ 786. Lead taken for a long time causes the blood to be impregnated
with uric acid. In 136 cases of undoubted gout, 18 per cent, of the
§ 7^6. ;86a.]
LEAD.
629
patteQts were found to follow lead occupational aud prcBented signs of
load impregniition.*
Elleuberger aud Hofmeister t found that, with chronic poisoning of
sheep with lead, excretion of hippurio acid ceased, and the output of
uric acid was diminiBhed. This may be explained by the formation of
glyeocol being arrested.
§ 7S6, There are some facts on record whtch would seem to counten^
ance the belief that disease, primanlj caused by an inorganic body like
lead, may be transmitted. M. Paul (ft^.) has related the history of the
offspring (thirty-two in number) of aeyen men^ who were suffering from
lead' poisoning — eleven were prematurely born and one still-bom ; of the
remaining twenty, eight died in the first year, four in the second, and
five in the third year, so that of the whole thirty-two only three survived
three years*
The influence of the poison on pregnant women isj indeed, very
deleterious. M. Paul noted that in four women who M^ere habitually
ei posed to the infiuence of lead, and had fifteen pregnancies, ten termi^
nated by abortion, two by premature confinement, three went the full
term — but one of the three children was born dead, a second only lived
twenty-four hours ; so that, out of the whole fifteen, one only lived fully.
In another observation of M. Paul, five women had two natural confine^
ments before being exposed to lead. After exposure, the history of the
thirty six pregaaucies of these w^omen is as follows : — there were twenty-
six abortions (from two to five months), one premature confinement, two
infantB born dead, and five bom alive, four of whom died in the first year*
Chronic poisoning may be nearly always accounted for by the inhaling
of lead dust, or by the actual swallowing of some form of lead ; but, if we
arc to acoept the fact narrated by the late Dr. Taylor, viz., that he him-
self had an attack of lead colic from sitting in a room for a few hours
daily in which there was a large canvas covei^ with white lead and
drying oil, and one or two other similar cases, J we must allow that there
is some subtle volatile organic compound of lead evolved. In the present
state of our knowledge, it seems more reasonable to account for such cases
by the suggestion that lead has entered the 8yatem by an unsuspected
channel
i^ 78$A, Lead in Drinldng Water. — Attention of recent years has
been directed to the contamination of certain moorland waters by lead,
* "On Lead ImiirefftiAtion in BeUtion to Gout," bj Dycfi Duekwortb, M.D., SL
Barth^ Mo^p. Repitrts^ vol. ivii, 18S1,
t Ardi^f. tciss, u, pra^. ThUriuilL, Bd, x., 1S84»
Z The gat€*keopQr of a gmvey&rd at Bordeaux continuftlly used the remimnts of
aroiiseJi, oovered with lead palut^ to replenish hh fir^ ; the chimtiey smok«d ; gnuiu*
ally pftralyidfi of the eitensora of the right wriat developed itself, and he suffered from
colio and other si^iu of le*d-poisoiun|{. — M&nniaAe, Qaz^ dM H6pU*i No. 25, IdSti,
630
POISONS: THKIB EFFECTS AND DETECTION. [| 786A.
and elaborate investigations have been made by the niedieal depart-
ment of the Local Government Board, the results of which are most
important and interesting**
Dr. Houston, in his extended experinisnts, found that ^'action on lead '*
by water could be conveniently divided into "erosive ability" and
** plumbo-solveut ability " ; neutral distilled water, pure rain water, and
pure snow water all erode lead, but possess little power of dissolving
leid. In ertiaioo the metal is detached in scales; it is a process
analogous to the rusting of iron — the product of the reaction is insoluble
in neutral liquids, and is only slightly dangerous to public health.
The plumbO'Solvent waters are mostly moorland wat^^ acid in
reaction, the plumbo-solvent power as a rule being in direct relation to
the degree of acidity as deteriuiued by titration, using lacmoid as an
indicator. Aceordtng to Houston, the acidity is produced in peat by
special forms of bacteria; in a few cases of pi urn bo-sol vent waters,
the water has been fouitd to be contaminated by a mineral acid
(sulphuric) derived from the oxidation of pyritea, over which the water
flowed or through which it percolated »
In 1882, a very interesting case ocourred at Xeighley, in which a
mechanic, aged 42, died from the supposed effects of lead-poisoning,
induced from driuking the town water, which was proved by Mr, Alien
to contain about f of a grain of lead per gallon. For six mouths be had
been out of health, and a week before his death he aufiered from colic,
vomiting, constipation, and a blue line round the gums, aud occasional
epileptiform seizures. After death the kidneys were found grauular,
and the heart somewhat enlarged. The viscera vrere submitted to
Mr- Allen for analysis; no lead was found in the heart or brain, a
slight, non-estimable trace in the kidneys, and about a grain was
separated from the liver aud spleen. Dr, Tidy, who was called in as
an expert, gave a very ^ guarded opiuiou rather against the theory of
direct lead- (xi boning ; and the verdict returned by the jury was to the
effect that the deceased died from granular kidney, accelerated by lead-
poisoning.
The usual test iu the absence of iron for lead in drinking wateni
is to add to 50 c.c, iu a Nessler cyliuder, ammonium sulphide;
a black colour or precipitate uot discharged or dissolved by hydro-
chloric acid or by potassic cyanide, i^ an indication of the presence
of load.
The lead may be estimated colorimetrically by imitating the dark
* "Oa thH Cauatis of Lcmi- Poison iJig,*' hj Mr* W. H, Powor^ F,E.13,, Tiemtth
third Anmial [import of (he Lof\ Govt. Bd., 1893-94 (aujuJeiucnt). R^iKjrt by Div
Houston on *' Moorland Watera in regaiNi of their Action on Lcad,'^ TMHiei/i Jnnuai
JUpori o/ihe Loe. Otfti, Bd,^ 1900-1 (■u^plement).
§786b]
LB AD.
e>^i
colour produced in a known solution of lead acetate bj ammouium
sulpbide. lo important rosearubes it may be advisable to estioiate the
lead by weight ; in this case a sufficient amount of the water is con-
cent i:m ted down, ammonium sulphide added, and the precipitate of
lead sulphide collected and washed ; after standing many hours, the
sulphide is cither weighed as sulphide, or treated by the electrolytic
process to be described.
Bemtrop* Bnds lead phoAphate absolutely insoluble in water con*
taining free sodic phosphate. He therefore examines waters by adding,
If necessary, calcium chloride and excess of sodium phosphate. The
precipitate which forms during twenty-four hours ts said to contain all
the lead as phosphate ; it is colleoted and dissolved in dilute nitric acid,
and identified by the usual teats.
g 786a The PlumBtead Murder Case, — Murder by the administra-
tion of doses of sugar of lead is rare, but such a case has occurred. At
the Central Criminal Court, in December ISSii, Louisa Jane Taylor
was indicted for poisoning Mary Ann TregiUis at Fhinistead, and con-
victed From the evidence it appeared that the prisoner, who was
thirty-six years of age, came to reaide with Mr. and Mrs. Tregillis, an
aged couple of eighty five and eighty-one years respectively. The
prisoner was proved to have purchased at different tiroes an ounce and
half an ounce of sugar of lead^ and to have added a white powder to the
medicine of Mrs. Tregillin. The illDesB of the latter extended from
about August 23 to October 23^a period of two months. It is difficult
to say when the first dose could have been given, but it was probably
some time between August 13 and 23, while the administration, without
doubt, ceased on or before October 6, for on that date different nursing
arrangements were made. The symptoms observed were nausea, vomit-
ing, pain in the pit of the stomachy burning in the throat, very dark
teeth, a blue iiue round the gums, and slight jaundice. There was
great muscular weakness, with trembling of the hands, and a week
before death there was paralysis of the right side.
Load was discovered in most of the viscera, which were in great
part normal ; but the kidneys were wasted, and the mucous membrane
blackened, The actual quantity of lead recovered by analysis was small,
viz., 16 "2 nigrms. (J grain) from the liver; from B ounces of brain,
3 3 mgrms. (^ grain) ; from half of the stomach, IS 2 mgrms. (J grain) ;
and from the spleen, the kidneys^ and the lungs, small quantities. It is^
therefore, probable that, if the whole body had been oj^erHted upjon, the
yield would have been more than ''15 grm. (a little over S grains) ; but
then, it must be remembered that the dece&sed lived, at least, seventeen
days after the last dose.
- Ckm, MtiL, IIM, 1020.
632
POl803*S: TtlKIR EFFECTS AKD DETECTION, [| 787, 788,
§ 781, PoBt-mortem Appearancefi.— lu acute cases of poisonitig bj
tbe acetate, there riiay sometimes be fout^d a slight inflammatory appeal^
ance of the mucoufl membrane of the stomach and intestines* Orfila
considered that streaks of white points adherent to the mucous membtane
were pathognomonic ; bat there have lieen several cases in which ouly
negative or doubtful signs of inflammatory or other action have presented
themselves. A general contractioti of the intestines has often been
noticed, and is of considerable signiflcance when present; so also are
ilaty patches on the intestinal mucous membrane ; in the Plunistead
case Dr. Stevenson found such patches contained lead, hence they are
probably caused by the deposition of lead sulphide. Loen found in dogs
and guinea-pigs^ poisoned by lead, local inflamraation areas m the lungs,
liver, and kidneyH| but in no case fatty degeueration of the epithelial
ceils of the liver, kidneys, or intestines. As a rule, no unabsorbed
poison will be found in the stomach ; the case related by Christison, in
which a person died on the third day after taking at a single dose some
large quantity of acetate of lead — -and at the autopsy a fluid was
obtained from the stomach which had a sweet metallic taste, on
evaporation smelt of acetic acid^ and from which metallic lead was
obtained — is so very extraorditiary in every respect, that its entire
accuracy is to be questioued. In deatb from chronic letid-poisoning^
there is but little that can be called diagnostic ; a granular condition of
the kidneys, and all the pathological changes dependent 01] such a ecu-
dition, are most frequently seen. If the patient has suflered from colic,
a constrictiou of portions of the intestine, has been noticed ; also, in casets
in which there has been long-standing paralysis of groups of muscles,
these muscles are wasted, and possibly degenerated. In instances, again,
in which lead has induced gout, the pathological changes dependent upon
gout will be prominent. The blue line around the gums, and sometimes
a coloration by sulphide of lead of portions of the intestines, may help a
proper interpretation of the appearances seen after death ; hut all who
have given any attention to the subject will agree that^ simply from
pathological evidence, It is impossible to diagnose chronic lead -poisoning.
§788. Physiological Action of Lead.— The action of lead is still
obscure, but it is considered to have an eflfect mainly on the nervous
centres. The paralysed muscles respond to the direct current, but not
to the induced^ leading to the suspicion that the intramuscular termina-
tions of the nerves arc paralysed, hut that the muscular substiince itself
is unattacked. On the other hand, the restriction of the action to groups
of muscles supports the theory of central action.
The lead colic is due to a true spasmodic constriction of the bowel, the
exciting cause of which lies in the walls of the bowel itself ; the relief
given by pressure is explained by the pressure causing an anemia of the
§ 789. 790-]
LKAD.
633
ititestiiml walla, and thus lessening their Beugibility. The slowing of the
pulse produced by small doses is expUlned as due to a stimulation of the
inhibitory nerves ; and, lastly, many uerYous phenomena, such as epi*
lepsy, eto., are in part due to imperfeet elimination of the urinary excreta^
causiEig similar coaditiona to those observed in uneniia.
§ 789. Eliminatiail of Lead— When a large dose of acetate or car-
bonate is taken, part is transformed into more or less insoluble compounds
— some organic, others inorganic ; so that a great portion is not absorbed
into the ttody at all, but passes into the intestines^ where, meeting with
hydric sulphide, part is changed into sulphide^ colouring the alvine evacu-
ations black. Some of the lead which is a barbed is excreted by the
kidneys, but the search often yields only traces. Thudichum* states
that in fourteen caaes of lead-poisoning, in two only was obtained a
weighable quantity from a day's urine ; in the remaining twelve lead was
detected^ but only by the brownish colour produced in an acid solution
of the ash by hydric sulphide.
The elimination of lead by the kidneys is favoured by certain medi-
cines, such, for example, as potassic iodide, Aunuschat found in dog«
poisoned by lead from 3 '8 to 4*1 mgrms, in 100 ex, of urine ; but, after
doses of potassio iodidcj the content of lead rose to 6-9 and even to H
mgims. Lead appears to be eliminated by the skin, being taken up by the
epithelial cells, and minute, insoluble particles coming away with these
cells. If a person who has t^iken small doses of lead for a time be placed
in a sulphur water-bath, or have hi» skin moistentjd with a 5 per cent,
solution of sodium sulphide, the upper layer of the epidermis l& coloured
dark; but the perspiration excited by pilocarpiu or other agency contains
no lead.
§ 790. Fatal Dose— (a) Sugar of Lead.— It may almost be said that
it is impossible to destroy human life with any single dose likely to be
taken or administered. In three cases an ounce {2B*3 grms.) has been
taken without fatal result. Although it must be allowed that repeated
modera.te doses, extending over some time, are more dangerous to health
and life than a single large dose, yet there seems to be in some indi-
viduals a great tolerance of lead, Christison has given '18 grm. in
divided doses daily for a long time without any bad effect, save the pro-
duction of a slight colic, Swieten has also given daily 3*9 grma, (60
gmins) in ten days without observing toxic effects. That, in other cuiei^
less than a grain per gallon of some lead com[>ouud dissolved in drinking-
water, or in some way introduced into the economy, causes serious ilhies4,
is most iuexplicablet
(h) The Basic Acetate iu solution is more poisonous apparently than
the aoetate^ — 60 ex. ( 1 1 drms. ) have caused serious symptoms.
634
POISONS: THEIR EFFECTS AND DETECTION, [§ 791,792.
(c) The Carbonate of Lead. — Doses of anything like 28 gmas. (iin
ounce) would probably t>e very dangerous to an adult ; the only case of
death on record is that of a child who took some unknown quantity
— probably, from the description of the size of the lump, about 10 grms.
(2 J dmis.)^
§ 791. AntidoteB and Treatment. — 8olnb(e sulphates (especially
magnesic sulptmte) have been given largely iu both acute and chronic
cases; in tbe acute, it stands to reason that it is well to ensure the
presence of plenty of sulphates in the stomach and intestines, in order
to form the sparingly soluble lead sulphate, should any residue remain,
bat to expect this double deconi position to go on in the blood and tissues
is not based upon sound observation. Tlie chronic lead- poisoning is best
treated by removal from the source of mischief, tbe ad ministration of
large quantities of distilled water, and medicinal doses of potassic iodide.
§ 792; LocaliBation of Lead.^In a dog, which wos killed by chronic
lead -poisoning, Heubel found in the bones O'lS to 0'27 per 1000 of
lead; in the kidneys, 0*17 to 0*20; liver, O'lO to 0'33; spinal cord,
0'06 to 0*11 ; brain, 004 to 005 ; muscles, 0*02 to 0'04 j in the intes-
tines, traces, O'Ol to 002 - in the spleen, the blood, and the bile he also
ouly found traces. Ellenberger and Hofmeister found iu tbe kidneys of
the sheep, 0*44 to 0*47 ; liver, 0*36 to 0-65 ; pancreas, 0*54 ; salivary
glands, 0^42; bile, 0*11 to 040 ; bones, 0^32 ; faeces, 0^22 ; spleen, 0*14 ;
central nervous system, 0'07 to 0*18; blood, 0'05 to 0*12; tiesh, 0^05
to 0"08 j urine, 0 06 to 0*08 ; and in tbe unstriped muBcles and the lunga^
0 03 per 1000 of lead.
Without going so far as to say that lead is a natural constituent of
the body, it is certain that it may be frequeutly met with in persons
who have been apparently perfectly healthy, and quite free from all
symptoms of lead-poisoning, Legrip found in tbe liver and spleen of a
healthy person, 5*4 mgrms. of lead oxide in every kilogramme ; Oidtmann,
in the liver of a man fifty -six years of age, 1 mgrm. of lead oxide per
kilogramme, and in the spleen 3 mgrms. per kilogramme. G. Meillere *
has also found tracer of lead in a majoriiy of subjects examined. Hence
the analyst, in searching for poison, must be very careful in his con*
elusions. Grave and serious errors may also arise from complications ;
suppose, e.^., tb^it a deceased person previous to death had partaken of
game, and inadvertently swallowed a shot^ — if the analyst had not care>
fully searched the contents of the stomach for ttolkl bodies, hut merely
treated them at once with acid solvents, he would naturally get very
decided lead reactions, and would possibly conclude, and give evidence
to the effect, that a poisonous soluble salt of load bad been administered
shortly before death.
* Ctympi, Ititui> Soc, iM., 1903.
I 793i 793^]
LKAa
6JS
§ 793. Detection and Estimation of Lead.— A grtjiit number of
fluids (such its hBQTy wines, vinegar, water, etc.), if they contain
anything like the amount of one- tenth of & milligramme in 100 ex,,
will give a very marked dark colour with SH^. It is, however, nftfest
to destroy all organic matter by evaporating to dryness and incinera-
tion at a very low red heat in a muffle; the incineration should be
lairly complete, for it has been shown that carbon retains lead with
considerable tenacity*
If (in the usual courae of routine research) a hytlrochloric acid
solution is obtained from the treatment or destruction of organic sub-
stancei by that agent, and lead sulphide (mixed possibly with other
sulphides) is filtered off, any arsenical sulphide may first be extracted
from the filter by ammonia, and any antimonioua sulphide by sodic
sulphide ; then the sulphide may be extracted by warm hydrochloric
acid, which will leave undissolved such sulphides as those of cop|>er and
mercury. On diluting the liquid, and tilteringat a boiling temperature,
crystals of lead chloride will l>e deposited on cooling*
In the case of sulphate of lead, which may be always produced in
an ash ^m organic substances by previous treatment with sufficient
sulphuric acid, a very excellent method of identificatiou is to convert it
into sugar of lead. To do this, it is merely necessary to boil it with
carbonate of ammonia, which chiiDges it into carbonate of lead ; treat-
ment with acetic acid will now give the acetate ; the solution may (if
the lead is in very small quantity) be concentrated in a watch-glass, a
drop evaporated to dryness on a circle of thin microscopic gUisSj and the
crystals examined by the microscope ; the same tilm uext exposed to the
fumes of HH.-^, which will bhicken it; and lastly, the solution (which
should be sweet) tasted* A crystalline subatance possessing a sweet
taste, and black eii in g when exposed to SH^, can, under the circum
stances, be no other substance than aeetate of lead.
Lead in solution can be converted into sulphide ; in this case it i^i
however, [ibaolntely necessary that there should he no great excess of
acid, since as little as 2*5 per cent, of free hydrochloric acid will pre-
vent all the lead going down, Ou obtaining the sulphide, the latter, as
already describefl, can be converted into chloride by hydrochloric acid,
and the crystalline chloride is extremely characteristic,
S 793a. Tetra-methyl-diamino-phenyl methane as a Test for Lead
Peroxide. -^Thc salt is the leuco-deri vative of malachite green, it may be
made by the reduction of malachite green and by various processes ; Imt
the most convenient method of preparation is to bojl 30 grma of dimethyl-
aniline with 25 c.c. of a 40 per cent solution of formaldehyde, the
solution being made up to 200 c,c. with water. The excess of dimethyl-
aniline is got rid of by blowing steam through. On cooling, the tetra-
636
POISONS : TH£IR EPFICTS AND DETECTION. [§ 793B, 794,
methyl compound cry stall ises out, and should be dissolved in hot alcohol
and recryBtallised from that solvent.
The test solution in made by diaaolviug 5 grms, of the crystals
in 100 c.c. of water, with the addition of 10 c.c. of acetic acid.
The solution is very sensitive to light and air. Paper dipped in the
solution and dried in the dark will readily "print" if exposed behind a
negative, the unshaded parts of the paper becoming green,
A fragment of lead biuoxide or manganese binoxide strikes with the
reagent a deep blue or blue-green colour — chlorhiej chroniic acid, and
oxidising substauees generally also reproduce, in more or leas purity,
malachite green (which, by the way, is not a true green, but a blue
green). Hence if utilia«d as a teat for lead binoxide or peroxide, the
test roust be used m such a way as to exclude |K^^sibility of confusion
with other oxidising substances* This is fairly easy when the test is
applied to the results of an electrolytic operation ; under such circum-
stances the test is of great delicacy, a just visible speck of lead binoxide,
or a just visible stain of the same substance deposited by the galvanic
current on a platinum wire, giving at once a blue colour.
§ 793b. Electrolytic Method of Separating Lead as Dioxide.— Lead
can be separated, estimated, and identified in the most minute quantity
by an electrolytic method under exact conditions of acidity, strength of
current, and temperature.
The lead should be converted into nitrate; the proportious of lead,
acid, and water in 100 ex. should be not more than 0^2 lead, 13—14 c.c.
nitric acid (14 specific gravity), and the solution made up to 100 with
water. The temperature should be from 60*-70', the current from
3*7-4*0 volts aud 11-13 ampt'res^ and it is best to use a rotating
cathode ; *" under these conditions the lead is thrown down mainly
as dioxide within twenty minutes. The him is washed with water
without interrupting the current, and then with alcohol and ether.
The pole with deposit should be dried for half an hour at a tempera-
ture of 2OO'-230', and then weighed. It is usual to multiply the
weight found by 0'8643 ; but, according to Hoi lard {BulL Soc.
Ohim.f 1904), if a platinum anode roughened by the sand-blast be
used, the ratio of Pb : PbO takes a constant value represented by the
factor 0*855,
After weighing the lead dioxide, the identity of the substance may
be confirmed by the tetra uiethyl-phenyl test.
§ 794, Estimation of Lead. — By far the greater number of estima-
tions of lead is made by weighing as lead sulphate, first precipitating as
*ulphide ; careful oxidation with nitric acid of the latter converts it
rapidly into sulphate. Recently, ammonium pei^ulphate has been
* Ralph A, StiJtth, Journ Jmm\ Ckefiu Soc.^ 1&05,
I 795-7970
COPPKK.
^17
recommended ''^ as a precipitant with a view to estimation. Ammonium
persulphate a^dded to au acid ^lution of a Lead salt, preeipitatoB the lead
quantitatively.
The beat precipitant is a 2 per cent, ammonium persulpliate solution
containing a trace of silver nitrate ; this is heated to 80', and
the lead solution added to it drop by drop. The solution should be
kept at SO" for tfirea hours, then filtered and washed with a 3 per cent,
solution of ammonium sulphat43 ; finally, the preoipitate, conmiting of
lead oxide, lead peroxide, and lead sulphate, is converted into lead
sutphate by igniting with a drop of aulphuric acid. Every 100 parts of
lead sulphate equal 73'6 PbO,
Estimation as biooxide and the oolonmetric method have already
been described.
Lead is also estimated as chloride, as chromate, and as sulphide, but
the processes detailed are sufficient for the toxicologist.
2. COPPER.
§795. Copper, Cu^63'5; specific gravity, from 8^921 to 8*952;
fusiag-pointj 109 T (1996' F,). Copper in auttlyais occurs either as a
Blm or coating on such metals as platinum, iron, etc., or in a state of
fine division, or, Bnally, as a bead. la thin films, copper has a
yellowish or a yellowish-red colour ; it dissolves readily in nitric,
slowly ill hydrochloric acid. If air be excluded, hydrochloric acid fails
to dissolve copper^ nnd the same remark applies to ammonia; but, if
there be free access of air, ammoDia also acts as a slow solvent.
Metallic copper in a fine state of division can be fused at a white heat
to a bright bluish-green globule, which, on coohng, is covered with
black oxide.
% 796. Cupric Chdde, CuO = 79^5 — specific gravity, 6*5; composition
in 100 parts, Cu 79*90, 0 20*10 — is a brownish-black powder, which
remains in the absence of reducing gases unaltered at a red heat. It
is nearly insoluble in water, but soluble in CIH, NO3H, etc*; it is
hygroscopic, and, as everyone who has made a combustion knows, is
readily reduced by ignition with charcoal in the presence of reducing
gases*
§797, Cupric SulpMde, CnS= 95-66, produced in the wet way, ia
a browtiish powder so insoluble in water that, according to Fresentus,
950,000 parts of water are required to dissolve one part. It is not
tiuite insoluble in CIH, and dissolves readily in nitric acid with separa-
tion of sulphur. By ignition in a stream of H it may be converted
into the subsulphide of copper. It must always be washed by SH^
* Max Dittmh aaid A. Reiae, Btf. d^ tieuixh. eh&n. Gts,^ 1905*
638
POISONS: THBIR EFFECTS ANP PBTKCTION.
[§ 798.
u'ater. It is slight ly soluble in the alkaline polysiilphideSj especially
ill the presence of sulphides of arsenic, aQtimonyi and tin,
g 798. Solubility of Copper in Water and Various Fluids,— The
solubility of copper in water and saline solutions bas been very care-
ful ly studied by Camel ley.* Distilled water exerts some sol van t action^
the amount varying, as might be expected, according to the time of
exposure, the amount of surface exposed, the qnantity of water acting
upon the copper, etc. It would appear that, under favourable oircum*
stances, 100 c.c. of distilled water may diusolve "3 mgrm. of copper
('2 grain per gallon).
With regard to salt% tho€e of ammonium exert a solvent action on
copper more decided than that of any others known. With the others,
however, the nature of the hjise exerts little influence, the action of the
salt de}>etiding chiefly on the nature of its acid radical. Thus, beginuing
with the least eflfective, the following is the order of dissolving strength
— nitrates^ sulphates, carbouateSj and chlorides. It will then at once
be evident that a water contaminated by sewage, and, therefore, con-
taining plenty of ammonia and chlorides, might exert a very considemblc
solvent action on copper.
Almost all the oils and fats^ as well as symps^ dissolve small
quao titles of copper \ hence its frequent presence in articles of food
cooked or prepared In copper vessels. In the very elaborate and careful
experiments of Mr, W. Thompson,! the only oils which took up no
copper^ when digested on copper foil, were English neats^-foot oil,
tallow oilf one sample of olive oil^ palm-nut oil, common tallow oil, and
white oil, which was protected from the air by a thick coating of oxidised
oil on its surface.
The formation of copper compounds with the fatty acids takes place
BO readily that Jeaimel * has proposed the green colouring of fats by
oopper as a test for the presence of copper ; and Bottger § recommends
a brandy holding copper to be shaken up with olive oil to free it
from copper,
Lehmann has made some useful researches on the amount of copper
taken up by fats under different conditions. 100 c.o. of strongly rancid
fat dissolved in fourteen days 87 mgrms. of copper ; but when heated to
160" for one hour, and then allowed to stand, a similar amount was
found. Some rancid butter was rubbed into a brass bowl of 90 c.c
capacity, and then allowed to stand for twenty-four hours ; the butter
became of a biue-green colour. Into this dish, thus partially attacked
• /m*rtt. Chmfi. Soe, ^ 187^, vol. ii, p, i.
t *' Action of Fatty Oila on Metallic Copper," Ch^pt. NtWR^ vol. xxxiv. pp. \7n,
200, S18.
S 798.1
OOPPKR.
639
by f&tt^ ttcide, 50 o.c* of FaBoid butter was poured in a melted cou*
dition, and aliamed to stand for twenty- four hours. The h mount taken
up was found to be eiqual to 10 mgrms. of copper for every 100 o.c. of
fluid butten
Bilger found a fattj soup, which had stood twelve hours in a clean
copper vessel, to contain 0*163 per cent, copper. According to Tscliirch>
the easiest fatty ssilt to form is the oleate, hydrated copper oxide diasolv*
ing in oleic acid with great ease, and even copper oxide dissolving to
some extent ; tlie ptilmitate and the stearate are not ao readily produced
—hence the amount of copper dissolved is p^reater in the case of olive oil
and butter (both rich in oleic acids) than in the case of the firmer
animal fats. Copper oleate, accord ii]g to H. Baum and R. Seeliger
{2kiL offentl. Ch&ni,^ iv* 18l-2lO)t is ujore poisonous than either the
aoetate or aulpliate. Acid solutions, such aa clarets, acetic aoid,
vinegars, and so forth, as might be expected, dissolve more or leas
copper- The amount likely to be dissolved in practice has been
investigated by Lehmann* He steeped 600 square inetros of copper
sheeting or bmss sheeting in vessels holding 2 litres each of acid claret ;
the sheets were in some of the experiments wholly immersed, in othera
partly so. More copper was dissolved by the wine when the copper
was partly immersed than when it was wholly immersed ; and more
copper was dissolved from braijs sheeting than from pure copper sheeting.
With a sheet of copper, partly immersedi claret may contain aa much
as 56 mgrms. per litre. Lthmann also investigated the amount of
copper, as acetate, which coidd be dissi>lved in wine before the taste
betrayed its presence : with 60 mgrms, per litre no copper tjtste ; with
100 mgrms, there was a weak after-taste ; with 150 mgrms, it wns
scarcely drinkable, and there was a strong after-taste; with 200 mgrms,
per litre it was quite nndrinkable, and the colour was changed to bluish-
green. Vinegar, acting luider the most favourable circumstances on
sheet brass or copper, dissolved, in seven days, 195 ragrms* of copper
per litre from the copper sheet, 1 95 from the brass sheet.
Lehmaon discusses the amount of copper which may be Uiken at a
meal under the circumstance that everything eaten or drank has l>ecn
arfcidcially coppered, but none " coppered '* to the extent by which the
presence of the metal could be betrayed by the taste j and tl*e following
ia, he thinks, possible ; —
SOO ce, of aoup boiled in a copyier vessel, . . * *
1 litre of wine which has been Bt&uding in a cop}mr vessel ^
50 o,(v vioegar whioh has been kept in a c&pjier veaset,
50 grmi. of £at whioh baa be^n uned for fryhig in t oop|>iir
vessel, t , . . . ♦ * * ,
200 grms. of strongly copf^erad fM>&3, , . . «
500 gnuH^ of strongly civpjiered bpead. . , , .
20 loin'ins. Oil
50 ,,
10 ,.
640 POISONS : THEIR EFFECTS AND DETECTION. [§ 799.
The total amoimts to ii^5 ingriiu}. of copper, which only slightly exceeds
a high medicinal dose. The metal is tasted more easily in liquids, such
as wine, than in bread; bread may be coppered so that at a meal a
person might eat 200 mgrms. of a copper compound without tasting it.
It is pretty well accepted that cooking in clean bright copper vessels
will not contaminate any ordinary food sufficiently to be injurious to
health.
§ 799. Copper in the Vegetable and Animal Kingdom and in
Foods. — Copper is widely distributed in the vegetable kingdom, and is a
constant constituent of the chief foods we consume ; the following quan-
tities, for example, have been separated from the chief cereals : —
Wheat, 5*2 to 10*8 mgrms. per kilo.
Rye, 5 mgrms.
Oats, 8-5 „
Barley, 11*8 „
Rice, 1-6 „
Bread, 1*5 to 4*4 mgrms.
It has also been found in vermicelli (2-10 mgrms. per kilo.), groats
(r6-3 mgrms. per kilo.), potatoes (1*8 mgrm. per kilo.), beans (2-11
mgrms. per kilo.). In similar small quantities it has also been found in
carrots, chicory, spinach, hazel-nuts, blackberries, peaches, pears, figs,
plums, tamarinds, black pepper, and many other fruits and apices. The
most common food which has a high copper content is cocoa, which con-
tains from 12 mgrms. to 29 mgrms. per kilo., the highest amount of
copper being in the outer husk ; copper has also been found in many
supplies of drinking water, in aerated waters, in brandies, wines, and
many drugs.
It has been calculated that the ordinary daily food of an average man
contains the following : —
Copper.
900 grms. bread, 0*45 mgrm.
260 grms. meat, 0*25 ,,
200 grms. fruit and vegetables, . . . 0*25 ,,
0'95 mgrm.
That is to say, that, neglecting altogether foods artificially contaminated
with copper, each of us eats daily about 1 mgrm. of copper (0*015 grain).
In the animal kingdom it is a constant and natural constituent of
the blood of the cephalopods, Crustacea, and gasteropods, and is nearly
always present in the liver and kidneys of domestic animals, as well
as in men. Dr. Dupr^* found '035 to '029 grain (1*8 to 2 mgrms.)
in human livers, or about 1 part in 500,000. Bergeron and L. L.
Hote's researches on fourteen bodies, specially examined for copper, fully
* Analyst, No. 13, 1877.
§8oo.]
COPPEF.
641
Bubetantiate those of Dr. Dupr^ ; iti twelve the copper was foiuid in
quantities of from *7 to 1 '5 mgmi, ; in the rematnitig two the amount of
copper was very minute, aud was not estimated.* Copper is also found
normally in the kiduejs* and Duprt^ f detected in human kidneys about
1 in 100,000 parts ; it is also found in the bile, and in minute traces in
the blood. |
In the kidneys and livers of the ruminants copper may always
be found, a sheep^s liver containing about 1 part in 20^000.^ Chureh
found copper in the feather of the wings of the turaco; melopsitt in
the feathers of a par roquet {Melopsiitams ufidulatwt).\\ In these cases
the copper enters into the compoaition of the colouring matter to which
the name of *Huracin*' has been given. Turacin contains 7 per cent, of
copper, and gives to analysis numberg which agree with the formula
of CgaHgiCu^N^Ojg.
Copper has been discovered in aerated waters, its presence being due
to the use of copper cylinders, the tin lining of which had been rendered
defective by corroijion*f
Accidents may also occur from the nse of copper boilers. T^tr. W,
Thompson found in one case "** no less than 3*575 grains in a gallon (51
mgnns, per litre) in water drawn from a kitchen boiler
At Roubaix, in France, aulphide of copper had been deposited on the
roof, as a consequence of tlie use of copper flues; the sulphide was
changed into sulphate by the action of the air, and washed by the rain
into the water-tank.tt
That preserved vegetables are made of a bright and attractive green
colour by impregnation with copper, from the deliberate nae of copper
vessels for this purpoaei is a fact long known. Oreen peas especially
have been coloured in this way, and a number of convictions for this
offience have taken phice in England,
§ 800. The ** Coppering" of Vegetables. ^The fact that green
vegebableS) such as peas, beans, cucumbers, and so forth, preserve their
green colour, if boiled in copper vessels, has long been known. In this
"coppering" the French have been more active than the Eriglbh
traders ; the French operate in two different ways. One method is, to
dip from 60 to 70 litres of the green vegetables in 100 litres of 0 3 to
0*7 per cent, of copper snlphate, to leave them there for from five
to fifteen minntes^ then to remove them, wash and sterilise in an
autoclave. A seoond method is to put the vegetables into a copper
* Campt, Eetid., voU kix. p. 'MB. f Op. ciL
t H oppeSeyler J FfiTU^^iwA ifcr p%*io%ist' A. Analyae., p. 416,
i Dupr^, op. rii. \\ €hnn. Ntim, Jix^lij. 212.
1! '*0a the Prc^nce of Le&d and Copper m Aumted Wnt^rfl/' by Dr. Jaoim
MUna, Ch^m, iV«(w, %xxL p. 77.
** ChJ^, Ntws, Jinci* No. 801. tt Blfth, Didiifmir^ it/ ffp^n^, p. IS?.
41
642
POISONS: THEIR EFFECTS AND DETECTION.
[§8oo.
Teasel, the wall Qf which is con nee bed with the negative pole of an
electric current; the positiYe pole dips in a solution ot salt in the
same vessel, the current is allowed to pass for three minutes, and
the vegetables are afterwards sterilised. Fruits are airaply allowed to
stand with water iu copper vesHels, the natural acidity of the juice
disaolving sufficient copper.
The amount of copper taken up in this way is appreciable, but yet
not so much as might be expected. The prosecutions for selling
** coppered ^' peaa in England have been based upon quantities varying
from I to 3 grains per lb, ; the highest |mblished amount of eopper
found in peas artihcially coloured is 0'27 per kilo., or 18 '9 grains
per lb.
The reason why vegetables preserve their jrreen colour longer when
treated with a copper salt has been proved by Tscbirch * to be owing to
the formation of a phyHocjauate of cropper*
Phyllocyauic acid is a derivative of chlorophyll, and aUied to it in
composition j the formula of C.j^HogNaO^ has been ascribed to it. Under
the action of acids generally, mineral or organic, chlorophyll eplits
up into this acid and other cora pounds. Capper phyllocyanate>
{C24H^7N20jj)^Gu, contains 8^55 per cent of copper; it forms black
lamellie, dissolving easily in strong alcohol and chloroform, but in-
soluble in water; it is a little soluble in ether, insoluble in petroleum
etherj and dissolved neither by dilute acetic acid nor by dilate nor
concentrated hydrochloric acid. The compound dissolves in caustic
alkali on warmiog. In alcohol it forms a beautiful n on -fluorescent
solution. A solution of 1 : 100,000 is still coloured strongly green.
This solution, in n stratum 25 mm, thick, gives four absorption
bands when submitted to spectroscopic observation, and Tschirch has
workefl out a proces«( of eat! mat ion of the amount of copper phyllo-
cyanate based upon the disappearance of these bands on dilution*
Green substances^ so carefully treated that they only contain
phyllocyanate of copper, would yield but small quantities of copper^
and probably they would not he injurious to health ; but the coppering
is usually more e^ctensive, and eopper leguminate and other compounds
are formed — for the vegetables^ when exhausted by alcohol, give a
residue which* successiirely exhausted by water, by soda-lye, and lastly
by hydrochloric acid, parts with copper into the three eolventa
mentioned*
It might be argued that, from the insoluble character of the phyllo-
cyanate of copper, and especially seeing that it does not dissolve iu
strong hydrochloric acid, that it would be perfectly innocuous ; but
Tschirch has proved that, whether the tartiute of copper (dissolving
* Das Kup/er, Stuttgart, 1899*
§ Sol]
COPPEE^
643
easily in water), or copper o^ide {not disBolving at all in water» hut
soluble in hydrochloric acid), or phylloojanat© of copper (insohible both
ill water and in bydro^'hloric acid) be used, the phyaialogieal etlect i&
the game.
Copper may be found in apirits owing to the use of copper eon-
densera, a remark whicb applies also to the essential oils, such as oleum
(^aJefftUej 7mntlm, etc* In France, it has been added fraudulently t*t
abgintbes, to improve its colour, t Green sweetmeats, green toys, green
papers, have all been found to contain definite compounds of copper to
a dangerous extent,
§ 801* Preparations of Copper used in Medicine and tbe Arts.
(1) Medicinal Preparations:^
Sulphate of Copper, Cupri Sulphas, Uu80^5n.30» — This well-lcnowii
Siilt is aolul^le in water at ordinary temperature^ 3 parts of water
dlsaolving 1 of the sulphate; but boiling water diaaolves double ita
weight. One part of copper sulphate dissolves in 2i of glycerin ; it
reddens litmus, and is slightly efflorescent ; its solution responds to all
the usual tests for copper and sulphuric acid, A watery sohition of the
a».lt to which twice its volume of a solution of chlorine hag been addei^,
gives, when treated with ammonia in excess, a clear aapphj re-blue solu-
tion, leaving nothing undissolved, and thus showing the absfcnce of
iron. Besides iron, sulphate of cop|)er has been found to contain ssincic
sulphate*
Nitrate of Copper, Cu{N03)33H20, ia officinal ; it is very soluble.
Cuprum AlumtnatniiL^A prepiration, called eupnim alumiuatutn
{Pierre divim}^ is in uae in Franco and Germany, chiefly as an
external wa^h. It is composed of 16 part^ cnpric sulphate, 16
potaasic nitrate, 16 alum, fused in a crucible, a little camphor being
afterwards added,
Ucgular and irregular medical practitioners, veterinary surgeons,
farriers, and grooms, all ime sulphate of copper (bluestone) bm au appli-
cation to wounds. Copper aa an hdet-udi retnedy is not in favour
cither with quacks or vendonj of patent medicines,
(2) Copper LQ the Arts. — Copper is uaed very extensively in the
arts; it enters into the composition of a number of alloys, is one of tho
chief constituents of the common bronzing jiowdeni, la contained in
many of the lilac and purple fires of the pyrotechuiat, and in a great
variety of pigments. The hist^ mentioned, being of special imjjortance,
will be briefly deacHbed : —
• Accord ini? to Eulenbcti? {Gtmerbe SygwjWj p, 71C), OUum eajipnte, MmiK
pip»t Mttusit, Ta^jtitcMi^ et<?., ttre almost alway^i contamiuttted with oopper*
644
P0TS0N8 r THEIR EFFECTS AND DlTECTinN. [| 802, S03,
Pigments : —
Schweinfurt and S cheek's Green * are respectively tbe aceto-arsanit^
aud the arsenite of c;oi>per (see art. " Ars^enic "),
Brighton Gre^H is a mixture of impure acetate of copper aud chalk.
Binmswick Green, originally a crude chloride of copper, is now
generally a mixture of carbonate of copper aud chalk or alumina.
Mountain Green, or Mineral Green, is the native green carbomite of
copper, either with or witljout a little orpiment,
Keowieder Green m either the same as mountain green, or Schwein-
furt green mixed with gypsum or sulphate of baryta*
Green Verditer is a mixture of oxide and carbonate of copper with
chalk.
Verdigrifl is an acetate of copper, or a mixture of acetates. Its
formula is usually represented as {CgHgOj)CuO. It is much used in the
artSi and to some extent as an external application in medicine* Its
most frequent impurities or adulterations are chalk and sulphate of
copper,
§ 802 Dose— Medicinal Dose of Copper — Since sulphate of copper
is practically the only salt administered internally, the dose is generally
expressed va so many grains of sulphate. This ialt b given in quantities
of from *016 to *1*29 grm. (J to 2 grains) as an astringent or tonic; as
an emetic, from *324 to -648 grm. (5 to 10 grains).
The sulphate of copper is given to horses and cattle in such large
doses as from 30 up to 120 grains (1*9 to 7'7 grms,) ; to sheep, from
1^3 to 2^6 grms. (20 to 40 grains); rabbits, ^0648 to '1296 grm.
{1 to 2 graiuB).
§ BO 3. Effectfi of Soluble Copper Salts on Animals, — Hamack baa
made some experiments on auimalH with an alkaline tartrate of copper,
which bns no local action, nor does it precipitate albumin. J to |
mgrm. of copper oxide in this form, administered subcutaneously, was
fatal to froga, 05 grm. to raljhits, *4 grm. to dogS- The direct excita-
bility of the voluntary muscles was gradually extinguished, and death
took place from heart paralysis. Vomiting was only noticed when the
poison was administered by the stomach, f The temperature of animals
poisoned by copper, sinks, accorditig to the researches of F. A. Falck,
many degrees. These observations are iu agreement with the effects
of copper salts on man, and with the experiments of Oriila, Blake,
Cp Ph. Falck, and others.
* The Kyaonyras for Schweiofurt gi'eeii are extremely numerous : — Mitic gneiii
Yiennic green, impt^ml greeu^ emerald green, are the princijial terms iu actual use,
t < Ja tho other hand, Brunton a»d West have observed vomiting produced in
animals after injwtion of copper peptone into the jvigukr vein.'^Barth. Bosp, itf'/*.,
1877, xii.
S 803-1
COPPER.
64s
Roger ■* experimented on the effect of copper leg am in ate which was
administered Bubcutaueoualy ; he found gradual increasing paralysis of
the motor spinal tracts, which finally destroyed life hy paralysis of the
breathing centre. The heart heat after the breathing had stopped* The
irritiibihty and contractility of the mnscles of frogs were lost* while
sensibility remained. Ho also found that, if the copper was injected mto
the intestinal vessels, the dose had to be doubled in order to destroy life ;
that is, doubtless, because the liver, as it were, strained the copper oflT
and excreted it through the bile. lUjger was unable to destroy life hy
large dosetj of copper given by the mouth, for then vomiting supervened
and the (foiaon in great part was renmved,
Bernatzic t considers that the poisonous properties of copper are
similar to ih<me of zinc and silver. He says ; "Silver, copper^ and ^ino
are, in their medicinal application, so much allied that, with regard to
their action, they graduate one into the other and show only minor
diftcreuees; copper, which is a little the more poisonous of the three so
far as its remote action is concerned , stands between the other two. If
taken, in not too small a quantity, for a lung timet the liiuetional activity
of the muscular and nervous systems is influenced injuriously, the
development of the animal cells is inhibited^ the number of the red
blood corpuacJea decreased, and therefore the oxidising processs and
metabolism are likewise diminished, leading ultimately to a condition
of marked cachexia. . « . From a toxic point of view, the three
metals named ^dso st^md near each other^ and their compounds di0er
from other metals injurious to the organism in this, that they do not
produce notable changes of the tissues or coarse functional disturbances
leading to death as other poisonous metals, and therefore are not to be
considered poisons in the sjinie sense m lead, mercury, anicnic, antimony,
phosphorus are considered poisons; for, on stopping the entry of the
|K)ison, any injuriona eft*ect is completely recovered from and the
functions again become normal/'
Lehmann I also has experimented on the a Sects of copper ; his
experiments were made on both animals and men. He found that
small quantities wore more thorovighly absorbed than medium or large
doses; the method of separation appeared to be different in different
animals — thus, the chief copper-excreting organ in dogs is the liver, in
rabbits the intestine, and in man the kidneys. Of 3 mgrms, of copper
taken by a man in three days, I mgrmi., or a thiid^ was recovered from
the urine, t^hmaim experimented on 6 rabbits, 4 cats, and 1 dog.
During the first few days the animals were given 10 to 30 mgrms. of
• Mtmr dc Miderine^ 1877. Xli.
t Xmqfdop^i. il. (fen, ileilkmufift :ri. B. 4*19^
646
poisons: theib effects and detection
[§ 804.
copper, in the form of a salt, in their food ; then the dose was raised to
50 mgrms. or even to 100 mgrnis*, And the experiment continued for
from two to four months ; in one case, six months. The sulphate,
acetate, chloride, oleate, butyrute, atid lactate were all tried^ but no
essential ditlerence in action was diiHJovered ; apart from slight vomiting,
and in a few caaes, as shown by iwst-murtem, a slight catarrh of the
stomach, the animals remained well A few increased in weight.
Nervous symptoms, cramps^ convulsions, diarrhceai or the reverse^ were
not observed. The analysis of the orgtms showed considerable copper
absorption ■ ihe liver of the cats gave a mean amount of 12 mgrras, of
copper, and in the other organs there was more copper than is found in
cases of acnte poisoning*
Lehmaun has also made eiperiments upon himself and his pupils on
the effect of the sulphate and the acetate when taken for a long time : —
One of the experimenters took for 50 days 10 mgrms, daily Cu as
sulphate.
*>
tl
aeti for 30
„ 20
»s n
the]
r took for 3 days
5
mg
rms, as acetate,
1}
then for 10 days
. 10
i» 11
»>
1. 1 day
. 15
jf n
J*
19 days
. 20
ij n
rl
„ IS days
. 30
it i»
None of these tlaily doses Imd tho least eU'ect.
Five further exijoriments showed that 75 to 127 mgrmB. of copj>er
in jiejvs and beanSj divided in two nicaltj, could be taken daily without
effect ; but if 1 27 mgrms. were taken at one meal in 200 grms* of jKias,
tl»en, after a few hours, there might lie vomiting ; and Lehman n con-
cludes that doses of eopp^.T in fooii of about 100 mgrnis. may produce
some transient derangement in hoalth, such as sickness, a nasty taste in
the mouth, and a general feeling of discomfort, but nothing more. Some
slight colicky pains and one or two loose motions are also possible^ but
were not observed in Lehinann's experimentB.
§ 804* Toxic DoB@ of Copper Salts. — This is a diiicult question,
liecause copper salts generally act as an emetic, and therefore very large
doses have been taken without any great injury* In fact, it may be laid
down that a medium dose taken dally for a eonsiderable time is far more
likely to injure health, or to destroy life, than a big dose taken at once.
In Tsehirch's* careful experiments on animals, he found 10 mgrm, dosea
of CuO given daily to rabbits, the weight of which varied from 12t>0
to 1650 grms,, caused injury to liealth — that ts^ about 3*5 mgrms. per
kilo. If man is susceptible in the same proportion, then daily doses c»f J
* IM» Kn^fir, Sluttgart, 189S,
|8os-]
COPPER.
647
S!27'5 mgrras* (or abotit 3 J gniiti^) would cause serious poisououa
ajinptoms; althougb double or treble that quantity might in a single
dose be swallowed and, if thrown up speedily, no great harm result,
120 grms, of snlphate of copper have been swallowed, und yet the
patient recovered after an illness of two weeks.* Lew in t mentions
the case of an atlult who recovered after ten days' illness, nlthough the
dose was 15 grnis. ; there [a also on reconl the aisti of a child, four and
a half years old, who recovered after a dose of 16 '6 grm^* (a little over
half an ounce). On the other hand, 7 '7 gnns. Imve been with diffieulty
recovered from.l A woman died in seventy -two hours after taking 27
grms, (7 drnis.) of copper sulphate mixed with 11*6 grme. (3 drma,) of
iron sulphide ; 56 "6 grms. (2 om.) of copper acetate have caused death
in three days, 14*2 grms. (0 5 oz.) In sixty bours.g
§ 805. Gases of Acute FoiBOoing. — Acute poisoning by salts of
copper [s rare : in the ten years ending 1903, there were registered in
England 5 deaths from tJira cause — 3 siiicidul (2 mulesj I female)
and 2 accidental (males). The symptoms produced by the snlphate
of copper are those of a powerful irritant poison : there is immediate
and violent vomiting; the vomited matters are of a greenish colour —
a green distinguished from bile by the colour changing to blue on the
addition of ammonia* There is pain in the stomach, and in a Httle
time affections of the nervous system, as shown bj- spasms, cramps^
paralysis, and even tetanus. Jaundice is a frequent symptom^ if life is
prolonged sufficiently to admit of its occurrence-
One of the best examples of acute poisoning by copper sulphate is
recorded by MaHchka,|| A youth, si Jt teen y*^ars old, Ujok an unknown
large dose of powderi/d copper sulphate^ mixed with water. Half an
hour afterwards there wasi violent vomiting, and he was taken to the
hoepitah There was thirst, retchings constriction in tbe throat, a cop-
pery taste in the mouth, and pain in the epigastrium, wliich was painful
on pressure. The vomit was of a blue colon r* and small undissolved
crystals of copper sulphate were obtained from it, Tiie patient was pale,
tbe edges of the Hps and tbe angles of tiie mouth were coloured blue»
the surface of the tongue had also a blue tint, the temperature wa»
depresse<i, the extremities cold, nails cyanoticj and the pulse small and
quick. Several loose greenish -yellow evacuations were passed ; there
was no blood. The urine was scanty, but contained neither blood nor
albumen. During the night the patient was very restless ; the next
morning he had violent headache, puin in the epigastriiun, burning in
* Refomsd bo by Beniatxic, on the authority of Ki^tli, in SneycL d. ^1.
EeUkunde, xi 8. 433
+ TosekGl0gi4t S. 133. t T»ylor, v^k <iL f Sonneascheiji, op. dt,
II Winner med, ir««A*HJcAn, 1871 » Nra 25, p, S28,
648
POISONS: THKIR KFFBCTS AND DETECTION, [§ 806-S08.
the mouth and gullet, but no Yomitmg. The urine was scanty, con-
taiued b1ood| albumen^ and colouring matter from the bile* On the
fourth day there was marked jaundice. The raucous membrane was
very paH the temperature low, puke fref|ueut ; and great weakness,
cardiac oppression, and reBilessuees were eiperieuced* There were
dlarrho&a and tenesmus, the mottoim l>ehig streaked with blood ; the
urine also contained much blood. The liver was enlarged. The patient
died in a state of collapije on the seventh day.
In 1836 a girl, mxtcen monthfj old, wa^ given blneatone to play with,
and ate an unknown quantity ; a quarter of an hour afterwards the
child was violently aiek, vomiting a bluiBh-green liquid containing some
pieces of sulphate of copper. Death took place in four hours, wit bout
convulsion^ and without diarrhoBa.
§ 806. Subacetate of Copper^ Subcbloride, and Carbonate, all act
very similarly Iq the aulphatc when given in large doses.
g 807. Post-mortem Appearances. — In ila&chka'a case, the chief
changes noted were in the liver, kidneys, and stomach. The substance
of the liver was friable and fatty ; iu the gall-bladder there was but a
few drops of durk tenacious bile. The kidneys were swollen, the
cortical substance coloured yellow, the pyramids compressed and pale
brown. In the mueouij membrane of the stomach there was an excori-
atiun the nke of a ahilUug, in which the epithelium was changed into a
dirty brown mass, easily detached, laying bare the muscular substance
beneath, but otherwise normal.
In a case of poisoning by verdigris (subacetate of copper) recorded
by Orrtla,* the stomach was bo much inHamed and thickened that
towards the pyloric end the open in <^ into the intet^tino waa almost
obliterated. Tbe small intestines throughout w^cre iuHamed, and per^
fo rati on had taken place, so that part of the green liquid had escaped
into the abdomen. The large intestines were distended in some parts,
QontriLcted in others, and there was ulceration of the rectum. In other
cases a striking discoloration of the mucous membrane, being changed
by the contact of the salt to a dirty bluish-green, baa been noticed^ and,
when present, will afford valuable indications.
g 808. Chronic Poisomiig by Copper. —Symptoms have arisen among
workers in copper or its salts, and also from the use of food accidentally
contaminated by copper, which lend support to the eiistence of chronic
poisoning. In the symptoms there is a very great resemblance to those
produced by lead. There is a green line on the niargin of the gums
Dr- Clapton t found the line very distinct in a sailor and two working
coppersmiths, and the two men were also seen by Dn Taylor, Cases of
* Tomitf^logi^^ vol- i. p, 787 (5tlicd,),
t At&i, Tim6s and OaadUj June 1358, \k 65 a.
§ 80S.]
COPPER.
649
chronic poisoning among coppersmiths have also Jjeeii treiit-ed by Dr.
Cameron,* but tbiis symptom was not noticed. Corrigan speaks of the
line round the gums, but doaeribea it as purple-red. Among workert^ in
copper, Lancereans t has seen a black coloration of the mucous oiem-
brane of the digestive canal ; itu cbemical characters appear to agree
with tboBo of carbon.
Metallic copper itself is nut poisonoua. A Mr. Charles Heetl has
published a letter in the Cheittirmi Net€» of Jan, 12, 1894, atating that
ho was, when a boy, wounded in the shin by a copper percuasioncfip,
and the cap remained in the tissues; it was removed from the shin
after a sojourn there of some twelve years; about the year 1873 he
noticed that whenever a piece of clean iron or steel came in contact with
his perspiration it was at once covered with a bright coivting of copper,
and this continued until the percussion*cap was removed. Presuming
the trnth of this, it shows conclusively that metallic copper deposited in
the tissues is in itself not poisonous, and further, that one method of
elimination is by the skin. The experiments already cited throw doubt
as to whether repeated small doses of copper taken for a lon^ time
produce, in a sci entitle sense, chronic poisoning ; those which apparently
support the view that there is such a thing as chronic poisoning by
coppdr have been produced by copper mixed with other metals, and
there ia the possibility that these causes are really due to lead or arsenic
And Dot to copper. The great use of late years of solutions of copper
sulphate as a dressing to plauts, for the purpose of preventing the
ravages of vanous parasiteSj hai^ proviiteil, so far as animals are concerned,
much material for the judgment of this t|ueBtion, Sheep have been fed
with viues which have been treated with copper sulphate^ oxen and pigs
have consumed for a long time griuss treated with a 3 {>et cent, of copper
sulphate, without the least health disturbance. Mach % has fed cows
with green food coppered up to 200 mgrms. of copper sulphate, without
observing the slightest bad eJTect, for long periods of time ; and Tachirch g
summarises the evidence as to chronic poisoning as follows; — *^So it
appears the contention that there is no chronic poisoning in men or
animals is at present uncontnuiicted; it is further to be considered
proved that the small amounts of copper naturally in food, or carefully
introduced into food, are not injurious to the health of those that take
such foodf because the liver, kidneys, and other organs excrete the
copper through the urine and bile, and prevent a pernicious accumu-
lation." At the same time, Tschirch does not consider the question is
* Mtd. Tim^ mnd QmetU, 1870, voL i. p. 681.
t Macli, Berieki fli«r ffif SrffthnUnr'd^ tm ./oArn 1886 aitstjffiihrim Verw%tehe tur
M^kam^/ting (Ur Pi^ttmtfifiJOTa^ St. Miulivk*, Tyrul. § Op, cU,
6so
POISONS: THEIK KFFBCT8 AND DETECTION.
[§809.
dedultely Bettkd ; the ex|>or]meut.^ should^ he thiuksi have been con-
tinued not for moiithfi, but for years, to obtain a trustworthy jndgnietit.
It nifty also be remarked that, if we are to rely upon the separation
of copper by the kidneys and the liver, those organs are presumed to be
m a healthy state, which Is not the case with a percentage of the popu-
lation; to persons whose liver or kidneys are unsound, even the small
amtjunts of copper found in '* coppered ** pea« may act as a poiison, and
the experiments prevtuusly detailed throw no light upon the aobion of
uopper under such circimistauces.
g 809. Detection and Estimatiou of Copper, — In routine analysis,
a solution of inorganic salts, acidified only mtxleratcly with hydrochloric
acid, will have been satumted with bydric sulphide, and any precipitate
treated with ammonium sulphide to dissolve out the sulphides of arsenic,
antimonj, and tin ; the sulphides remaining inHoluble may be silver,
mercury, bismuth, lead, copper, cadmium, zinc, and there may be, if
pUtinnm veasela have been used, a tmce of platinum sulphide. These
mixed insoluble sulphides are attacked by nitric acid, diluted with its
own volume of water, and the niixtura boiled. Soluble nitrates are
formed of most of the metals, but svdf»hide of mercury will not be dis-
solved, nor platinum sulphide — the lead sulphide, if present, will also
in great part have been converted into sulphate, so that these, with
free *mlphur, can be filtered off". In the uitric acid solution, any silver
may be detected and separated by hydrochloric acid, lead by dilute
aulpburic acid» and hismuth by adding an excess of ammonia and
Altering otf any white precipitate, 8hoidd copper he present, the
ammoniacal liquid will be of a blue colour To separate the copper the
liquid may be evaporated to dryness, and the nitrate deeomtjosed by
heating with ti little sidphuric acid ; the resulting sulphate is dissolved
ill water, boiled, and to tlie boiling liquid hyposulphite of sodium
solution added, v^hieh produces a precipitate of cuprous sulphide,
Cn^S, mixed with sulphur. This sulphide may be readily converted
into a soluble copper salt iiud further identified by tests,
ElectrolysiB of Copper Salts, — Both as a means of detection and
estimation of copper, electrolysis is muoh used. Copper is readily
deposited from an acidified solution on either bright iron or bright
zinc. An old method of estimating copper was to treat a solution with
Kinofoil and dilute sulphuric acid, but this somewhat crude process is
now but little used. The ordinary process of electrolytic deposition of
copper m to dissolve up to I'b grm, of the substance containing copper
in dilute sulphuric acid, to add a small quantity of nitric acid, Mid to
dilute up to 130 c.c, with water, usiug platinum poles; the anode may
conveniently be a platinum dish. The solution te heated to about
60'-65^ and the current should be 2 '5-3 amperes %nd 2 voUb. The
§8io;
GOPFKE.
651
deposit is wnsherj (without iuterrupting the current) fitni with water,
then with alcoholj and finally with ether, and i^ then careful Ijf dried and
weighed. Should iron, nickel, or cohalt be present, Kufferath* adds
2 grniH. of fornmldehyde, which prevents their deposition.
Special Teste for Salts of Copper. — llplrazhie Sulphate.^ A 3 per
cent, solution of [k^'drazine sulphate added to a eolution of a oopper
saltj hi presence of an excetis of sodium hydroxide, precipitates the
copper as metallic copper] the metal may bo filtered ott", dried, ignited,
and weighed as ciiprto oxide, f
IHpheni/l'Caibasitle Te^^t, — A cold sa turn ted &otutioii ol the carbamide
in ben^enet i^^itated with an aqueous solution of a copper salt^ produces
a violet compound which dissolves in the lienzene^ I Carbai^ide gives
colours similarly with a number of metals, but the hue of the copper
compound differs from all others-
Fonnaldoxime. — Formaldoxime m made l>y adding hydroxy himiue
hydrochloride to formaldehyde in solution in the proportion 1:5. This
solutiou is mixed with the solution to be tested for copper and a slight
excess of potash solution ; should copper be present, a violet colour
results. It is stated that one part per million of copper in aqueous
solution may be detected by this reagent.§
The Bromine Ted. — On evaporating a solution containing a copper
salt to dryness, and then adding bromine water and again evajjorating
to dryness, a black residue of copper bromide is formed ; this will,
according to Vitali, detect one part of copper sulphate in a fnillion of
water I J
MierO'Chemif*ai Ttst» for drpper. — ^A dilute solution of a copper
salt, to which aajrnonia ha^ been ailded, gives a precipitate with
potassic ferrocyauide of ammonium ferrocyanide of copper (Fe{CN)^Cu^„
4NH3, H-jO) it! pale yellow characteristic crystals ; the crystals, without
changing their form, gradually lose ammonia, and then the colour
becomes a red- brown or brick-red.
A copper salt diasohed in a concentrated solution of potassium
ni trite, to which acetic acid in excess has been added and then a small
fragment of lead acetate, is converted into a triple nitrite of potassium,
copper, and lead 2NO3K, (NO-)jjPb, (N0^)2Cu eH^O ; this salt is in
highly refractive cubes» and is very eliaract eristic.
g 810. Volmnetric Froceises for the Eatimation of Copper. — A
number of volumetric processes have been devised for the estimation of
• ZeiL anffcw, Chem.^ It04,
t P»ul Janniiach and K* Bledermami, Em'.^ 1900.
t Paul CazeDeuy«, Compi, RefuL, l&OO.
g Dun^tun and Eogsl^ Joum. Cltem* Soc., Tramt^t IS&S. A. Bmb., Compt*
Mend., 1899.
J D. ViUii, B&IL Chim. /Iftrfrk, aycxvilL
6s2
POISOJiS: THI5IR %¥¥ECTB AND DITTICTION. [§ 8II-8T4.
copper, bat for tlie piirposea of this work it ia unnecossary to detail
tliem* When copper ia in too bihbII a quantity to be weighed, it may
then ho cati mated by a colorimetric process.
One of the tjost of these is based upon the brown colour which ferro-
eyauide of potash produces in ?ery dilute aolutiona of copfHsr. A
ataudard copper aohition ia obtained hj dissolving sulphate of copper in
a litre of water, m that each c*c. contains 0*1 lugi-ra. Cn, and a solution
of ferrocyanide of potash in water is prepared, atretigth 4 per cent It
m alwo convenient to have a solution of nitrate of ammonia, which is
fountl to rendc^r the reaction uinch more deUcato,
The further details are on the well-known lines of colorimetric
estitnationa*
3. BISMUTH.
§ 81 L Bismuth, Bi - 210 ; spediic gravity, 9"799 ; fusing-poiut, 264"*
(507*2" F»). — Bismuth, a« obtained in the course of analysis, is either a
black nietallio powder or an extremely brittle bead of a reddish^whtte
colour. The compounds which it wiU be necessary to briefly notice are
the peroxide and teiiitilphtde.
§812, The peroxide of bismuth, Bi203 = 468 — specific gravity, 8*211 ;
BJ| 89'64 per cent. ; 0, 10*36 per ceufe,^-a9 prepared by igniting the car-
bonate or nitrate, is a pale lemon-coloured powder, which vim be fused
without loss of weight, but is reduced on charcoal, or in a stream of
carbon dioxide, to the metallic state. It la also reduced by fusion with
pottissic cjauiiie or by iguitiou with ammoninm chloride,
§813. The Sulphide of Bisniuth, Bij,8^ = 516— Bi, 81-25 per cent. ;
S, I8*7i) per eont. — oceurs, in the i'ourso of analysiB, as a brownish-
black or ijuitc bUck precipitate, insoluble tn wutt^r, dilute acids, alkaliea,
alkaline sulphides, sulphate of soda, tmd cyanide of poti\ssinm» but
dissolving in moderately concentrated nitric ncid with separation of
sulphur. It continually in creases in weight when dried in the ordinary
way, and is completely reduced when fuaed with cyanide of potassiiniL
§814. FreparationB of Bi&niiith used m Medicme and the Arts.
(1) Phaniiaceutical Preparations;—
Biflmuthi Subiiitraa, BiON03 H^LK — A heavy white powder, insol-
nble in water, and responding to the usual tests for bismuth and nitric
acid. The formula should yield 77 per cent of bismuth oxide.
Commercial preparations, however, vary from 79 to 82 per cent.
BiBmuth Lozenges {Trochisci bismuthi) are composed of subnitrate
of hiEsmuth, magnesia ccirbooate, precipitated lime carbonate, sugar, and
gum, mixed with rose water* Each lo2^enge should contain 0*13 grm.
(2 grains) of subnitmte of bismuth.
§Sis.8id]
BTSMUTK,
6S3
Salution of Citrate of Bismuth and Ammonia (Liquor Biemuthi et
Amntonise citratis)^ a colourlesa neutral or slightly alkaline t^iiid,
Bpecific gravity 1*07, responding to the tests for bismuth and ammonia.
Aa an impuritj lead may be present, citric acid being bo frequently
coutaminated with lead. Carbonate of bismuth {Bismuthi curbomts),
(B'uO.J^'0^),^l{fi^ h a fine white powder auBwering to the tests for
carbon dioxide and bismuth ; it should yield 89^1 per cent, of bismuth
oxide.
A Nitrate of Bismuth, Bi(N03)g, an oleate of bismuth, an oxide of
bismuth^ a subgallate of bismuth (derjtmtol)^ and a subiodide of bismuth
aro also used in medicine.
(2) Bismuth in the Arts.^
The cliief use of bismuth is in alloys and solders* The chromate is
employed in calico print ing^ and the subnitrate as a paint onder the
name of pearl-white.
The salts of bismuth also nccur in washes for the hair, and
pearl-white is used as a cosmeticj but ooly to a small aictent.
I 815. Medicinal Boseg of Bismuth. —The subnitrate and carbon-
ate are prescribed in dotsea from *0648 to P296 grm. (I to 20 grains) j
the valerian ate J from *1296 to ^648 grm. {2 to 10 grains) ; and the
solution, from 17 ex. to 5-2 c.c. (J drachm to 1|^ dnichin).
§ 816. Toxic Effects of Bismuth. — From the researehes of Meyer
and Steiufeld t on animals, it appears that if birds or mammals are
poisoned with bismuth salts introduced subciitaneously, or by direct
injection, into the veins, death fallows in from twenty -four to forty*
eight hours, the fatal issue being preceded by convulsions ) after death
the colon is intensely blackened, and it may be ulcerated, while the
small intestines and the stomach are healthy. If, however, sulphur
preparations are given by the mouth, there is then blaokenitig of the
stomach, and there may also be ulcers. Meyer is of the opinion that
SR, precipitates bismuth in the parenchyma, anil the particles occluding
the capillaries thus cause small local necroses ; that which escapes pre-
cipitation is mainly excreted by the kidneys* Poisonous symptoms in
man have been known to occur from the treatment of wounds with
bismuth prepamtions ; I the symptoms have been somewhat similar to
mercurial poisoning ; there have been noticed stomatitis with salivation,
loosening of tho teeth, a black colour of the iiuk'Ouh tiiembrane of the
itmuth, and ulceration — also catarrh of the intestines, and the inilamma"
* Bkmuth id coiitalued in all oopj^er coiaago— from the llttctriftu uuins to our
own ; in all cupreouH or^, except the carhouiLt^, uud in nearly a1! specinieu!i i>r
eotnmoroiifcl copper. — Field, Cherts, Metus^ xxxvL^ 261,
+ L F«yder- Meyer, Mmskn^h's phar^ak. UnUrs,, iii*^ 1882, No, 2S ; Steinfijld,
Ifitkioi^dtB Wiim^ut. Imiug. Dfta,, f^^jrpP-t, ISS4 ; Arth. rjr/*. A» Bd» xx, 1886,
i if, M^ Jimrml, 1387. I 740.
6S4
FOISOHS: TQBIB EFFBCTS AND DETECTION.
[§ 817-
tory condition of the kidneys usual when that organ has to excrete
metallic substancea not nattiml to the body, the '^ metftllniere,'^ or metal
kidney, of the German writers. One case ia recorded of death in nine
days of an adnlt after ttiking 7 "7 grois. (2 dmiB.) of bismuth subnitrate.
The recorded symptoms were a metallic taste in the mouth, pam in the
throat, vomiting, purging, coldness of the surface, and spasms of the
arms and legs. A post-mortem examination showed iiiflamumtory cliauges
in the gullet, windpipe, and throughout the intestinal canal < Recovery
has, however, taken place from a single dosse three times the amount
meutioued. It is possible that the fatal case was due to impure
bismuth.
§817. Extraction and Betectinn of Bismuth in Animal Matters,
— Biamuth appears to be excreted principally by the bowels as sulphide
of bismuth ; but it has also been detected in the urine, spleen, and
liver^ and Lubinsky has found it in the saliya and in the epithelium of
the mouth of j>ersoiis taking one uf ite preparations. Without denying
the pusaibiLity of its existing in a soluble state in the saliva, its iiroseuce
in the mouth may, under such circumstances, be ascribed to the
lodgment of pirticles of subnitrate or subcarbonate of bismuth iu the
interntices of the teeth, etc. It will then be evident that, if a person is
supposed to have been poisoned by a large tloft>e of bismuth, and the
analyst fail to find it in the stomach, the contents of the bowels should
be next examined.
The extraction of bismuth must be undertaken by nitric acid, and
boiling for at least two hours may be necessary to diBSolve it out from
the tissues. Such organs as tlie liver and spleen are boiled in a finely
divided state with a litre of dilute nitric acid (strength, 5 per cent), for
the time me ti tinned, filtered, and the filtrate eva{>3 rated to dryness ; the
remainder is then carbonised by strong nitric acid ; and, finally, the
charcoal is l>oiled with equal parts of nitric acid and water, and
the whole evaporated to dryness. By this method every tmce of
bismuth is extracted. The dry residue may now be brought into
solution and tesited for bbmuth. The beet solvent for the nitrate of
bismuth is dilute nitric acid 50 per cent. ; the dry residue is therefore
dissolved in 100 or 200 c.c. of the acid, and fractional parts taken for
examination : —
(1) The solution^ poured into a large volume of warm distilled water,
gives a crystaHine precipitate of subnitrate of bismuth. The only metal
giving a similar reaction is antimony, and this is excluded by the
method employed.
(2) The filtered fluid gives on addition of sodic chloride a precipitate
of oxychloride. This again is disti nguished from oxycli loride of antimony
by its insolubility in tartaric acid.
§ 8i8.]
BISMUTH.
655
(3) Any bismuth precipitate, fused with aoda on charcoal, gives ft
brittle bead of bismuth. The charcoal iH coated, whilst wartiij a dark
orange-jellow ; on cooling, citron-jellow*
(4) The bead maj lie identified bj powdering it, placing it in a short
aublifuiug tube^ and passing over it dry chlorine. The powder iirst turns
black, then melts t^ an amber-yellow fluid, and finally, by prolonged
heating, sublimes as terchloride of bismuth*
(5) A very delicate test proposed by Abel and Field, in 1863,*
specially for the detection of biimnth tn copper (but by no means con^
fined to mineral analysis), utilises the fact that, if iodide of lead be
precipitated from a Huid containing the least trace of biamuih, instead of
the yellow iodide the scales assume a dark orange to a crimson tint. A
solution of nitrate of le^id is nsed ; to the nitric acid solittion ammonia
and carV>onate of ammonia are added ; the precipitate is washed, and
dissolved in acetic acid ; and, finally, excess of iodide of potassinm is
added. It is said that thus so small a quantity as '00025 gvm. may be
detected in copper with the greatest ease^ the iodide of lead becoming
dark oninge ; '001 grain imparts a reddish-brown tinge^ and *01 grain
a crimson,
(6) A solution of bismuth salt^ which must contain no free HCl, when
treated with ten parte of water, 2 of potassium iodide, and I part of
cinchoniuej gives a red orange precipitate of einchonine iod.-bismnth.t
(7) Van Kobeirs test^ as modified by Hntchings,| and proposed more
especially for the detection of bismuth in minerals, is capable of being
applied to any solid compound suspected of cootaining the metal :— A
mixture of precipitated and purified cuprous iodide, with an equal
volume of fiowerti of sulphur, is prepared, and 2 parts of this mixture
are made into a paste with 1 part of the substance, and heated on a slip
of charcoal on an aluminium support by the blowpipe flame. If bismuth
be present, the red bismuth iodide will suldime, and on dean aluminium
is etisily distinguishable,
Micro-Chemical Test. — Either cti^sinm or rubidium chloride, added
to a hydrochloric acid solution of bismuth salts, gives a double chloride
crystallising in hexagonal tables.
g 8 IB. EstimatioB of Biflmuth,— The eatimatitm of bismuth, when in
any quantity easily weighed, is, perhaps, beat accomplished by fusing the
sulphide, oxide, or other compound of bismuth, in a porcelain croc j hie
with cyanide of potassium ; the bismuth is reduced to the meullic state,
the cyanide can be dissolved out, and the metallic powder washed (hrst
with water, Instly with spirit), dried, and weighed.
* Joum. Chtm. Si>e,t 1^^2| vob liv. \k 290 ; Chmn. Mws, vol %xxvi ^, Mh
t K L<;giir, SulL d^ in S<k. Chim., voL iv. /1 888, 91.
X Chcm. IS^ews, vol, iiivi. p, 249.
656
poisons: their effects and detection.
[| 8i8-
Mr- FattiBou Muir has ehowu "^ tlmt biamuth uiaj be Beparated from
iron, atummLiim, chromiunif and manganeaej bj adding aEunionia to the
aeid solutions of these metalsp
This obsermtiou admits of many applications, and may be usefully
taken advantage of in the separation of bismuth from t!ie nitric acid solu-
tion of such aninial matters as liver, etc. Tlie acid liquid is partially
neutralised by ammouia^ and, on diluting with warm water containing a
little sodium or ammonium chlorid&t the whole of the bismuth is precipi-
tated m oxych bride, which may be ooltected, and fused with cyanide of
potassium, as above*
If the bismuth precipitate is in small quantity, or if a number of
estimations of bismuth are to be made, it is must convenieut to use a
volumetric process. In the case first mentioned, the oxjchlonde could
be dissolved in nitric acid^ sodium acetate added in excess, and sulMcieut
acetic acid to dissolve any precipitate which has been produced, and then
titrated by the following method, which we also owe to Mr. Pattiaou
Muir : —
DBtiinatian of Bismuth by Potassium Bichromate. t — A solution
of recrjstalUsed jxitfiwaium dichromate (strength, 1 per cent,) is
piepaied* A known weight of pure bismuthous oxide (Bi^O^) is
dissolved in excess of nitric acid, and a solution of sodium acetate is
added to this liqnid until a copious white precipitate is thriiwn
down ; acetic acid is then added in quantity sufficient to dissolve the
precipitate completely ^ and to insure that, when the liquid is made
up with water to a tixed volume, no precipitate shall be formed. A
certain volume of this liquid is withdrawn by means of a pipette,
placed in a beaker, and heated to boiling ; the potassium dichromate is
then grailurdly run in from a burette, tlie liquid being boiled between
each addition of the solution, until a drop of the supernatant liquid
gives a faint reddish-brown coloration when spotted with silver nitrate
on a white slab.
Another very generally applicable volumetric method for bismuth lias
been profKJsed by Mr. Jlnir4 This depends on the fact (observed bj
Sonchay and I^ussen),§ that normal bismuth oxalate splits up on boiling
into a basic oxalate of the comjioaition Bh/\2C/X^-^0H.^ but. slightly
soluble in nitric acid. The iirocess is perfornied by precipitating the
bieniuth by excess of oxalic acid, dissolving the precipitate (first purilied
from free oxalic acid) in dilute hydrochlorio acid, and lastlj, titrating by
* Fiittia^n Muir oii "^'Certain Bismuth Compound^,'* Jcuf%. Chem, Soe^, p.
7, 1875.
t PtttiEum Muir ott *' Certain Biflmuth Compaundsi*' Jmtm, Chmu Soe.f p. 65^,
187d.
; Ihid,i 1&77. § ^ntt. Ch^i. Pfmrm.t vol. ev. pi 24S.
§8t9-82i.]
SILVER.
657
perniangauat€. The abaenc€ of free hydrochlorrc acid before precipitating
must be inaured.
Electrolytic Estimation. — An ndherent deposit of bismuth
from the aiilpbate or nitrate^ suitable for quantitative estimation,
may be obtained by diaaolving up to 0*6 grui. with 3-4 grms. of
carbamide or formal deb yde or acetaldehyde in 5-6 c,c* nitric acid
and diluting to 150 g*c, with water ; the solution may be warmed
to from 80'-90' ; the current density Hhould ho tram 0 04-0 08
amp^t^ej aud tiie E.M.F, from 1"5-1'9 volts. The preui pita ted metal
is iraahetl without stopping the current^ and ultimately dried at
100" a*
Karl Wumnenauert uses 1-2 c.c, of glycerol, and lays stress on the
imi>ortatice of agitating the solution constantly (which ia ermiest
effected by using a rotating cat 1 1 ode). Ho rucomtnemk a current of
0*1 amptjre ; tbis, shijuhl indications of pei"oxide be detected, ia
reduced to 0'05 anipt^re. The tem[ierature of the solution 'm to be
raised to 50" and maintained at that tempemiturc.
4. SILVER.
§ 819. Silver=l08; specific gravity, 10%"*^ fustug^point, 1023*
{1873" F,)* — Silver, m separated in analysis, m either a very white,
glitteriug, metallic bead, or a dull grey powder. It does not lose weight
on ignition, and is Hulublo iu dilute nitric add*
§820. Chloride of Silver, AgOl^ 143*5— specific gravity^ 5^552 j
Ag, 75-27 per cent. ; CI, 24 '7 3 per cent.— ^is a dense, white, curdy
precipitate when pro<Juced in the wet way. It is very insoluble in
water, dilute nitric aeid^ and dilute sulphuric atnd ; in many warm
solutions (cHpeeially aqueous solutions of the chlorides generally, the
alkaline and alkaline-eartliy nitnvtes, and tartaric acid solntioufi) the
silver is diBSoUed to an appreoiai>lo extent^ but deposited again on
diluting and cooling. The complete solvents of chloride of silver are —
ammonia, cyanide of potassium, and hyposulphite of soda. Cbhirido
of silver Ciinnot be fused at a high heat without some slight losi^ by
volatiiisation ; on charcoal in the H*F., it fuses very easily to a globule.
It can with soda be reduced to metal, and can also readily be reduced
by ignition iu a current of hydrogen, carbon oxide, or carburetted
hydrogen gas*
§ 821, Sulphide of Silver, Ag.S ^ 248-^pecific gravity, 7 '2 ; A*^, 87' I
per cent ; 8, 12-^ per cent. — when pivpared in the wet way, is a black
precipitate, insnluble in water, dihito acids, and alkalitJe sulphides. I f
* Dmitry ItalAchowaky, UmnpL Mmd,^ exxsi. 19O0.
i ^iL tuufrijuti^ Chrmtft %\v\L 1901*
42
658
POISONS: THKIR EPFECTB AND DETECTION,
[§ 822-
ignited in hydrogen it may be reduced to the metalLic state ; it is soluble
in nitric acid, with separation of sulphur.
§ 822, Freparationfi of Silver uBed in Medicine and the Arts.
(1) Medicinal Preparations: —
Kitrate of SOver, AgNOj,; Ag, 63'5] per cent, j l^^O^, 36-49 per
cent. — This salt is oither sold crjutallised in coloarlcse rhombic priamB,
or in the foimof small white pencils or sticks. It gives the reactions for
silver and nitric acid, and stains the skin bliick. 100 parts, dissolved in
distilled water, should give, with hydrochloric acid, a precipitate which^
when Wflshed and dried, weighs 83 "4 parts. The silver is, however, far
more f^uickly estimated by the blowpipe than in the wet way. One grm.
fused in a cavity on charcoal should give a little globule of metallic
silver, weighing about *6351 grm. The chief adulteratious of tbia
substance are copper, lead, and nitrate of potash. If all the silver is
precjpitrtted by hydrochloric acid, carefully filtered oflT, and the filtrate
eva(>orated to dryness, any residue will denote adulteration or impurity.
Argeuti Oxidum, Oxide of Silver, Ag/}^232; Ag, 9319 per cent.
— A diirk olive-lirown powder, soluble in ammonia and nitric acid. By
ignition it readily yields metallic silver. The P.B. directs that 29 grains
of the oxide should yield 27 of metallic silver*
Nitrate of Silver and Fotasb (Argentum mtricum cum kali
nitrico), AgNO-^+KNOg. — This preparation is in moat of the pharma-
copoeias^ Austrian, German^ Danish, Swedish, Russian, Swiss, and the
British ; it is directed by the B.P. to be composed of 1 part of silver
nitrate and I part of jmtassic nitrate fused together, A "toughened
silver nitrate"' ia made by fusing together potassic nitrate 5, silver
nitrate 95, MiH caustic points are u«ed by oculists by fusing 1 of
silver liitrate with "2^ 3, 3i, and 4 parts of potassic nitrate*
(2) Silver in tlie Arts. — The uses of the metal in coinage, articles for
domestic purposes, for omamentj etc,, are too well known to require
enumeration. The only forms in which silver is likely to give rise to
accident are the salts used in medicine, photography, iu the dyeing of
hair, and in the manufacture of marking inks,
Hair-Byes, — About one half of the hair-dyes in use are made with
nitrate of silver. The following are only a few of the reci^>es :^
Aqua Orientalifl, — Grain silver 2 drms*, nitric acid 1 oz*, steel filings
4 drms,, distilled water IJ oz. — the whole finally made up to 3 J fluFd
07M.J and filtered*
Argentan Tincture. — Nitrate of silYer 1 drachm, rose water 1 fluid
oz., suffieient tiitrate of copper to impart a greenish tint
Eau d'Airiqtie. — Two solutions — one of nitrate of silver, the other
of potash, containing ammonium sulphide.
§ 823. 8240
SILVER.
659
The photographer u&e^ varions m\tn of silver, the chief of which are
—the nitrate, iodide, bromide, cya-nide, and chloride of silver,
Maxklng-InkB. — Some of the more important recipes for marking-
ink are as follows : —
Nitrate of silver, 1 ^0 part ; hot distilled water, 3*6 parts ; mucilage,
previously rubbed with sap-green, 1*0 part. With this is sold a " p<3unc€>,"
or preparation cotisisting of a coloured solotiou of sodic carl>onate.
Another preparation is very similar, but with the addition of ammonia
and some colouring matter, such as indigo, syrup of buckthorn, or sap-
green. A third is made with tartaric acid and nitrate of silver, clis-
iolved in amniouia solution, and ooloured.
Bedwood'B Ink consists of equal parts of nitrate of silver and potns-
sic bitartrate, diaaolved in ammonia, with the addition of archil green
and sugar J according to the formula^ 100 parts should equal 16*6 of
silver nitrate.
Soubeirail*8 Ink is composed of cupric nitrate 3, argentic nitrate 8,
eodic carbonate 4, and the whole made up to 100 parts, in solution of
ammonia. In one of Mr. Reade's inks» besides silver, an atnmoniacal
solution of a salt of j^fold is used.
g 823* Medicinal Dose of Silver Compounds.— The nitrate atid th«
oxide of silver are given in doses from '0163 to "1206 grm, (J grain to 2
grains). Anything like '1944 to "2592 grm. (3 or 4 grains) would be
considered a large^ if not a dangerous dose ; but nothing definite ii
known as t-o what would he a poisoncms dose.
§ 824, Effects of Nitrate of SUver on Animals. — Nitrate of silver
is changed into chloride by the animal fluids, and also forms a eom-
pound with albumen. Silver chloride and silver albuminate are both
somewhat soluble in solutions containing chlorides of the alkiilies, which
explains how a metallio salt^ so rery insoluble in water, can be absorbed
bj the blood.
The action of soUible salts of silver on animals has been several times
inv^tigated. There appears to be some difference between its effects on
warm- and cold-blooded animals. In frogs there is quickly an e^Ealtation
of the functions of the spinal cord ; tetanic convulsions appear^ similar to
those induced bj strychnine ; later, there ia disturbance of the respiration
and cessation of vohiutary motion.
The first symptoms with dogs and cats are vomiting and diarrhciMi ;
muscular weakness, paralysis, disturbance of the respiration, and weak
clonic convulsions follow, Houget^ as well as Curci, considers that the
action of silver is directed to the central nervous system ; there is first
excitement, and then follows |Kiriilysis of the centres of respiration and
movement* Death occurH through c^entral asp!iyjtla» According to the
rtjsearuhes of h\ A. Falck, subcutaneous injections of sUver nitrate into
66o
POISONS: THEIH EFFICTB AND DETS!CTION, [§ S25, 826,
rabbits cause a fall of teniperature of 6^7* to 17*6'', the last being the
greatest fall which, in hia uutiiorous rescarchtja on the effect of poisons on
tamperature, he ha.s ae€n.
Chronic poisoning, according to the experiments of Bugoslowsky on
animals, produces erauciation, fatty degeneration of the livery kidneys, and
also of the muscles — a statement confirmed V>y others.
g 825. Toxic Effects of Silver Nitrate in Han— (I) Acute Poifion^
ing^^Thia is very rare. OrJila relates an attempt at stiicide ; but moat
of the cases have been aecideotiilj and of these, in recent times, al>out
five are recorded, mostly children. The accident is u*iually due to the
application of the ^lid nitrate to the throat, as an escharotic, the
stick breaking or becoming detached, and being immediately a wallowed j,.
such an accident is related by Seattergood.* A piece of silver nitrate
I inch long, slipped down the throat of a child, aged fifteen months-^
vomiting immediately oecurred, followed by couvulisionH and diarrhcea ;
chloride of sodium was administered, but the child died in six hours. In
other ciisea fmmlysis and an unconscious state has been ohaervod*
(2) Chronic Foisomng, — Salts of silver taken for a long period cause
a pGcn liar find iiideli hie colour of the skin. The body becomes of a grey ish-
blue to black colour; it begins first around the nails and fingers, then
patches *»f a similar hue appear in different partii of the body, and
gradually coalesce, being most marked in those parts exposed U) the liglit
The colour is not confined to tbe outer skin, but is also seen in the
mucous membranes. There is also a slight inflammation of the gumi^
and a violet line around their edge. Ginpoii observed this line after two '
months^ treatment of a patient by silver nitrate ; the whole quantity taken
beinx 3 '9 grms. (about 60 grains). The peculiar colour of the skin is
only seen after large doses ; after 8 grms, taken in divided doses Clmillon
could not observe any change, but after 15 grins, had been taken it was
evident. So also Riemer has recorded u oise, in which, after a year's use
of silver nitrate (total quantity 17*4 grms.), agreyish-hlack colour of the
face was produced, and, when nearly double the quantity had been taken,
the colour had invaded the whole iHxdy.
§826. Post- mortem Appearances.— In the acute case recorded by
Sc^ttergood, the mucous membranes of the gullet, of the great curva-
ture of the stomach, and parts of the duodenum and jejonum were
eroded, and i>articles of cunidike silver chloride adhered to the mucous
nicmbnine.
In the case recorded by h'ienier of the long-continue<i uae of silver
nitrate^ the serous and nmcons ntembranos were coloured dark ; the
chorcud plexus was of a blue-black ; tlie endocardium, the valve,s of the
heart, aiul the aorta pale tu dark grey, as well as the rest of the vessels ;
• Brtl Jf^Mjf, Juitm., U&y 1871.
§ 827-]
SILVER.
66r
the t!olouriug was confiuctl to the intima. The liver and kiiiney alsn
showed similHf pigmentation. The pigment (probahly me tall ie silver)
was in the form of vety fine grains, and, as regards thc^ skin, was situate
under the reie Malpighia in the upper lajer of the corinni, and abo in
the deeper connective tiasne and iti the sweat gluiKis* Ltouville baa
also found the kidnejs of a wmiiaii similarly pigmented, who took silvor
nitrate daily for 270 dnjSj in all about 7 grms., five years before her
death.
§ 837, Detection and Estimation of Silver,— The examination of
the solid salts of silver usually met svith (viz.^ the nitrate, bromide,
iodide, cyanide, and chloride) is most speedy by the dry metbofi on
uharcoal ; in this way in less than 1 20 seconds any practicul ehemist
could identify each compound. The nitrate, bromide, iodide, and
eyanide, all, if ignited on charcoal, yield buttons of metallic diver —
deflagration, bromine vapours, itxline vapoursj and cyanogen vapour?
being the respective phenomena observed. Chloride of silver fuses to a
pearl-grey, brown, or black globule on charcoal, according to its purity \
but is only in the R,F. gradually reduced to metah With soda, or fused
in hydrogen or coal givs^ the reduction is rapid enough.
Nitrate of Silver in golutioo might be identiBod by a very large
number oF tests, fliuce it formss lo many insoluble salts. In practice one
is, however, satisfied with three tes^ts, viz.: (I) A curdy precipitate of
chloride, on the addition of hydroehloric aeid or alkaline chlorides, 8<duble
only in ammonia, cyanide of potassium, or hyposulphite of soda; (2) a
yellow predpitate^r but little soluble in ammonia, on the addition of
iodide of potassium ; and (3) a blood>red precipitate on the addition of
ebromate of potash.
The separation of silver from the eon ten ta of the atomach is best
ensured by treating it with cyanide of puta^tum ; for» unless a very
large quantity of silver nitrate haa been taken, it is tolerably cert*iiu
that the whole of it has passed into chloride, and will, therefore, not Ijc
attacked easily by acids. The contents of the stomach, then, or the
tissues themselves, are placed in a flask and wanned for some time with
cyanide of potassium, first, if necessary, adding ammonia. The fluid is
separated from the solid matters by subfttdenee (for an alkaline fluid of
this kind will scarcely filter), and then decomjioaed by hydrochloric acid
in eiccess. The flask containing this fluid is put on one side in a warm
place, and the clear fluid decanted fiom the insoluble chloride. The
latter is now collected on a filter, well washed with hot water, and then
dried and reduced on charcoal ; or it may 1)6 put in a little porcelain
crucible with a rod of jsinc and a few drops of hydroehloric acid. The
ailver is soon deposited, and must be washed with water, then with
sulphuric acid. By the aid of a wash-bollle the [lartigles of silver arc
662
POISONS: TBEIH Ei^KEOTS AND DKTKCTION. [§ 828--83O.
now oollecbed on a Bnmll filter, agaiu waf^hedj aud ou the oioi^t mass a
crystal of nitrate of potaBli and a littla carhonate of scKla laid. The
whale ig then tlrii?dj und all the filter cut away, m.\e the ^mall portion
cou tail dug the aitver. This small portion is now heated on eliarcoal
until a little button of pure silver is obtained, which may first be
weighed, then dissolved in nitric acid, and tested by the methods
detailed.
In a alnular way hair, suspected of being dyed with sLlver, can be
treatetl with chlorine gas, and the chloride ilissolved in potasstc cyanide.
Splits 011 liiieUj and, generally, very small quaiititieB of silver, may
be detected by a simple galvanic process : — The substance is treated
with solution of cyanide of potassium, and Kuhmitted to a weak galvanic
current, using fur the negative plate a slip of copper, for the positive,
platinum ; the silver is deposited ou the former.
5. MERCURY-
§828. Mercuiy, Hg = 200.; specific gravity, 13^596; boiling-point,
350' (662' F.) ; it becomes solid at - 39 '4 ( - 39 F.). This welMcuown
and familiar Huid metal evaporates and sublimes to a minute extent at
all temperatures above 6*,
When precipitated or deposited in a finely divided state, the metal
can be united into a single globule only if it is fairly pure ; very slight
fatif/ impurities especially will prevent the union. It is insoluble in
hydrochloric acid, soluble to a slight extent iu dilute cold sulphuric
acid, and completely soluble iu concentrated sulphuric and in nitric
acids. It combines directly with chlorine, bromine^ and iodine, which
iu presieuce of free alkali, readily dissolve it. It m unalterable at 100",
andy when exposed to a high tempeniture, sublimes unchanged.
Mercurous Chloride {Calomel, HgCl = 235*5 ; specific gravity,
7'178 ; subliming temperature, 111*6"; Hg, 84'94 per cent., CI, 15*06
per cent*), when prepared iu the wet way is a heavy white powder,
absolutely insoluble iu cold, but decomposed by boiling water. It may
be converted into the mercuric chloride by chlorine water and aqua
regia. Chloride of ammonium, potassium, and sodium, all decompose
calomel into metallic mercury and mercuric chloride. It is easily
reduced to metal in a tube with soda, potash, or burnt maguesia.
g 829. Sulphide of Mercury (HgS, Hg, 86^21 per cent., S, 13'7D per
cent.) is a black powderj dissolving in nitromuriatic acid, but very in-
soluble in other acids or in water. It is insoluble in alkaline sulphides,
with the exception of po tussle sulphide.
g 830. Medicinal Preparations of Mercury. — Mercury in the liquid
state has been ocoaaionally administered in constipation; ltd Internal
830.]
HKBCDBY.
663
use is uow (or ought to be) obaolote. Gtiielm has found sampleEi con-
tamiuated with metiillk bistuutLi — a metal whichouly slightly dimiumhes
the fluidity of mercury ; the impurity Diay be detected by shaking the
mercury in air, and thua oxidising the bismuth. Mercury may also
coutaiu various mechaniciil impurities, which are detected by forchig
the metal by meaus of a vacuum pump through auy dense filtentig
substance^ Tin and zinc may he dissolved out by hydrochloric acid, and
all hxed impurities (such as lead and bismuth) are at once discos e red
on subliming the metal
Mercury and Chalk (Hydrargyrum cum ere ta).— Mercury, 33*33
per oeiit ; chalk, 6 6 '67*
Blue Pill (Piliila hydrargyri). — Mercury in a finely divided ^tate,
miaed with confection of roses and liquorice root ; the mercury ijhould
be in the proportion of 33*33 per cent,'"'
Mercury Flaster (Emplastrum hydrargyri). —Made with mercury,
olive oil, sulphur, and lead plaster; it should contain Hg 33 per cent.,
sulphur IS per cent.
Ammoniac and Hercury Plaster (Emplastrum a^nmoniaci cum
bydrargyro). — (tuui, amaionia, juercury, olive oil, uud sulphur; it
should contain 20 per cent, of H^, and *1 per cent, of sulphur.
Mercurial Ointment ( Unguent um hydrargj^ri). — Mercury mixed
with lard ami ttuet ; the strength should be nearly 50 per cent, mercury
— commercial iaaniples often contain as little m 38 per ceot.
Compound Mercury Ointment (XTnguentum hydrargyri composi
turn ).^ J lade with ointment of mercury, yellow wax, olive oi], aud
camphor ; it should contain !2'2*2 i>er cent. Hg.
Liniment of Mercury (Liuimentum hydrargyri) is made of
mercurial ointment^ solution of aumiouia^ aud liniment of camphor i it
contains about lOi-per cent, of mercury*
Mercurial Suppositories (Suppositoria hydraiTgyri).--CouipoBed of
' The uheuiiciil <^ompcKiitiuu of blue pill varies according to its age* Huruld
Senier 1ms niadi) & c&r^fal series of ftaatj^sia, with the following reault {Pimrm,
J<mni., F«h. 5, 187e) ;—
A«..
Bieunic
M«rciirio
MsrcurolLi
Ath.
Offanlc
Mercuij^.
Oitlde.
OxLd».
Umcer.
1
18 hmra,
3^*49
aooeu
A trace.
1*20
66-31
2
S weeks.
32-2(S
•Oft
*2&
1-20
66*20
3
S moDtb«, .
31*60
-24
'62
1-18
fie*3ti
4
3 „ ■
31 i 6
-44
1*60
112
6.V69
0
6 ,, ^ .
32*44
'50
'80
1-70
fl4'S6
f
U ., , .
29 gS
n
2-60
1*20
6&'3e
7
Id M . '
ai-5&
'50
2 '60
I'OO
d4'4l
8
2 ytrars,
28*40
vm
4-22
2-10
63*48
ft
0) ^ .
30-23
1*06
3-24
1-OS
6444
664
POISONS: THEIR tEPRKUTS AND DKTKCTION.
[§ 830.
ointDient of mercury and oil of theobroma* Each suppository should
weigh 15 gmitis and contain j of its weight of mercurial oiutracut.
Acetate of Mercury (Mercurona acetate) la not contaiued in the
B.P.J but ib ulhcimil ou the Continent. It i« a salt occurring in white
micaceoun goalee, aoluble in 133 pari^ of cold water^ giving the reaetioiig
of ticetic acid and mercury, atid very readily flecom[>osed.
Mercuric Ethyl Chloride (Hydrargyrnin ©thylo-cMoratum) isu&etl
as a medicine on the Continent. It oceurs in white, glittering, erystal-
liue scales J which take on pressure a metallic appearatice, and possess a
peculiar ethereal odour; it is but little soluble in water and ether, with
difficulty in cold alcohol, but ct>pioualy soluble on boiling', and depositing
crystals ou cooling. It sublimes at about 40* without residue ; on
quick heating it burns with a weak flame, developiog a vapour of
metallic taste and ?jopleasant odour. It gives no precipitate with silver
nitrate nor with albumen.
Corrosive Sublimate (Mercuric chloride^ HgCljj=^271; Hg^ 7S"8
per cent. ; 01, 26-2 per cent. — In commerce this salt occurs in trans-
parent, heavy, colourless nmasei}, which have a crystal line fracture ; if
placed in the Eiubliming cell dcc^cribed at p, 260, it sublimes at about
82'2'* (180" F.), and melts at higlier tenipcraturcs* The sublimate is
guuerally in groups of plates drawn to a point at botli euds, in crystalline
needles, or in octahc<Jra with a rectangular base. It dissolves in 16
parts of cold water and about 3 of boiling, and is very soluble in
solutions of the alkaline chlorides; 100 parts of carbon disulplnde
dissolve '031 at S" ; *055 at 25*. One part of sublimate dissolves in
14 parts of glycerin. Acetic ether, methylal, and beuKeue all dissolve
to some extent corrosive sublimate ; it dissolves also in etlier, and can
be, to a great extent, withdrawn from aqueoita Bolutions by this agent.
Alcohol dissolves ni^rly one- third its weight of the salt, and its own
weight when boiling. It coralmies with albumen^ gives, in solution, a
precipitate of mercuric oiide when tested with solution of potash, a
white preciijitate with ammonia^ a scarlet with iodide of potassium,
and a black precipitate of finely divided mercury with prgtotthlorido of
tin. If a crystal (when placed in the subliming cell) gives a orystallino
sublimate at about the temperature mentionedj and this subliniate
becomes of a red colour when treated with a droplet of iodide of
[jotassium, it can be 00 other substance than corrosive sublimate.
Solution of PercMoride of Mercury {Liquor hydrargyri per-
cbloridi) is siiuply 10 grains of perch loiide of mercury and chloride of
ammonium in a pint of water; 100 c.o, therefore should contain 144
ingrms corrosive sublimate.
Yellow Mercurial Lotion (Lotio hydrargyri fiava), — Perchloride
of mercury^ IB grains, mixed w^ith 10 ounces of solution of lime.
§83^]
MKRCURT,
665
Calomel * (Hydrai'gyri siibchloiidiim). — The properties of t^lomel
have been alrefidy ilejsctib^ad. It Komethut\'j contains aa an impurity
corrosive sublimate, which may be dissolved out by ether, Carboiiitte
of lead, Bulpltatc, and carbnuate of baryta, gum, iind starch, are the
uEjual adnlterants mentioned. If ou ihe application of heat cjilomol
entirely subllmeB, it muBt be free from the aiib^tancea ennmerated.
Oleate of Mercury (Hydrai^yri oleattmi} j^ composed of 1 part of
yellow oxide and 9 part« of oleie ncid.
Black Mercurial Lotion (Lotio bydrargyri nigra),— (;alomel» 30
grains, mixed witli 10 flnid ounces of lime* water.
Compound Pill of Subcldoride of Mercury, — Calomel and sulphur-
ated antiniuuy, each 1 ounce, gnaiac resin 2 ounces, caator-oil 1 fluid ounce.
One j^raiu (0648 grm,) of calomel, and the same quantity of antimony
sulphide, are eoutained iu every 5 grains (324 mgrms-) of the pill mass,
ue* calomel 20 per cent.
Ointment of Subchloride of Mercury (Unguentiun hydrargyri
subchloridi), — Calomel mixed with benaoated lard ; strength about
I : 6i.
White Precipitate (Hydrargyrum ammoniatum, NH^HgCl).— A
white, heavy powder, enbliming by heat without residue, and insoluble
in water, alcohol, nnd ether. With soda, it yields a metallic sublimate.
When boiled with pot^ish, ammonia is evolved, the yellow oxide of
mereury formed, and chloride of potassium passes into solution. It
should contiuii 79 5 per cent, of meruury.
The fusible white precipitate of the pharmacopceia of the Nether-
lands does not appear to be of constant composition, varying between
6^ '4 to 65 '6 per cent, of mercury, t It melts on heating, and leavci* aa
a residue chloride of sodium.
Commercial white precipitate is frequently adulterated ; Barnes has
found carbonates of leiul and lime, the latter to the extent of nearly 2 per
ceut-l Calomel, according to NiGklcs,§ has been substituted for white
precipitate, but this waa seyeral years ago. The methods for detection
are obvious.
Ointment of Ammoniated Mercin-y (Unguentum hydrai-gyTi am^
moniati). — 1 part of ammoniated mercury tniied with 9 parts of simple
ointment.
Eed Iodide of Mercury (Hydrargyrum iodidum rubrum, Hglg), —
A crystalline powder of a scarlet colour, becoming yellow ou gentle
• It \*ould dpinair that in America a cusmetic ii in ase, o^mslsttng of oiloniel
mixed i&to a [mata witli water. — Fide **^ Dangeroiis Cosmetic/* by C, IL PiMni
^fiaipl(^5)« 1S7S, {1. 24!.
t HirtMih, Die FrU/ung dcr Arten^imUid*
t Proceed. BrU. Pfttmn Omf,^ lg«7, \k 10.
I Jcmm, PhurtiL H (him., !e Sitip, 1S&8, v.L viij. [>, 3&0.
(566
POISONS : THEIR EKFEXITS AND DETECTION.
[§830.
heaiiug. It is spariDglj Bobible in water, one part requiring from 6000
to 7000 pjirts; tiolable in 130 parts of cold, 150 of bot alcohol; and
diBKolviug freely in etber, or in a<iLieous solution of itfdide of pofcaetsiuiu,
Ointtuent of Bed Iodide of Mercury (Ungueutum hydrarg^ iodidi
rubri), — 16 grains of the aubstanee mixed wttb aii ounce of simple
ointment*
Green Iodide of Mercury (Hydrargyri iodidum viride, HgI).^A
dingy, grt'etiiah -yellow powder, darkening on exposure to light, and
eawily ti'ausformed by heat into the red iodide.
Red Oxide of Mercury (Hydrargyrl oxidum rubnim), UgO = 216;
Hg, 92"12 per cent.j specific gravity, 11 to 11*3; Bnmll, red, shiniDgj
crystalline scales, slightly soluble in water, requiring about 20,000 parts ;
entirely sohible in hydrocbloric acid. By a heat below reduess it may
be volatilised, and at the same time decomposed into mercury and
oxygen. Its principal impunty is nitric acid, readily detected by the
UKUal tests, or by heating in a teat-tulje, when, if nitric acid is present,
orange vapours will be evolved. Fixed red powders (such as brick-dust
and minium) are detected by being left as a residue, after the application
of beat sufficient to volatilise the mercury. An ointment {strength 1 : S)
is officinal.
Sulphate of Mercury.^ A white crystalliue powder, eon verted by
water into the very filightly soluble bsisic salt of mercury, known as
Tityhifh mhiernl, HgSO/JHgU
Turbith, or Turpeth, Mineral is contained in the French pharma-
copoeia, lIg80^2HgO^ Hg, i<2'i per cent; specific gravity, 8*319. It
requires for solution 2000 piirts of cold and COO of boiling water, but
dissolves with tolerable ease in bydrochloric acid.
The Sulphide of Mercury, known in commerce under the uame of
Kthiofit vdncralt is officinal in France, the HetberlaiidB, and Germany-
Its properties have been already described. The German aud Dutch
pharmacopoeias require in it 50, the French only 33 1 per cent, of
metallic mercury.
Halmaman's Soluble Merciiry (Hydrargyrum solubile Hakuemamii)
is officinal in the Dutch pbarmacopcaia. As found in commerce it aoa-
tains metal he mercury, nitric acid, and ammonia. The mercury should
be in the prajxirtton of ^6 33 per cent., the ammonia ii'44 per cent.
CrystalUsed Nitrate of Mercury (Hydrargyrum nitiicum oxidu-
latum) is officinal in the pbarmacopo?ias of Germany, Swiuerland, and
France, The SiUt is in white crystals, giving the reactions of nitric acid
and mercury, decomposed by the addition of water, but fully soluble in
water, if first moistened with nitric acid, Tbe formula of the neutral
salt is Hg2NOjjHg02Hj>0, which requires 694 per cent, of mercury.
An acid solution of merctinc nitrate is officinal
§S3Kl
MKRCDRT,
667
An Ointment of Kitrate of Mercury (Uitgueiitiiiii hydrargyri
iiiti*atis)^ofteQ called citrine uiutmeut — m contained in the E.P. ; it ib
mad a with 4 parts of meruury, nitric acid 12, krd 15, olive oil, 32; the
itreugth is ahout 1 in 15|.
A Chloride of Mercury and ftuinme exists in commerce, prepared
by mixing I part of corrosive aubUmute lu solution with three parts of
quinine chloride^ evaporating, and crystallising.
Cyanide of Mercury, HgCy, h contained in the French pharmar
Gopcuia. It occurs in Hmali, colon rlesis, pri&rLiatic crystals, easily soluble
in water, I f to the solution chloride of tin be added, a black prei^ipitate
of reduccKi metal and stannous oxide ia thrown dowti, and the odour of
prussic acid is developed.
Mercuric Sulphide (Sulphide of Mercury, Cinnabar, Vermilion) is
officinal in Germany, the Netherlands, and France ; HgS = 232 ; apecific
gravity, solid, 8"2^ Hg, 86"21 percent, 0, 1379 per cent. For medicinal
purposes it is made artificially. It ih a beautiful red powder insoluble in
all alkaline and all acid liquids, with the exception of aqua regia. The
solution gives the reactions of a t^ulphide and mercury. On heating, it
must burn away entirely without residue ; adultemtions or impurities
are— minium, lead, copper, and other metals. The detection of minium
is conveniently executed in the dry way. Pure cinnabiir, when heated
in a matmss, gives a black sublimate, which becomes red on friction*
If minium is present, sulphide of lead remains as a residue, and may he
recognised on coal ; the s^ime remark applies to sulphide of antiuKJny,
[f it lie desired to take the percentage of mercury in cinnabar, etjnal
imrts of oxalate and cyanide of potassium shuuld he well mixed with
the cinnjibar, and heated in the bent tube described at p. 685 ; by this
means the whole of the metallic mercury is readily obtained,*
§ 83L Mercury in the Arts. — The use of mercury in the arts is so
extensive, that any one in analytical practice is almost certain occasion-
ally to meet with eases of accidental poisoning, either from the vapour t
or some of its combinations.
Quicksilver is used in the extraction of gold, the silvering of mirrors,
the construction of barometers and various scienliHc instruments and
* Dr, Sutt'o hws pi]blished a case (quaU<d by Taylor), iti which the vapour of
V(*n]]i1ion, ai^ilied exterimlly, prfxluc«d [loisonona symptoms ; yi^l, aecotditig to
Pobk, the PersiaDs inhale it medipinallyr uaokiiig it with tc»boc€o, <»teobu, mud-
lager ^tc. , tb<» only bid effect being an oocafiien&l aloiji&titis. — Etilt^nberg, Getcm^
H^gitn^i p. 741,
t A sitigular oaae h cited by Tardieu {Mud* mM^'Ugai sur PEmpoiiojimemimt}f
ID wluch A timn, &nptK>diag he had ^ome miuerali ooutaiijing gpld, attempted the
exti'actioa by amalgamation with merottry, H« wted m portable funmee (fi>r the
purpart} of volatiliaing thu uivircary) in a. fimall room, and liis wtfe^ who assisted him,
fiulTcrod from a very wuU -marked stomatitis aud marcuml eruptiou.
fy6R
rOTSHNS: THETB EFFKCTTS AND T»KTEOTTON.
[§ 832.
ripplinnct's ; alno for the preaervatiou of insects, and ociyisionally for tlieir
destnictiou,'^ Au alloy witLi ziuo aud cadmium m employed by dentists
for stopping teeth ; but there is no evidence that it has bueti at all
injurious^ the mercury, probably j being in too powerful a state of com- '
binatioD to be attacked by the fluids in the mouth, f Cimiabar haa
ako been employed to give a red colour to confections, and it may be
found in tapers, cigarette paperSi and other coloured articles. The
nitrate of mercury in solution finds application in the colouring of horn,
in the etching of metals, iu the colouring of the finer sorbs of wool, Aud
in the hat manufacture.
The snlphooyanide of mercury givesi when burnt, a moat abundant
aali, a fact utilised in the toy known as Pbaraoh*s serpent ; the products
of combustion are mercurial vapours and anlphurons anhydride. That
the substance itself is poisonous is evident from the following experi-
ment!— '5 grm. was given to a pigeon without immediate result; but
ten hours afterwards it was indisposed, refused its food, and in forty
hours died without convulsions.!
§ 832, The more Commoa Patent and ftuack Medicines
coiitaining Mercury.
Mordant's Norton^B Ihropa. — This patent medicine its u niiiture of tlie tincture
of getiiicfci) ^nd giugBr, holding in aolntlon n little Vichloride of mercuiyj and col oared. |
with coclnncal,
Salomon^i A&ti-impetiginee ia a solution of bicblonde of mercaiyf Hflvoured
and colouretfj*
Poor Mftu*B Frietid^^Au ointmeiit of nitratii of morcuty.
Brown's Lozenges. ^Kacb lozengo contains | gmin of e4Llomel^ dud 3} grains of
maiaous extrii^^t of jaL^p - ttiti rust m white sug&r jiod tragsojinth.
Ohiiig'« Worm Lozenges. —E^h lo?^nge contains 1 grain of calomel ; the rest
whiU HUgnr u.nd tragacanth, with Ealfron &» a co^ouriEig matter.
Storey^a Worm C^kes. — Kacli cake contains 2 graina of cUomelg 2 grains of
ciimal^ar^ 6 >;i-ain<4 of jakp, & gruiDS of ginger, and the remainder sugar and water.
Wright's Pearl Ointitient is said to be tnadc up of 3 om. of white precipitate
rulibcKl Ui IS cream hi I (liiit of Ooulard^a extract, &nd Uj the mixtnrc is ftddcd 7 lbs.
of white wa:x: and 10 lba» of olive oil.
Eeysor'a PiUe. ^The receipt for tbeae piUa is — red oxide of niereuij 1 4 o*. , dis-
tinixi vinegar (dilute acetic octd) I pint ; dis^lve^ add io the resulting solution
manna 2 lbs. , and triturate for a long time before the ft re until a proper conBist^ncc
ifi attained ; kstLj, divide the mass into pilla of 1^ grain eaclu
Mitcholi'a Pilla» — Each pill contains aloes 'S grain, rhubarb 1'6 grain, calomel
'16 grain, tartar emetic '05 grain.
Many Antlbillonfl PtUa will bo Ibuad to contain calomel, a few tnercnry in «
finely divided state*
* Forty- three |>ersone were salivated frtim fnmi^'ating rooms witb mercury for the
purpo&e of destroying hugs (Senncnachmn's EAJtdbuch, p. 96),
1' Mor« diinger is to be apprelionded from the vulcaniBi^d rubber for artilioial
tet^tb ; and| according to Dr. Taylor, accidents have uccurrod from the uae of ^uch
supports or pUtea, :; Eulonherg, op. cit,, p, 472.
§ 3??-85>] w«?.'. n «x>
lor tibe fj. Azii vTiiusoTe p:wrr^«£ :c jc«kc *£&£ tif^c :=. ^tfTenl
emn lo d» -wbsK &:S£cu«i '-t *&* ifsce^r^r. ^rr^ruiS. cr the
U> its potfrioiGS cf f:*:?a.
I 8^ Miwftrinal ad Falsi Hase— Honn.— Ci-xarar l4-e enii&
(4 QOLi, eal<jffz>el l4-f ztz:j^ ^ -m. or =j:re. .xrr:e:TT >":irI:niA:e -15 to
"38 gnn. i2 :o o gr&izxs ;. izti aa ^sr^tz, \s I'o jnii. f>j -rrauijS' have been
giTen in iftjcr.
Cattle. — Merrorr wiih ch&Ik 3-5 w 11-5 firrnisw 1 :*> 3 'lrra*.K
calomel 3-d to 7 7 jtojs. 1 m- 2 inxi=. fir ttths : -65 to IS ^.ttii. (10
to 20 gnins) as an alteratf re : £th>jps n^nemL 7 7 to 15*5 ^rmis. ^'J to
4 dnUb).
BogB. — Ethiops or Turperh minend -13 to 1*3 gnn. 1 2 to 20 grains),
aoooiding to the siie.
Fowia. — Mercurr and chalk are giTen in fractions of a grain.
Hoga are also treated with mercury and chalk ; the d«.>60 usually
given does not exceed -32 gnn. (5 grains ^
It may be remarked that many of the doe>es quote<i api>oar very
ItLTge ; the writers cannot but consider th:it 20 grains of corrosive sulv-
limate administered to a h<irse would be more likely to kill the aninml
than to cure the disease.
Man. — Corrosive sublimate has been fatal in a dose so smull
as '19 gnn. (3 grains); white precipitate has rauseil dunizorous
symptoms in doses of from 1*9 to 2*6 gnn. (30 to 40 grains); the
cyanide of mercury has killed a person in a dose of 'tU grni. (10
grains) — Christ iaon ; and Turpeth mineral has proved fatal in doses
of 2*6 grms. (40 grains).
Other preparations of mercury have also been fat^il, but a doubt has
existed as to the precise quantity. Sometimes, also, there is proluibly a
chemical change in the substano,e, so that it is impossiblo to state tlio
fatal dose. For example, it is well known thiit ealoinol, \nuior the in-
fluence of alkaline chlorides, can be converted into the bichloride — a
fact which probably explains the extensive corrosive lesions that have
been foimd after death from large doses of calomel.
§ 835. Poisoning by Mercury — Statistics.— In the Uogistmr-
Gcncrars death returns for the ton years ending 190.*^ it apptnirK thut
* Twenty-five tons of blue ointment are said to liave Iwcn hoM to rarnit<i-s by u
diiiggist in Boston, Lincolnsliirc, in the course of a Kiiiglo yoar.- Trtybn*M .1M/iV«i/
Juriifprudencey vol. i. p. 279.
670
POISONS 1 TEEIR EFFICTS AND PFTKCTION.
[§836,
in England the tlco-ths from rn ere u rial poiaouing * were 62 maleB,
35 females ; of these, 48 males and 18 females were cases of suicide,
the remainder were referred to accident.
g 836, (1 ) Effects af Mercurial Vapour, and of the Non CorrogiTe
Compounds of Mercury,
The effects of the difterent compounda of mercury may be divided
into two groups, viz, * (1) Those caused by the finely divided metal and
the non-con-osive compounds; (2) the effects caused by the corrosive
compounds,
(a) Vegetable Life. — Priestley and Bousaingault have shown that
plants under a glass shade in which mercury ia exposed in a saucer,
first exhibit black spots on the leaves ; ultimately, the latter blacken
entirelyj and the plants die.
(b) Atumal Life, — Mercury in the form of vapour ia fa till to animal
life, hut it in only so hy repeated and intense application, Eulenberg t
placed a rabbit under a large glaas shade, and for four days exposed it
daily for two hourj^ to the volatilisation of 2 grms. of mercury on warm
sand; on the sixth and seventh day 1*5 grm. was volatilised. On the
fifteenth day there was no apparent change in the aspect of the animal ;
5 grms. of mercnry were then heated in a retort, and the vapour blown
m at intervids of ten minutes. Fourteen days afterwards the gums
were reddened and swollen, and the appetite lost ; the conjnuctiviB
were also somewhat inflamed. The following day these symptoms
disappeared, and the animal remained well.
In another experiment 20 grms. of mercury were volatilis^ed^ and a
rabbit exposed to the vapour under a small glass shade. The following
day the conjunctivte were moist and reddened ; two days afterwards 10
grms. of mercury were volatiUsed in tlie same way ; and in two days*
interval other 10 grms. were volatilised in three-q^uarters of an hour.
There was no striking change noticeable in the condition of the animal,
but within forty-eight hours it was found dead. The cause of death
proved to be an extravasation of blood at the Imse of the bniin. The
bronchia were reddened throughout and the lungs congested. Mercury,
as with man, is also readily absorbed by the broken or unbroken skin ;
hence thousands of sheep have lu^cn poisoned by the excessive and
ignorant external application of mercurial ointment as a remedy against
the at t neks of parasites. The sheep become emiioiated, refuse food, and
seem to be in pain, breathing with short quick gasps.
In experiments on rabbits, dogs, and warm-blooded animali generally,
* The deaths are registered uuder the terra ** Mttrc%iry^^
poison in p by ** C^rrmitie SMimate.*''
t Op. tik.p. 728*
but the mapjotity *ni '
§ ^m
MBRCUST.
671
BBiliYation and stonmtltlii are found to occur as regularly as in man ; m
also in animals and maD, paralytic and other nerx'ous affectiotiB have
been recorded,
§837. {c) Effects on Man,— Tn 1810* an extraordinary accident
produced^ perhaps, the largest wholesale poisoning by mercurial vapour
on record* The account of this is as follows :-— H.M.S. Triumph^ of
seventy-four guns, arrived in the harbour of Cadiz In the month of
Fehniary 1810; and in the following March, a Spanish vessel, laden
with mercury for the South American mine% having been driven on
shore in a gale, was wrecked. The Tri^iinph saved by her boats 130
tons of the mercury, and this was stowed on board. The mercury
WiiH first confined in bladders, the bladders again w^ere enclose<l in small
barrels, and the barrels in boxes. Tiie heat of the weather, however,
wag at this time cousiderable ; and the bladders, having been wetted
in the removal from the wreck, soon rotted, and mercury, to the
amount of several Ions, was speedily diffused as vapour through the
ship, mixing more or less with the bread and the other [iroviyions. In
three weeks 200 men were affeetefl with ptyalism, ulceration of the
mouth, partial paralysis, and. in many instances, with diarrhcen. The
Triumph was now ordered to Gibraltar, the provisions were removed,
and efforts wore made to cleanse the vessel, Oti restovving the hold^
every man so employed was salivated, The effects noted were not
confined to the officers and ship^s company, for almost all the stock died
from the fnmesi — mice, cats, a dog, and even a canary bird sliared the
same fate, though the food of the latter weis kept in a bottle closely
corked up. The vapour was very deleterious to those having any
tendency to pulmonic affections. Three men, who had never complained
before they were saturated with mercury, dietl of phthisis ; one, who
had not had any pulmonic complaint, was left behind at Gibraltar,
whore his illness developed into a confirmed phthisis. Two died from
gangrene of the cheeks and tongue* A woman, confined to bed with a
fractured limb, lost two of her teeth ; and many exfoliations of the
jaw took place.
Accidents from the vapour of mercury, quite Independently of its
applications in the arts, have also occurred, some of them under curious
circumstances ; such, for example^ is the case mentioned in the footnote
to p* 667. Witness, again, a csise mentioned by *Seidel,t in which a
female, on the advice of an old woman, inhaled for some affection or
other 2*5 gnus, of mercury poured on red-hot coals, and died in ten
days with all the symptoms of mercurial poisoning.
* *' An Acooiuit of the EfiTect of Mercurial Vftpoura on tho Crew of Hta Majestj*s
Ship THnmpK in the year 1810/'^ P\^. 7W«jr., 113, 182S,
672
POISONS : THEIR EFFECTS AND DETECTION; [§ SjS, 839.
The metal taken in bulk into the alomaeh has been coniidered non-
poisououa, and J probably, when perfectly pure, it ie bo; we baTe,
however, the case of a girl who swallowed 4| ozs, by weight of the
liquid metal, for the purpose of procuring abortion — this it did not
effect ; but, in a few days, she suffered from a trembling and shaking
of the body and loss of muscular power. These symptoms contiimefl
for two uiouihs, but there wa^ no sativatiou aud uo blue marks ot» the
guma^ This case is a rare one, and a pound or more has been taken
without iujury.
g 838- Absorption of Mercury by the Skin. — Mercury in a fiuely
divided form, rublxHi into the skin, is absorbed, and all the effects of
merciirialism result. This method of administering mercury for niedi-
ciiulI purposes has long been in use, but, when the iu unction ia excessive,
death may occur rhiia, Leiblinger records a case In which three pei-aonft
were fouiKl dead in bed ; the day before they hud rnbbc<i into the body,
for the purpose of curing the itch, a salve cmitaining 270 grms. of
mercury finely divided.
It is di^cult to say iu what proporliou workers iu mercury, such as
water-gilders, etc., suffer. According to Hirt, not only do 1"5 to
2*1 per cent, of the workmen employed iu smelting mercury ores
suffer acutely, but as high a proportion m 8*7 per cent, are slightly
affected,
'^ 839, Symptoms of Poisonmg by Mercury Vapour, -*-The symp-
toms of poisoning by mercury vajjcmr, or by the Hnely tlivided metal, are
the same m those which arise from the corrosiye salts, ^vith the exception
of the locjxl nction. In mdd cases t!iere is pallor, languor, and sore mouth
(from slightly inflamed guuis), foetid breath, and disorder of the diges-
tive organs* If the action is more intense, there is an iuflanmmtiou of
the gums and, indeed, of the? whole mouth, and salivation, which is
sometimes so profuse tliat as much as two gallons of stiliva have been
secreted daily. The saliva is alkaline, hna a bad odour, and its specific
gravity in the early stages is increased, but nltiraately becomes normal ;
tile gmuw are raised into slight swellings, which gradually enlarge and
coalesce. The teeth that are already carious, decay more rapidly ; they
Wcomo loose, and some may be shed; the iufiammatory action may
cxt€!nd to the jaw, aud necrosis of portions of the bone is uo unusual
occurrence. On recovery the cheeks somofiraes form adheisions with the
gums, and cicatrices alwu,ys mark the loss of substance which such an
affection entails. Witii the stomatitis there are disturbiinct5s of the
gastro-ititestinal tract — nausea and vomiting, ptin in the stomach, and
diarrhrea uUtTuating with coustrpation. Conjimctivitis is very common,
both iu nmu and animals, from exposure to mercury vapoui"a. The
further action of the metal is »Iiown in lis profound efTectB on the
§ Ho.]
MKKCVKY,
673
neTYous system* The patient is changed iu his disposition, ha is excit-
able, nervous, or torpid ; there are sleeplessness and bad dreams, at the
same time headache, noisea in the ears, giddiness, fain tings, etc.
g 840, Mercurial Tremor. — Mercurial tremor* may follow, or ac-
company the above state, or it may be the ebief and most prominent
eflfect. It specially aftects the arins^ partly withdrawing the muscles
trom the control of the will, so that a pe(soii affected with mercurial
tremor is inoapaciUited for following any occupation, especially those
requiring a delicate and steady touch. In cases seriously affected, the
tremor spreads gradually to the feet and legs, and finally the whole
body may be invaded. The patient is no longer master of his muscles
-*the muscular system is m anarchy ^ each muscle aimlessly contracting
and relaxing independently of the rest — the movement of the lega
becomes uncertain, the speech stuttering, the facial expressions are
even distorted into grimaces, and the sufterer sinks into a piteous sttvfce
of helplessness. The convnlsive movements generally cease during
sleep. The tremors are accompanied by interference with the funotiong
of other organs: the respiration is weakened and dil^cult ; dyspnoea, or
an astlmiatic condition, results ; the pulse is small and slow ; paresis,
deepening into paralysia of the extrismities, or of a group of muacleS)
follows ; and, lastly, if the condition is not alleviated, the patient
becomes much emaciated and sinks from exhaustion. Pregnant women
are liable to abortion, and the living infatits of women suffering from
tremor have also exhibited tremor of the limlm.
In the case of the ''mass poisoning" on Ixiard the Triumph, It
has been mentioned that several of the sailors bi^oame consumptive, and
the same efiect has been noticed among all workers in the metal ; it is
now J indeed, an accepted fact that the cachexia induced by mercurial-
ismus produces a weak habit of body specially liable to the tuberculous
infection.
The course of the poisoning is generally more rapid when it haa
resulted from the taking of mercury internally as a medicine than when
luhaled by workers in the metal, bjj. a patient sulleriiig from mercurial
tremor showti to the Medical Society by Mr. Bpencer Watson in 1872,
had resisted for seven years thQ influence of the fumes of mercury ; and
then succumbed^ exhibiting the usual symptoms. Idiosyncrasy playa a
• A omfs of mereuriftl tremor {in Btrieht^ dts K. JT, ^Igem, Kranktnhaujm sn
Wien im JtUir« lS72f Wieti, 1S73) ir Intemsiting, as showing the iiifluepce of pn-g-
Duicy, A wnman, twenty years of age, employed in making ban^nneters, had, in
1609, mercuritl li'^emot- jiud HAliv-^tiuti. During a three months* progn&noy the
tremoT cp^aed, but again ftpp<^red after she had abortecL She again be<.iame preg-
nant, and the tremor ceased until after her ocintinemeiit in November ld7U The
tremor wae so violent that the patient could not walk ; ahe alfo had stomaiitla ; hut
ultimately, hy tret*tment with gdlvaiii^m and other reniediesi she rwovertsd*
43
674
POISONS : THEIR EFFECTS AND DETECTION,
[§ 841.
eonaiilerable r6l& ; eopie persons (and especially those whose kidneys are
diseased) bear snmll doses of mercury ill, and are readily salivated or
aflbcted ; this is evidently due to imperfect eliminafcioD,
U 8il. Mercuric Methide, Hg(CHg)o. — This corapound is obtained
by the action of methyl iodide oq sodium amalgam in the presence of
acetic ether. It is a dense, stable liquid, of highly poisonous properties.
In 1865, mercuric methide, in course of preparation in a London
laboratory, caused two caa^ of very serious slow poisoning.* One was
that of a German, aged 30, who was engaged in preparing this eom-
pound for three months, and dnriug this time his sight and hearing
became impaired ; be waa very weak, his gums were sorej and he was
nltimiitely admitted into SL Bartholomew's Hospital, February 3rd,
1S65. His urine was found to be albuminous, and bis mental faculties
very torpid. On the 9th he became noisy, and had to be put under
mechanical restraint. On the 1 0th he was semi-comfltose, hut there
was no paralysis ; hh breath wits very offensive, his pupils dilated ; at
intervals he raised himself and uttered incoherent howls* There was
neither sensation nor motion in the left leg, which was extended rigidly ;
the knee and the foot were turned slightly inward* On the 14 th he
died insensible.
The only appearance of note seen at the autopsy was a congestion of
the grey matter in the brain ; the kidneys and liver were also congested,
and there were ecchymoses in the kidneys.
The second case — a young man, aged 23, working in the same
laboratory — was admitted into the hospital, March 28th, 1865. In the
previous January he had been exposed to the vapour of mercuric
met bide for about a fortnight : during the illness of the other assistant
he felt ill and weak, and complained of soreness of the gums and loose-
ness of the teeth. He had also dimness of vision, pain and redness of
the eyes, giddiness, nausea and vomitiug, the ejectefl matters being
greenish an<l watery. At the beginning of March his sight and taste
became imperfect— all things tasted alike ; his tongue was numb and
his gums sore, he was also salivated slightly* A week before tul mission
he lost his hearing, and first his hands and then his feet became numb ;
on admission his breath was very offensive, his pupils dilated ; the sight
impaired ; he waa very deaf, atid his powers of speech, taste, and smell
were deficient. There was aneSHthe^ia of the body, and the movement of
the limbs was sluggish and difficult. He continued in the hospital for
nearly a month, with but little change. On April 24t.h, it was noticed
that he was getting thinner and slightly jaundiced i he moved his arms
aimlessly in an idiotic manner, and passed hia urine involuntarily. On
April 27 Lh he was more restless, and even violent, shrieking out, and
* St BaHK Bosp. Eeport^^ vol I.. 18«6, p. Hi.
§ 842]
MERCURY.
making a loudH, iucsohereii't noise, or kugbitig foolbhly ; he passed his
motions firnl urine beneath him* On July 7th he was in a simiUr stiite
— perfectly id to tic. He died on April Tth^ 1866^ about a year and three
months from his first exposure to the vapour ; the immediate cause of
death was pneumonia. The post-mortem appearances of the brain and
mem bran OS differed little from the normal state ; the grey matter was
pink, bnt otherwise healthy ; there was a considernhle amount of
oerebro'spinal fluid ; the arachnoid along the longitudinal fissure was
thickened j the total weight of the brain with medulla was 41 om. The
stomach was of enorraouH siae ; the pyramids of the kidneys were con-
jeatedj as was also the small intestine ; the luugs showed the usual signs
of pneumonia.*
§ 842. Eflfects of the Corrcmve Salts of Mercury, — The type of tlie
corrosive salts Is mercuric chloride, or corrosive sublimate— a compound
which acts violently when administered, either externally or internally,
in lar^e dosos»f If the f^oison has been swallowed, tlie sym[)toma come
on almost immediately, and always within the tirst half hour; the whole
duration also is rapid. In 36 cases collected by F. A* Fiikk, 11 <lied on
the firat or second day, and 1 1 on the tifth day ; so that 61 per cent* died
in ^ye days — the remainder lived from six to tweuty-six days* The
shortest fatal case on record is one communicated to l)r, Taylor by
Afr. Welch; in this instance the man died from an unknown quantity
within half an hour.
In the very act of swallowingt a strong metallic taste and a painful
sensation of constriction in the throat are experienced. There is a burn-
ing heat in the throat eitending downwards to the stomach. All the
mncons membranes with which the solution comes in contact are attacked,
shrivelled, and whitened; so that, on looking into the month, the appear*
ance has been described as simitar to that produced by the recent appli-
cation of silver nitmte. The local changes may be so intense as to cause
cedema of the glottis^ and death through asphyxia. In a few minutes
violent pain is felt in the stomach ; so much so, that the sufferer is
drawn to^ether^ and is in a fainting condition ; but there are rare cases
in which pain has been absent* There are nausea and vomitings the
ejected matters being often streaked with blood ; after the vomiting there
is purging; here also the motions are fre<|uently bloody, j The tempera-
• SL Barih. Mmp. EiporU, vol. ii* p. 211.
t The effects on animals are iiiinilar to those on man^ Richard M^ad K*Te s dt>g
with bread 3*8 grms. (00 grains] of commivc sublimate: — '* Within a quarter of an
hour he fi^lJ iuto t<?rri)ile convuUiotia, editing U|i frequQtitly a viscid fitjthy tnucuii
uvt^ry time more and more bloody, till, tired and upeai with this bard service, be \a,f
ilown qnietly, as it wctAi to sleiep, but died the next moming,"
t The mixture of bloofl with the evftcuAtions is more coDstautly oliavi ved in
poiuaoing by corrasiV(9 aubtimiilo tluia lu poisoiiiiig by anenio, cop^r, or load.
676
POiaONS: TTTRIR EFFECTS AND T>ETl5CTinN. [§ 843^845.
ture of the body sinks, the reapimtion is difficult, and the pulse small,
frequent, and irregular. The urine ia geuerally suanfcy, and sometimes
completely auppreesed,'*^ Sometimes there is profuse ha3morrhage from
the boweU stomach, or other mucous membrane, and euch cases are
accompaTiied by a considerable diminution of temperature. lu a case
recorded by Loewy^t after a loa^ of blood by vomiting and diarrhosa, the
temperature sank to 33^4". The patient dies in a state of collapse, or
insensibility J and death is often preceded by convulsion a,
§ 843. Two remarkable cases of death from the external use of corro-
sive sublimate are recorded by Anderseck. An oiiitmeut, containing
corrosive aubhmate, was rubbed into the skiu of two girls, servants, in
order to cure the itch. The oue^ during the inunction, complained of a
burning of the skin ; the other also, a little while after, suffered in the
same way. During the night the Bkin of each swelled, reddened, and
became acutely painfuL There were thirst and vomit rng, but no ditirrho^a.
On the following day there was ati eruption of blebs or little blisters.
On the third day they had diarrhoea, tenesmus, fever, and diminution of
the renal secretion ; on the fourth day, feet id breath, stomatitis, hyper-
lestheaia of the body^ and a feeling of '^pins and needles'* in the hands
and foet were noted. The first girl died in the middle of the fifth day,
fully conaciona ; the other died on the sixth. So also Taylor I gives the
case of a girl, aged 9, who died from the efleots of an alcoholic solution
of corrosive sublimate (strength, BO grains to the oz.) applied to the
scalp aa a remedy for ringworm. The same author § further quotes the
case of two brothers wfio died — the one on the fifth, the other on the
eleventh day — from the effects of absorbing corrosive sublimate through
the unbroken skin.
g 8i4. The HitrateB of Mercury are poisons^ but little (if at all)
inferior in corrosive action to mercuric chloride. Death has resulted
from both the external and intern nl use. Application of the nitrate aa
an escharotlc to the os uteris in one case, || produced all the symptoms of
mercurial poisoning, but the woman recovered ; in another case,1l its use
as a liniment caused death.
§ y45* When taken internally, the symptoms are scarcely diflerent
from those produced by corrosive sublimate. It seems an unlikely
vehicle for criminal poisoning, yet, in the case of Hey. v. B, Smith
(Leicester Summer Assi^jes, 1857)^ a girl was proved to have put a solu-
* In o e»fi« reuorded by Dr. Wegeler (Casper's IVochenM^rift, January 10, 1846,
p* 80), a youth, aged 17^ swallowed 11*6 gnus, (3 drachms) of the poison, No pain
WIS experieticod tin pressure (^f the alxlomei* ; he died ou the sijcth day, and iiuring
the last thi^e days r>f life no urine wi^^ secreted,
t Fierkljahrssehr. fur ffer, MuL^ 1864» vol i. p, 187,
% Op, tih g Poiams ISiS, [>. 394.
kl M$d. GaMk, vah xlv. p. lOZS, % Mdhh Monthly Jour mil, 1864, p. 167*
§ 846-849 ]
MERCUET.
677
tion of nitrate of mercury in some chamomile tea, which had been pre-
scribed for the prosecutrix. Tlie iiauseoiia ta«Le prevented a fatal dose
being tiikcii ; but the sjmptorui^ were seriouH,
§ 846. Ilerctmc Cyanide acta in a maoner very similar to that of
corroaive Jiublimate, 13 grm, (about 20 grains) iu one caae,* and in
another t half tbc quantity, having destroyed life,
g 847. White Precipitate (ammoniateii mercury)^ aa a poison, la weak.
Out of fourteen eases collected bj Taylor, two only proved fat^l ; one of
thBse formed the subject of a trial for murder, Refj. \\ Moore (Lewes
Lent AssizeSj 1860), The eil'ecta protluced are vomiting, piir^^ang, etc,,
as in corrosive sublimate. J Other preparations of mercury, such as the
red iodide, the pertsulphitle* and even calomelj § have all a more or leas
intent poisonous action, and have caused serious syoiptoms and death*
§ 848. Treatment of Acute and Chrome Poisoning.— In acute
poisonings vomiting usually throws off some of the poison, if it has been
swallowed ; and the heat treatment seems to be, to give copious albu-
minous drinks, such, for example, as the whites of eggs in water, milk,
and the like. The vomiting may be eucourage<i by subcutaneous,
iujcctions of apomorpiiine. The after-treatment should be directed to
eliminating the poison, wliich is most safely effected by very oopioua
drinks of distilled water (see ** Appendix *^).
The treatment of slow poisoning is mainly symptomatic ; medicinal
doses of iinc phosphide seem to have done gocw:! iu mercurial tremors*
Potassic iodide is also supposed to assist the elimination of mercury,
g 849. Post-mortem Appearances.— The pathological effects seeu
after chronic poisoning are too various to bo distinctive* In tfie museum
of the Royal College of Surgeons there is (No. 2559) the portion of a
colon derived from a lady aged 74, || Tliis lady had been accustomed
for forty-three years to ttike a grain of calomel every night ; for many
years she did not suffer in health, but ultimately she became emaciated
and cachectic, with anasarca and allniminuria. The kidneys were found
to be granular, and the mucous membrane of a great part of the
intestine of a remarkable black colour, mottled with patches of a lighter
hue, presenting somewhat the appearance of a toad's back. From the
portion of colon preserved, mercury was readily obtained by means of
Ueinsoh's test. The black deposit is in tlie submucosa, and it is,
without doubt, mercurial, and probably mercury sulphide. In acute
poisoning (especially by the corrosive salts) the changes are great and
* Orfilii, L p. 736. t CUristiaon, p. 427,
X Sec Dr. Tlu Steveosoii^ ** PoiBoning by White Procipitato/* Quy^s HmpitiU
JUporU, vol. xix. p. 416.
§ S«idd quotes a caao from Haaselt, id which a father, tor the purpose of
obtaining infiuraDce monoyt killfHl hxa ohild by caloiiteb
I PalK mSoc, Tram., xviil IIL
678
POISONS: THKIB KFrKCTS AND DKTECTION.
[§ 8S0.
Btfikitig* After rapid death from corrouive subiiiiiaie, the escbarottc
wUitetiing of the inoutlii tlii'oat, ami gvillet, aheady described, will be
seen. The mucous rnembrauL* right throughout, from mouth to anus,
is more or kss affected and deetroyeJ, according to tlic dose and cou-
ceutratioii of the poison. Tht; usual appeiiraiicea iu the stomach arc
thoac of intense congestion, with cccliymoses, and portions of it mfky be
destroyed. Sometimes the cotita are very much blackened; Him is
]irolmb}y due to a coating of Eiulphide of mercury.
hi St. George's Hospital Mu^'um (Sor. ix, 43, y. 337) there is % stomach, father
Urgi«, with thickeiitd tnui^imj^ coats, and lidvLtii^ on the mucous^ 8urfacii n r^Hds of
fittiiilld block, or black-brown UruM of dc|M75it ; it wafi durived from a |«itknt who
dietl fiom taking currosjive sublimati?. With the severn charges mentioniid, jier-
forftiion is rare.* lu iha intestiiios there ure fouiid hyperfPinia, eitravivsatii^na,
looa^riini:^ oftlie mucQUH mejnbmnt^, and other chungos. The action is purticukrly
interisaci cibout the cajcum and sigmoid flejmre ; in one case, t indeed, there was littlo
irtfkmmiitury redness of the stomach or of the greater jK>rtion of the intcstinf', Imi
I ho Avhole snrfiice t>f the cjecitm Wiig of a deep hhirk-red colour, and then? were
patcheti of sloughiug in th^ coats. Tbo kidrieys are ofti^u swollen^ oottgi^stedj r^r
iuQatned ; changes in the respiratorj organs are not constantly seen^ hut in a majorit)'
of tbei>a$©!t there have been redaass and awtUing of the larynx, trachea, and bronchi,
and £ometnnaii hepatisatiou of smaller ur larger portion si of the hing.
In ^t Geflriie'a Hospital Museum there arc (from a patient dying in the ln>apital)
pre [>a rations whicli well ilhistrato wliat pathological changes may be expt^ted in
any case survivinj^ for a few days. Tbo patient was Ii*raiieia L , aged 45, a4lmitted
to tUo huapital, February 27, 1842. He took a quantity of eorrosiive suhMmato spread
on bread and butter, was immediately siek« and was unable to take as much as h«
litid intended* Tke stomach pump and oiber romedies were used. On the follow-
ing day his mouth was sor«, and on March l^t his vision was diTii ; lih month vt&»
drawn over to the right side, and he lost power over the left eyelid, but ho had
no pfiln J he jiassed some blotjd from tbo boweh On the 2nd ho i»a£jiied much
bhxid, and was Rivaled ; still no pain. On March 4^ cm the evening of the
sixth day, he e?rpireil ; be was drowsy during the last day^ and jukified watery
evacuations.
Prep. Ha, Ser. is*, shows lb? pharynx, aeisopliagus, and tcmgue ; there is ulcemi'
tion of the tonsils, and fib rinou<i exudation on the gullet. The stomach (43b, 190)
shiiwa a Urge dark slough, three inches from the cardiac extremity ; the margin sur-
round ittg the slough is thickened, ulcerated, and irregular in shape, the submucous
tissue, to some extent, being also thickened \ there is lihrino m the ileum, pharynx,
and part of the larynx, 'I h^ action extended to the whole intestine ; the rectum iu
prep, 145a, 36, is seen to he thickened, and has numoroua patches of effuised flhriueti
It is a curious fact that the external application of corrosive suhlimate
causes inflammatory changes iu the alimentary canal of nearly the same
intensity as if the poison bad been swallowed. Thus, in the case of the
two girls mentioned mtfe (§ 843), there wm found an intense inflaaima-
tiou of the stomach and intestines, the raucous tisauea being scar let-
red, swollen, and svith numerous extravasatiouH,
g 850. Tlie etfects of the nitrate of mercury are similar to tlie pre-
* There is ouly one case of perforation on rword.
t Zaned, 1845, p. 700.
§ Sjl.] ^■i^P MEHCURY, 679
ceding; iu the ftJW cases which liave been recorUed^ tliere has been
intense redness, and iiiflammation of the ^tomiicb and iiiteetines, with
patches of ©echymosis. White precipitate, cyanide of mercury, mercuric
iodide, and mereurous sulphide (turpeth minem)) have all caused inflam-
mation, mora or less intense, of the intestinal tract.
§851. EUmination of Mercury, — The question of the channels by
which mercury h eliminated is of the first importance* It would
appear certain that it can exist in the body for aome time in an inactive
state, and then, from some change, be carried into the circulation ami
ahow its etlecfe§.* Volt ootisiders that mercury combines with the
albuminous bodies, sepirating upon their oiidatiou, and then becoming
free and active^t
Ullmann { found mercury aa follows i — Kidneys, liver, spleen, a
small quautity in the stomach, no mercury in the small intestine, but
some in the large intestine ; small weigiiable Ljuautities in the heart and
skeletal muaolea, also in the lungs; but no mercury, when the da^e
was small, iu brain, the salivary glands^ abdominal glands^ thyroid
glands, the bile, or the bouea.
The maia channel by which absorbed mercury parses out of the
body is the kidneys, whilst mercurial compounds of siuall solubility are
in great part excreted by the bowel. A. BynsseOjg after experimenting
with mercuric chloride (giving '015 to '15 grm., with a little morphine
hydrochlonitejs came to the conclusion that it could be detected in the
urine about two boura, and in the saliva about fonr hours, after its
ad mitjist ration ; he considered that the eliminatiou was finished in
twenty- four hours.
From the body of a hound that* in the course of thirty-one days,
took 2*789 grms. of calomel (2*368 Hg) in eighty -seven doses, aiiout 94
per cent of the substance was recovered on aualysig :—
Qrm».
In th« ffficee, 21176
„ uritie, .,.,*,,, 0*0550
,, bmin, hearty Irnigs, spleen^ puicreia, kidneys,
scrotum^ and petti« 0*0090
„ liver, t *..-,.. . O'OHO
2-2060
* Tuflon gave a mar«, finst, 4 ^aitis, and afttirwuida & grMns of corrosive «iib-
limate twice a day ; at the end of faurteen days, 111 u pint of uritie r»o mercury wm
detected, but ftt the end of threi^ weeks it w&» found »
t Voit, Phytioi, thetn. Unien^,^ Augsburg, 1857.
t CAotw UtiUr., 1892, ii. 941.
I J&umal d§ rAnoL el (k Phyml., 1372, No. 5, p. 500. On thi^ seiiaratlau of
mercury by tbe urinet bdo also Sft!kow§ky in YirQhow'i ArcMv^ 1600*
68o
POIBONS: THBIB KFFECTS AND DETKCTION.
tS 852.
ThiB equals M> of metallic merciirj/ Thus, of the whole 2 '2 gram,
of tnercuric sulphide aeparafced, over 95 per cent was obtained from the
fseeeB,
ThiB case is of considerable interest^ for there are recorded in toxioo-
logical treatisen a few cases of nu doubted mei^urial polaotiitjg iu which
no poison had been detected, although there wrs ample evidence that it
had been ttdmiiiiatered by the luouth. In »uch casess, it \6 probable
that the whole length of the intestinal canal had not been eiamined,
and the analysis failed from this cause. When (as not unfreqnently
happens) the mercurial poison ha.a entered by the skin, it is e^'iUent
that the moat likely localities are the urine, the liver, and the kidneys. t
In A case related by Vidal,:[ the Liquor BdkmtU (or solution of
mercurir nitrate) waa ordered by mistake instead of a liniment* Al-
though externally applied, it caused salivation^ profuse dtarrh(Ba« aud
death in nine days. The whole of the intestinal tract was found
inflamed with extravasations, and mercury detected in the liver.
In any case of external application, if death ensues directly from the
poison, evidence of its presence will probably be found ; but too much
stress mus*t not be laid upon the detection of mercury, for, as Dr Taylor
says, ** Nothing is more common than to discover traces of mercury in
the stomach, bowels, liver, kidneys, or other organs of a dead body."^
§ 85'i, Tests for Mercury; — Mercury, in combination and in the
solid form, ia most reiidily detected by mixing the substance intimately
with dry anhydrous sodic carbonate, transferring tho mixture to a glass
tubcj seated at oue end, and applying heat. 1 f mercury be present, a
ring of minute globules condenses iri the cool part of the tube. If the
quantity of mercury is likely to be very minute, it is best to modify the
proceiiS by using a subliming cell {p* 260), and thus obtain the Buhli mate
on a circle of thin glass in a convenient form for microscopical examina-
tiou* If there \^ any doubt whether the globules are those of mercury
or not| this may be resolved by putting a frt^ment of iodine on the
lower disc of the subliming cell, and then completing it by the disc
which contains the sublimate (of course, the supposed mercurial surface
must be underuioat) ; on placing the cell in a warm, light place, after a
time the scarlet iodide is formed, and the identification is complete.
Similarly, a glass tube containing an ill-defined metallic ring of mercury
can be sealed or corked up with a crystal of iodine, and, after a few
• Kiederer, m Huckner'a Ncue$ JUperL /, PAarm., Bd. iviL 3, 257, 18 §8,
t A woman died from the elf eels of & corrosive sublimate lotioti applied by a
tjuock to a wotiad in her leg. The senior liuthor found no pomm in the stxunach, but
aapamted « milUgmTnme of mottiUic mercury fram the liver ; the urine and int^tines
were not sent*
X Qfi£. d€w Mp., Juillat ]Sti4.
I Tnylor, Metikfri Jari}tprti(f€ac$^ i. p. 288.
8531
MKRCUBT,
681
hours, the yelk^w iodide, changing to uearlet, will become appareut.
There are few (if any) testR of greater delicacy than this.
Merciir}' in solution can \te withdrawn by acidulating the liquid, and
then inserting either simply a piece of gold foil, gold wire, or bright
copper foil ; or else^ by 11 galvanic arrangement, such as iron wire wound
round a gold t?<jin, or gold foil attached to a rixi of rAuc ; fir, lastly, hj
the aid of gold or cepper electrodes in connection with a battery* By
any of these methods mercury i& obtained in the metallic state, aud the
metal with itti film can be placed in a subliming cell, and globuteis
depcraited and identified^ as before described.
The Precipitating Beagents for mercury are numcroiifi : a solution
of staruioua chloride, lieati^d with a solution of mercury, or any com-
bination, whether soluble or insoluble, reduces it to the metallic state,
Mercuroug Salts in solution yield, with potash, soda, or lime, a
black precipitate of mereurous oiide ; Mercuric Salts, a bright yellow
precijutate of mercuric oxide,
Mereurous Salts yield black precipitates, witb sulphides of
ummonium and hydrogen, Mercutic Salts give a similar reaction, but,
with sulphuretted hydrogen, first a whitish precipitate, passing slowly
through red to black.
Mereurous Salts^ with solutions of the chlorides, give a white
precipitate of calomel ; the Mercuric Salts yield no precipitate under
timilar circumstances, Mereurous Salts, treated with iodide of
potassium, give a green mereurous iodide ; Mercuric, a scarlet.
§ 85 3, The Detection of Mercury in Organic Sul»itaiiceB and
Fluids. — Simple treatment of the orgnus or tissues with hydrochloric
iM^id may give quidit^itive evidence of mercury, for distinct evidence of
mercury in the liver has been obtained on a piece of copper gause in a
ease where a child had been given 2 grains of calomel before death,
** Four ounces of the liver were treated with hydrochloric acid and
water, aud a small piece of pure copper placed in the acid liquid while
wami, and kept there for about forty-eight hours. It acquired a slight
silvery lustre, and globules of mercury were obtained from it by
sublimation."
To detect the cyanide of mercury may require special treatineiit,
and Vitali* recommends the following process: — The fluid is acidified
with tartaric acid and netitralised by freshly precipitated CaCO^; a
slight excess of hydrio sulphide is added, and the flask allowed to rest
for twenty- four hours in the cold. Then a further quantity of SH^ is
added, and a current of hydrogen passed through the liquid ; the
effluent gas is first made to bubble through a solution of bismuth
nitrate in dilute nitric acid (fur the purpose of absorbing SHj), and
' VOfmi, mi. 181-1 &6.
682
poisons: their EFKECTS and DBTECrtON.
[§ 8S3-
then through aqucouss iiobash (to ulMorb UCl) ; in the first flask the
analyst will separate and identify Tuercury sulphide, while in the last
Hask there will be potassio cyanide, which will respond to the uaual
teats.
In those cases where no special search is made for raercury, but an
aeid (hydrochloric) solution is treated \*ith Mulphuretted hydrc^en^
mcTciiry is indicated by the preisence of a black precipitate, which does
not dissolve in warni nitric acid*
The further treatment of the black sulphide may be undertaken in
two ways v —
(1) It is collected on a |3orcelain dishi with the addition of a little
nitric acid, and evaporated to dryness in order to destroy organic
matter. Hy drochluric and a few drops of nitric acid are neit added ;
the action Is aided by a gentle heat^ the solutiou finally evaporated to
dryness on the water-bath, and the residue taken up by warm distilled
water, lite solution is that of a persalt of mercury, and the mercury
can be separated by electrolysis, or indicated by the tests already
detailed,
(2) The other method, and the most satisfactory, is t^ mix the sul*
phide while moist with dry carbonate of soda, ujake it int^o a pellet
which will easily enter a reducing or sublimiug tube, dry it curefnlly,
and obtain a sublimate of metallic mercury,
A neat method of recognising mercury when dejx>sited as a film on
copper has been proposed i>y E* Jirugnatelli : * the copper, after b^ing
washed, is trarisferred to a glass vessel, and a porcelain lid, on which a
drop of gold chloride solution has been placed, adjusted over the dish.
The vvhole is heated by a water-batih The Diercury vapour reduces the
gold chiorido, and gold is deposited as a bluish- violet stain ; ^^ mgrm.
mercury may by this test be identified.
Of special methods for the separation and detection of mercury,
Lud wig's t (or some modifications thereof) is the best when organic
matters have to be dealt with : the finely divided solid suljstauces are
boiled for some honrs with hydrochloric acid, strength 20 per cent. ;
then the liquid is cooled to 60**, and potaesic chlorate added in half-
gramme quantities until the dark liquid becomes clear; the liquid is
cooled at id filtered, and the substances on the filter w^ished with water.
To the filtrate 5 grms. of zinc dust are added, and the liquid is violently
shaken Iron) time to time; a second f:K>rtion is afterwards added, and
also vigorously shaken. After some hours the clear liquid is separated
from the zinc and the £inc washed, first with water, then with a little
soda solution, and finally^ again with water. The ^inc is now collected
• Gazzdta, lix. 418-422,
t Eeii, f. phf9i&lo^. Ch^mU, 1SS2, i. 495 ; €htm, CantrhU., 1892, it, 041.
§ 853A, S53B.]
MERCUKY.
€83
uu a [^lu^s-wool tilfccr, treated with abaoluLe itlcohol to remuvtr water,
aud dried by suutiou in a streiijii uf itir Tlie zinc is put iuto a combus-
tion-tube, t}ie tube beitjg drawn out into a thiu capillary eitremjty,
and a combustion made, the mercury collecting at the capillary part.
It ia a necessary rcifinouient, should the zinc be eoutttminated with a
triice of organic matter, to pack the combuiittou-tube as loUowa : — Firutj
tlie zinc dust on which any mercury present has been deposited, then a
plug of asbestos J next, some euprie oxide; and lastly, some pure mic
dust. Bondzynski * prefers to uae copper rather than lAnc ; for be say a
that mnc so frequeutly contains ciidmiutu, which latter metal also gives
a mirror, so that, unless tiie mercury is afterwards id^aiititied by turning
it into an iodiile, error may be caused,
CX Sclmmm {Zeif. anal. Chent.^ 1905) has made a number of
experiments showing that it is not necessary to entirely destroy the
organic matter of the organs in searehing for mercury. The organB
and tissues, finely divided, are treated with hydrochloric acid and potaasic
chlorate in a capacious tiask attached to an inverted (refliut) con-
denser, and then the tiltered fluid sijbmitted to electrolysis— the anode
being platinum foil, the cathode a piece of gold foil 10 mm. broad and
30 mm. long; the tensiou should be 4 voltSf and the electrolysis be
con tinned for twenty- four hours, I n a case of mercury-poisoning Sch u mm
fouml ilk the kidney 1^89 ragnn., liver 1 mgrnu, pancreas *44 mgrm,,
and lung '4 mgrm, — total separated, 3 '73 mgrms^t
^ 853a, Separation of Hercury by Hydrozylamme.^Paul Janni^isch
(B^., 1898) has shown that mercury may be separated quantitatively
from copper, bismuth, lead, nickel, cadmium, arsenic, antimony, and tint
by an ammoniacal solution of hydroi^ylamiuc. The mercery should
be converted into chloride, and^ to the hydrochloric acid solution,
tartaric aciif, ammonia, and hydroxy lamine hydrochloride are added in
excess, and the solution heated until the precipitation is complete ; the
mercury is collected, re^lissolved in fuming nitric acid, the solution
evaporated to dryness, the residue taken up with hydrochloric acid, and
the mercury precipitated as sulphide. Mercury may be similarly
separated from aluminium, chromium, or manganese in the presence of
oxalic acid ; mercury and cobalt may also be separated by the addition
of ammoniacal hydroxy lam ine to a slightly acid solution of their salts.
§ ^53^. Detectioii of Mercury in the Urine, — One of the best
methods is to acidify with concentrated hydrochloric acid, and add
* ^eit./. anal. ChfTn., xxxil 30'2-a05,
f ScUannn alsa «1ii»w» thiit n fluid capable of filtr&tion can be obtained by
digeHtmg or i:Dcubating nl 37^ with nn equal bulk of wKter to whidj, as &q antiseptic,
chloroform is added. Under thiisti circtimBlancefi in about a week auto-digeatioar td a
great ext^^ut, will have? tak«n [iIacb, For tha aame [larpu^e ht? «laq iiaes pepdn uid
hydrtM;hluric mid ; but such tLme^ogafiamiiig pioceHM are hardly pmetkal^
1
684
POISONB: THEIR RFFECTB ANU DETBCTION. [§ 8S3B.
potassic chlorate iu the proportion of about 1 grm. for every 100 ex* ;
the urine h heiited until it no longer smells of chlorine, and then mixed
with A dilute solution of stiLunoaH chloride ; in this miitture ii fiicce of
gilt platinum foil is placed for fifteen minuteB, the foil heatw3 with nitriu
acid, and the solution evaporated to a Bmall hulk and then tested with
hydrogen sul|ihide. This method will detect 0*07 mgrm, of nierLnirj**
Schumacher and W, Juny t use a siniilar process^ but add tfodiuni
chloride, and after boiling with the hydrochloric acid and potas^ic
chlorate, cool to 80* and add rasped siinc ; in about two hours the
undisBolved //nic is L^ollected, wa^sbedj heated with dilute potaHHiutn
hydro3tide» and again washed. It is then dissolved in 50 cx- of dilute
hydrochloric a<^id with the addition of potasaic chlorate ; after l>oiling
out moat of the chlorinoj the last traces are removed by the addition
of alcohol Hydrogen sutpliide h added, the mixture made up to 100
ex., and the yellowish-brown colour compared eolorometrically with
standard solutions of mercuric chloride.
£mBt Janecke (ZeiLf, anal. Ohsm.^ 1904) separates mercury from
urine on the foregoing prinmples, obtaining the metal f^rat on a spiral
of copper wire. The wire is washed with hot water and air-dried- It
is then put in a dry reagent tube, which is drawn out just beyond the
wire to a capillary tube ; by means of strong heat the mercury is then
distilled into the capillary portion. The capillary tube h then cut off,
and crushed in a reagent glass containing 5 ex, of dilute nitric and
Hulphnric acids. The mixture is warmed for an hour on the water-buth,
and then transferred to a watch-glass — bringing the whole up to 10 ex.
by a 5 per cent, solution nf potaasic sulphate. This solution is submitted
to the electrolysis of a platinum-gold couple, made of gold and platinum
wire. The gold wire weighs about 25 mgrms., and has a length of 1 8-20
cm., with a diameter of 0*1 mm. The gold wire is weighed carefully in
a Nernst J balance both before and after the electrolysis ; in each case it
ia carefully dried,
Acconliag to Bruno Bardach {Ohmn. Oentn, 1901), mercury in the
urine may be separated and estimated as follows i — -250-1000 ex, of the
urine are mixed with 0*8 grm, of finely -divided egg albumin ; 5-7 e,c.
of 30 per cent, acetic acid are added, and the album in precipitated on
the water-batb. The precipitate contains all the mercury; it is filtered
off and dissolved in 10 c.c, of hydrochloric acid of specific gratit/ 1'19*
This solution is heated for forty-five minutes with a clean copper spiral in
* Adolf Jolles, ZfU, nnaL Chmu, 1900, t llmL, 1902.
t The Nerust balance {Btr, JCJUtvL, 1003) m ft tnicixj-ltalwice with tiPiaioiml
Gdiitro], hatring u s^^iisitiyfmess of '038 tivgrui. jier ticuk diviBiou, iiud c-jipable of being
read to ^ dlviaiou. It can scarcely l>e in English commerDe at present, but can he
obtained from Spmdleir k Hoyer, Oottingeu ; it is an inatrmncnt likely to be of use
In tojteologiciil invcstigiition*
§854.855]
MERCURY,
68s
the wat^rbuth. The spiral h waehed with ^ater^ alcohol, and ether,
carefully dried between filter- paper, and then heated In a long glass
tube with a particle of iodine. The yellowish red iodide of mercury, if
preBentj will coiideime in the colder part of the tube,
§ 854. Estimation of Mercury, — All pharmaceutical substances
containing mercnry^ at well as the sulphide prepared in the wet way,
and minerals, are best dealt with by obtaining and weighing the metal
in the solid state. The assay is very si tuple and easy when carried out
on the method tliat was first, perhaps, proposed by Domeyko, A glass
tube (which should not be too thin), closed at one end, t^ bent, as shown
in the figure; the diameter should be about three lines, the length from
T to 8 inches, the shorter arm not exceeding 2 in^hea. The powdered
substance is mixed with two or three times its weight of litharge, and
introduced into the tube at a. The portion of the tube containing the
mercury is at first heated gently, but finally bruught to a temperature
sufficient to fuse the substance and soften the glass. The mercury
collects in an annular (ilm at /* in the cooler Hrab, and may now, witli a
little management of the lamp, be coneentratetl in a weU-defined ring ;
the portion of the tube containing this ring is cut off, weighed, then
cleansed from mercury, and re weighed. Many of the pharmaceutic a I
preparations do not require litharge, which is specially adapted for ores^
and heating with sodic carbonate {in great excess) %vill suffice. Mercury
mixed with organic matter must be first separated as described, by copper
or gold, the silvered foil rolled up^ dried, introduced into the bent tube^
and simply heated without admixture with any substance i the weight
may be obtained either by weighing the foil before and after the opera-
tion, or as above*
g 865. Volumetric Processes for the Eatimation of Heronry, —
When a great number of mercurial preparations are to be examined, a
volumetric process is extremely cotivantent There are several of these
processes, some adapted more particularly for mercuric, and others for
mercur^jus compounds. FW mercuric, the method of Personne * ta the
best. The conversion of the varions forms of mercury into corrosive
Bublimate may be effected by evaporation with aijua regia, c»re being
taken that tlie bath sliall not be at a boiling temperature, or there will
he a slight loss.
Personne prefers to heat with caustic soda or potash, and then pf^st^
• Vmtijd, lUniL, Ivi m ; SatUmV V&l, Ana!., 177.
686 POISONS: THEIR EFFECTS AND DETECTION. [§ 856.
chlorine gas into the mixture; the excess of chlorine is expelled by
boiling, mercuric chloride in presence of- an alkaline chloride not being
volatilised at 100**. The standard solutions required for this process
are : —
(1) 33*2 grms. of potassic iodide in 1 litre of water, 1 c.c. = 0 01 grm.
Hg, or 001 355 grm. HgClg.
(2) A solution of mercuric chloride containing 13*55 grms. to the
litre, 1 c.c. = O'l grm. Hg.
The process is founded on the fact that, if a solution of mercuric
chloride be added to one of potassic iodide, in the proportion of one of the
former to four of the latter, mercuric iodide is formed, and immediately
dissolved, until the balance is overstepped, when the red colour is
developed ; the final reaction is very sharp, and with solutions properly
made is very accurate. The mercuric solution must always be added to
the alkaline iodide ; a reversal of the process does not answer. It there-
fore follows that the solution to be tested must be made up to a definite
bulk, and added to a known quantity of the potassic iodide until the
red colour appears.
Mercurous Salts may be titrated with great accuracy by a deci normal
solution of sodic chloride. This is added to the cold solution in very
slight excess, the calomel filtered off, the filtrate neutralised by pure
carbonate of soda, and the amount of sodic chloride still unused found
by titration with nitrate of silver, the end reaction being indicated
by chromate of potash. Several other volumetric processes are fully
described in works treating upon this branch of analysis.
ITL— PRECIPITATED BY HYDRIC SULPHIDE FROM
A NEUTRAL SOLUTION.
Zinc— Nickel— Cobalt.
1. ZINC.
§ 856. Zinc — at. wt., 65 ; specific gravity, 6*8 to 7*1 ; fusing-point,
412* C (773* F.) — is a hard, bluish-white, brittle metal, with a crystalline
fracture. Between 100* and 150° it becomes ductile, and may be easily
wrought ; but at a little higher temperature it again becomes brittle, and
at a bright red heat it fuses, and then volatilises, the fumes taking fire
when exposed to the air. In analysis, zinc occurs either as a metallic
deposit on a platinum foil or dish, or as a brittle bead, obtained by
reducing a zinc compound with soda on charcoal.
The salts of zinc to be briefly described here are the carbonate, the
I HS7-860.]
XIKC.
687
oxide, and the sulphide —all of which are likely to occur in the separa-
tion and esttmatiou of zinc, and the sulphate and chloride — saltB more
especiallj found iu commeix;e, and cauaing accidetita from time to
time,
§ 857. Carbonate of Zinc, in the native form of calamine, contains, as
is well knowu^ 64 8 per cent, of oxide of zinc ; but the carbonate obtained
in the course of an analysis by precipitati(i|}^ the uentml hot solution of
a soluble salt of mic by carbonate of potash or soda, is carbonate of ^inc
plus a variable quantity of hydrated oxide of mic. Unlesij the precipi-
tation takes place at a boiling temperature, the carbonic anhydride retains
a portion of the oxide of zinc in eulution. By ignition of the carbonate,
oxide of zinc resiuUs,
§858, Oxide of Zinc (ZnO^Sl; specific gravity, 5*612; Zn,
80*24, 0, 19*76) is a white powder when eool, yellow when hot. If
mixed with suthcient j^iowdored siilphur, and ignited in a «treaui of
hydrogen, the sulphide is produced ; if ignitcwi in the pure state in
a mpid stream of hydrogen gas, metallic zine is obtained; but, if it
is only a feeble current, the oxida of zinc becomes cryatalline, a portion
only being reduced.
% 859, Sulphide of Zinc {ZuS == 97 ; s^iectiic gravity, 4*1 ; Zn, 67-01,
S, 32'99). — The sulpfnde obtained by treating a neutral solution of a
soluble E^alt of ^iuc by hydric sulphide is hydrated sulphide, insoluble in
water, caustic alkalies, and alkaline aulphides, but disfiolving completely
in nitric or in hydruchloric acid. When dry, it is a white pow^derj and
if ignited contains some oxide of ?4nc. The anhydrous sulphide is pro-
duced by ndxing the precipitated sulphide with sulphur, and igniting in
a crucible in a stream of hydrogen gaa.
Pharmaceutical Preparations.— Ti^e ofiQcinal compounds of zino uaed
in medicine are the acHaie^ mrbonat^, rkiorule, oxith^ mlphate^ mdpho-
rarbolaie^ and pahrianaie.
Sulphate of Zlqc (ZnSOJH^O =- 161 -H 1 26; specific gravity, crystals,
1-931). — This salt ii oflieinal in all the pharmacopoeias, is used in
calico-printing, and is commonly known as white mtrwt. By varying
the temperature at which the crystals are allowed to he formed,
it may be obtained with 6t 5, 2, or 1 atoms of water. The com-
mercial sulphate is in crystals exactly similar to those of E|i8om
salts] it is slightly efflorescent^ and gives the reactions of zinc and
sulphuric acid.
g 860. Chloride of Zinc i« obtained by dissolving zinc in hydro-
chloric acid, or by direct union of stinc and chlorine. Chloride of zinc
is the only couBtitucnt in the weUknown "^^ Burnett's disinfectant fluid."
A solution of chloride of zinc may be heated until it becomes water-
free : when this takes pLace it still remains flutd, and makes a convenient
688 POISONS: their effects and detection. [§ 86 1.
batb, for warmth may be applied to it above 370' without it emitting
fumes to inconvenience ; at a red heat it distils. A concentrated
solution of zinco-ammonic chloride (2H4NClZnCl2) is used for the
purpose of removing the film of oxide from various metals preparatory
to soldering.
§ 861. Zinc in the Arts. — The use of zinc as a metal in sheeting
cisterns, articles tor domestic use, alloys, etc., is well known ; oxide of
zinc enters largely into the composition of india-rubljer. Sulphide of
zinc has been employed as a substitute for white lead, and may possibly
supersede it. Zinc white is further employed as a pigment, and, mixed
with albumen, is an agent in calico-printing; it is also used in the
decoloration of glass, in the polishing of optical glasses, and in the
manufacture of artificial meerschaum pipes. '^
Ghromate of Zinc (ZnCrOJ is used in calico-printing, and there is
also in commerce a basic chromate known as zinf yellow. Zinc green,
or Rinman's green, is a beautiful innocuous colour, formed by igniting
a mixture of dry zincic and cobaltous carbonates.
The use of zinc vessels in the preparation of foods may occasionally
bring the metal under the notice of the analyst. When exposed to
a moist atmosphere, zinc becomes covered with a thin film of oxide,
perfectly insoluble in ordinary water; but, if the water should be
charged with common salt, a considerable quantity may be dissolved.
It may generally be laid down as a rule that the solvent power of water
on zinc has a direct relation to the chlorides present, whilst carbonate of
lime greatly diminishes this solubility, f
Milk may become contaminated by zinc; for, it is a matter of
common knowledge that milk contained in zinc vessels does not readily
turn sour. This may be explained by the zinc oxide combining with
the lactic acid, and forming the sparingly soluble lactate of zinc
2(C3H503)Zn + 3U2O, thus withdrawing the lactic acid as fast as it is
formed, preventing the coagulation of the casein. With regard to this
important practical subject, MM. Payne and Chevallier made several
experiments on the action of brandy, wine, vinegar, olive oil, soup,
milk, etc., and proved that zinc is acted on by all these, and
especially by alcoholic, acetic, and saline liquids. M. Schautfc^le
has repeated these experiments, and determined the amount of zinc
dissolved in fifteen days by different liquids from a galvanised iron
as well as a zinc vessel.
* Artificial meerochaum pipes are composed of zinc white, magnesia usta, and
casein ammonium.
t Ziurck, indeed, found in a litre of water contained in a zinc cistern no less than
1*0104 grm. of zinc, and the same water showed only 0*074 grm. of common salt to
the litre,— VurUyahrsschr. /Ur gei-iefU. Medicin, 1867, Bd. vi. p. 356.
§ 862, 863>] ^^iNU. ^^^^^V 689
The amount found was as follows : —
The Ijqnld ttQtn
The ILqaid Frani the g4iv&iiLt«d
Ibe doQ Vsuel — [fan veuel—
KHDi, p«r Utre. gru)a, per titfe.
Brandy, ,....* 0*95 070
Wine, ..,.,. 3*95 4^10
OmQge*flflwer water, . . . O^ftO 0"7E
Vinf^gar 3175 6075
Fatt>!!oup, 0'4fl POO
Wmktfoup, ,...,. D*fi6 176
Milk, 6'13 7-00
Siil t water, ,,,... i 75 0 "40
SijlU^r ^4ter, 0*35 0'30
Distilled w&ter, . _ . , . traces, irnces.
Ordlii&ry wa.t«r, ..... traces. its^m.
Olive oil none, none,
g 862. Effects of Zinc, as shown by Experiments on Animalfi. —
Ha r thick, in experiments witli sodiiim-^iinc oxide pyrophosphate^ baa
sliown that the esnentjal action of zinc salts ia to paralyse the muaclea
of the body and the heart, and, by thus affecting the circulation and
respiration^ to cause death ; these maiti results have boeu folly confirmed
bj Blake, Letheby, and C- Ph, Falck. For rabbtta the lethal duse is
*08 to '09 grm. of zinc oxide, or about *04 per kilogrm. The tem|>em-
ture during acute poisoning sluka notably — iiccording to F. A. Falck's
researches 011 rabbits, from about 7*3* to 13"0*. Kinc ia eliminated
mainly by the urine, and has been recogniaed in that fluid four to five
days after the last dose. It lias also been separated in small quantity
from the milk and the bile*
I 861 BflectB of Zinc Compounds on Man— {«) Zinc Oxide.— The
poisonous action of zine oxide is bo weak that it is almost doubtful
whether it fihould be considered a poiisou, Dr, Marcett has given a
pound (453*6 grm a.) during a month in divided doses without injury bo
a patient afflicted with epilepsy ; and the workmen in ziucmatiiifa<^tories
cover themselves from head to foot with the dust without very appjirent
l>ad effects. It is not^ however, always innocuoua, for Popoft' has re-
corded it as the cause of headache^ pain iu the headi, cnimpH in the
calves of the legs, nausea, vomiting, and diarrha^a ; and he also obtained
lelnc from the urine of those suffering in this manner,* Again^ a phar-
macy student t filled a laboratory with ostidc of zinc vapour, and
suffered from well'marked and even aerious poisonous symptoms, con-
sisting of pain in tlie heatl, vomiting, and a sliort fever. It must be
remembered that^ as the ordinary zine of commerce is seldom free from
* The so-caUkI ** zinu fearer *' lioa only been noticed in th« fotiuding pf brmsa ; il
ig alwayH preceded hy well-marked shivering, the other symptoma being aimi1»r to
tliuae des<*jibed, •
690
POISONS : THEIE EFFECTS AND DETECTIDN. [| 864, 865.
aTsenk, and some aamples contain gallium^ the preaence of these metalft
may possibly have a part in the prociuctioii of the symptoms described,
§ 864, (b) Sulphate of Zinc. — Sulphate of Kinc has been very fre-
quently taken by aceident or desigu, but death from it is rare. The
infrequency of fatal result is due, not to any inactivity of the salt, but
rather to its being almost always ejfpelled by vomrtingj wliich Ib so
constant and regular au el^ect, that in doses of 1'3 grni. (20 grains)
sulphate of aiuc is often relied upon in poisonitig from olher siibataneea
to quickly expel the contents of the stomach. In a case reported by
Dr. Gibb, an adult female swallowed 4*33 grms. (67 grains), but no
vomiting occnrred, and it had to be induced by other emetics; this case
is unique. It is difficult to say what would be a fatal dnse of tine
Bul|jhate, but the aeriona symptoms cauiied by 28 grnis. (1 oz.) iu the
case of a groom in the service of Dr. Mackenzie, leads to the view that,
although not faUil in that particular instance^ it might be in others.
The man took it in mistake for Epsom salts : a few minutes after^ he
was violently sick and purged, and was excessively prostrated, so that he
had to be carried to his home ; the following day be had cramps in the
legs, and felt weak, but was otherwise well.
In a criminal case related by Tardieu and Roussiri, a large doae
of zinc sulphate, put into soup, caused the death of a woman sixty
years of age in about thirty hours,* The symptoms were violent
purging and vomiting, leading to collape. From half of the soup a
quantity of zinc oxide, equal to 1'6 grm. of ^ine sulphate, was separated.
Zino was also found in the stomaeb, liver, iutestines, and spleen — (see
also a case of criminal poi&ouing recorded by Chevallier).t
g 865. {c) Zinc Chloride, — Chloride of zinc is a powerful poison,
whiuh may kill by its primary or secondary eflects; its local action as a
caustic is mainly to be ascribed to its intense affinit)' for water, dehy-
drating any tissue with whicli it corues in contact. The common use of
disinfecting fluids containing zinc chloride, such as Burnett's fluid, leads
to more accidents in England than in any other European country. Of
twenty-six cases of poisoning by this agent, twenty-four occurred in
England, and only two on tlje Continent, Death may follow the ex-
ternal use of ssinc chloride. Some years ago a quack at Barnstaple,
Devon, applied zinc chloride to a cancerous breast ; the wunnm died
with all the general symptoms of poisoning by sine, and that metal was
found in the liver and other organs.
• Taylor uaticea tUia caafi, but adds that a lie died in three day a. This is a mis-
take, as th^ soup wa» tak(?n oil tli(^ i2th uf Jutie, prohably at midday, »ad th«
wcimftn died ou the ISth, at 8 P.M.
t ''Obaarvattoas toxioukgiquewsur le line,^'' AnnaU» dtH-^gUm Pttblifm, July
187S, p. 15S.
§866.]
ZtMO.
691
The symptoms observed in fatal oaaea of chloride of xinc potsoDtiig are
— immediate pain in tbe throat, and burning of the lipe, tongue, etc.
There is diffic\ilty in swallowing, an increase in the secretion of aaliva,
vomiting of bloody nuittarSi diarrhosa, collapse, comttj and death. In
Bome oaHea life has heen prolonged for days • bnt, on the other band,
death has been known to occnr in a few hours, lu those cases in which
either recovery has taken place, or in which death is delayedj nervous
symptoms rarely fail to make tbeir appearance. In a case recorded
by Dr, R. Haasal, 3 oza. of BurnettV fluid were swallowed. Tbo usual
symptoms of intense gastro-iutestinal irritation enaue^l, but there
was no purging until the third day ; after the lapttc of a fortnight,
a train of nervous symptoms set in, imlicated by a complete perver-
sion of taste and smell. In other cases^ aplion^a, tetanic ailectionB
of groups of muscles, with great muscular weakness and impairment
of sight, have been noticed. Very large doaea of dnc chloride have
been recovered from, ejf. a man iiad taken a solution efpiivalent to
about 13 grms. (200 grains) of the solid chloride. Vomiting came on
immediately, and there was collapse, but he recovered in sixteen days.
On the other baud, '38 grm, (0 grains) lias destroyed life after several
weeka^ illness,
g 866. Postmortem Appearances. — In poisoning by sulphate of
zinc, tbe appeiirancea nan ally seen are intlammation, more or less intense,
of the niucous membrane of the stomach and buwela. In Hi. George's
Hospital Muaeum fcliere is (ser, i^* 43 and 198) the stomach of a man
who died from zinc sulphate, and whose case is reported in the Lanf^et^
1859* Tbe mucous membratie is wrinkled all over like a piece of
tripe J when recent it was vas^cular ami indnnitcd, but nniformly of a
dirty grey colour ; the lining membrane of the small intestine is very
vascular^ and in the rluoclenuni and upper part of the jejunum the colour
is similar to that of the atomaeh, but in a less marked degree ; the
stomach and intestines are contracted.
The |>athological appearances after chloride of m\c vary according to
tbo period at which death takes place* When it has occurred within a
few hoiiFs. tbe lining membrane of tbe mouth and gullet shows a marked
change in texture, bciii^' white m\4 opaque, ihe stomach hard ami leathery,
or much corrugated and ulcerated, in fases in which life has been pro-
longcfl, contractions of the gullet and stomach may occur very similar to
those caused by the mineral juiida^ and with a similar train of symptoms.
In a case whlish occurred under Dr, Markham^a* ohservatiou, a penjou
died ten weeks after taking tbe fatal dose, the first symptoms subsiding
in a few days, and the secondary set of symptoms not eonimeacing fur
tlirL*e weeks. They then couHtrtlpd mainly t*f v* uniting, ntitil the patient
' Med. Timii ami Uautir, Sww 11 « 1S5&, ^. 595.
6p2
POISONS : THEIR EFFECTS AND DETECTION.
[§ m^
sank from exhaustion. The atomach wapS Gonstricted at the pyloric end^
so that it would scarcely admit a rjuill
In Guy^s Hospital there is a good prepartttioii, 1799^\ from the case
of 8* R,, aged 22 ; she took a tablespoonful of Burnett's fluid, and died
in about fourteen weeks. There were at first violent vomiting and
purging^ but she Buffered little pain^ and in a day or two recovered
sufficiently to move about the house ; but the vonuting after food con-
tinued, everything being ejected about five minutes after swallowing.
Before death she suffered from pneumonia. The stomach is seen to be
much contracted — 5 iiicht^s in length ; it Is ulcerated both near the
pylorus and near the gullet ; at the latter part there is a pouch-like
portion of the mucous menibrajie of the stomach adherent to the spleen,
which communicates by a perforation with an abscess foroied and bounded
by the stomach, diaphrugni^ and spleen ; it contained 3 oas. of dirty-
looking pus. At the pylorus, in the centre, there is a second perfonition,
but extravasation of the contents is prevented by the adherent omentum
and transverse colon. The muscular coats are thickened.
% 867. Detection of Zinc in Organic Liquids or SolidB."In cases
where the poison has been cipelled from the stomach by vomiting, the
rnuseles and bonea would appear to be the best tissues to examine chemi-
cally ; for Matzkewitach investigated very carefully a dog poisoned hy
100 parts of zinc, suhcutaneoualy injected in the form of acetate, and
found it distributed over the several organs of the body in the following
ratios :— Muscles, 60'5 ; bones, *24'4 1 ; stomach and intestines, 4"63 ;
skin, 3'70; place of injection, 3'19 ; liver, r75 ; lungs and heart, 1'68 ;
kidneys, bladder, and urine, 114.
Finely-divided organic solids should he piirtially oxidised by nitric
acid and then oharred ; the charred mass is fused in a porcelain basin
with sodium cjirbonate and jK^tassic nitnite, and the ash dissfjlved in
nitric acid. The first group of metals is thrown out by sulphuretted
hydrogen, the iron and aluminium by ammonia; a small excess of acetic
acid is added to the filtrate, and the aiuc precipitated as sulphide by
hydric sulphide ; on the mutiue examination for metals the solution
will have been treated with iiydrochloric acid, and already tested for
arsenic, antimony, lead, etc., and filtered froio any precipitatep In such
a ctise the hydrochloric acid nnist first be replaced by acetic, which is
effected hy adding a slight excess of sodic acetate; the right quantity
of the latter is easily known if the liydntchloric acid originally added
was carefully measured, and its speciHc gravity Jtseertaiued— 3*72 of
crystiUlised sodic acetate saturating one of HCl In any of the above
cases, should a white^ dirty white, or lightish -coloured precipitate (which is
not sulphur) be thrown down, zinc may be suspected ; it will, however, be
absolutely necessary to identify the sulphide, for there are many sources
ihU
§ 868, 869.]
NICKEL^ — COBALT*
693
of error. The mmt uatisfactory ot all ideiitiHoatiotii h t\w pnxiitcUoii
of liinm^oi^H green. The iiuppcmed eulphide is dissolvt'd off' tho filter
with hot nitric acid, a drop or more (accord jug k* the quantity of the
original precipitate) of tfolutiou of cobalt nitrate added, the solution
precipitated with carbonate of soda and boiled (to expel all carbonic
anhydride); the precipitate m then collected on a filter, wanhed, dried,
and igtuted in a platinum diah* If zinc be preaent in ao small a
pro|>yrtion as llOOjOOO part^ the mass will be pernianoutly green,
g 8t>8. Other methods of procedure are m follows: — -The snpjKjaed
sine sulphide (after being well mished) is collected in a porcelain di^h^
and dissolved in a few drops of mdphurie acid, filtered, nitric acid lidded,
evaporated to dryness, itnd heated to destroy all organic matter* When
cool, the maas i^ treated with water acidulated by sulphuric acid, and
again tiltered. The solution may contain iron a^ well as i^inc, and if the
former (ou testing a drop with fcrrocyanide of potash) appears in any
quantity, it must be separated by the additlou of ammonia in eicesa to
the ammoniacal hltmte ; sodio i^rbouate is added in eiceas^ the liquid
well Ixiiled, and the precipitate collected on a filter and waahed. The
carbouatc of zinc tium obtained i» converted into dnc ojtide by ignition,
and weighed. If oxide of zinc, it will be yellow when hot, white when
cold ; it will dissidve in acetic acid, give a white [ireeipit^itc with sul-
phuretted hydrogen, niid, finally, if heated on charcoal in the oxidising
0ame, and raoistenml with cobalt nitrate solution, a green colour will
result- Zinc may al80 be separated from liquids by electrolysis. The
best results are obuiined from alkaline solutions and a ntroug current
at a temperature of 50".
2* NIOKEL— COBALT,
I 869. The salts of nickel and cobalt have at present no toscicolugicul
importance^ although, from the experiments of Andcrmn Stuart,* both
may he classed as poisonous. The experiments of ISmeUu Imd, prior to
Stuart's researches shown that nickel sulphate introduced into the
stomach acted as an irritant poison, and, if introduced into the blo<Kl,
caiused death by cardiac paralybia. Anderson Stuartj desiring to avoid
all local irritant action, dissolved nickel eirbonate in acid citrate of sofla
by the aid of a gentle heat; he then evai>orated the solution, and
obtained a glass wlnch^ if too alkaline, wus nentraliHed by citric acid,
until its reaction approximated to the feeble alkalinity of the blood; the
cobalt salt was produced the Hame way. The animals experimented on
were frogs, fish, pigeons, rats, guinea'piga, rabbits, eats, and dogs- —
in all 200, The lethal dose of nickelous oxide, when subcutaneously
* '*Nidkt!l And CoIj&II : thitir Fhytiological Action on the Animal Organism/' by
T* P* Atidt'r^Ji 8tii4it, M.b,^ Juitf'ti. ij/AnaL ntai Physiol *'"' i:*n., Oct* I8is2.
694
POISONS i THEIR EFFECTS AND DETECTION.
r§ 87a
iiijei^teii in ihe soluble 4.^01 nj ton nd dt^i^ribeil, was fauad to be as folbwH: —
frogs, "OS grni, per kilugmmme ; pigeoiiss, *06 ; gumeii-pigs, "030 ; I'ats,
•025; cats, *01 j rabbitSj '009; and dogs, '007. The cobaltoua oxide
was found to be much less active, requiring the above doses to be
irioreaaed about two-thirds. In other respects, its physiological action
seems to be very similar to thsit of nickclous oxide.
g 870. Symptoms— Frogs.— A large dose injected into tUe dorsal
lymph sac of the frog causes the followir^g ^symptoms : — The colour of
the skin all over the body becomes darker and more uuiform, and not
iufrei|ucotly a white froth is abundantly poured over the integument.
In an interval of about twenty minutes the froj^ sits quietly, the eyes
ret rue ted and shut ; if moleste<i, it moves clumsily. When quiet, the
fore limbs are weak^ and the hind legs drawn up very peculiarly, the
thighs being jammed up so again st the body that they come to lie on
the dorsal aspect of the sides of the frog, and the legs are so much flexed
that the feet lie ou the auimars back, quite internal to the plane of
the thighs- Soon fibrillary twitchings are observed in the muscles of the
abdominal wall, then feeble twitchings of the fingers, and muscles of the
fore limbs generally ; lastly, the toes are seen to twitch, and then the
muscles of the hind Umbs — this order is nearly always observed ; now
spasmodic gaping and incoordinate movements are seeu, and tlie general
aspect is not unlike the symptoms caused by picrotosin. After this,
tetanus sets in, and the symptoms then resemble those of strychnine ; the
next stage is stupefaction and volutitary motor pai'esis ; the respiratory
movements become feeble, and the paresis pasties into paralysis. The
heart heats more and more slowly and feebly, and deatii gradmiUy and
imperceptibly supervenes. The j>ostrroortem appeanmces are well marked
^i.t\ rigor mortis, slight congestion of tlio alimentary tract, the heart
witli the auricle much dilated aud filled with dark blood, the ventricle
Jnostly small, |mle, aud semi-contracted. For some time after death, the
nerve trunks aud muscles reaict to the induction current
Pigeons. —In experiments on pigeons the symptoms were those of
dulness and stnpor, jerkings ofdifierent sets of muscles, and then death
quietly.
Guinea-pigB. — In guinea-pigs there were dnlness and stupefaction,
with some weakness of the hind limbs.
Bate. — The symptoms in rats were almost entirely nervous; they
became drowsy and apathetic, and there was pamlysis of the hind legs.
Babbits, — In rabbits, also, the symptoms were mainly those caused
by an affection of the nervous system. There was paralysis, which
affected either the bind legs only, or all four limbs. The cervical
muscles became so weak that the animal was unable to hold its head up.
Diarrhoea occurred and persisted until deatli. If the dose is not large
§ s; I -875- J
NICKEL — COBALT.
695
enough to kill rapidly, the reflex irritttbility is decidedly increased, fio
that the slightest exuitutiott may eiiuse the animal to cower and tremble
all over* Now appear twitchingi and contractions of single groups of
muBcleSj and this excitement becomes general* The respirations also
become slower and more difficult, and sometimes there la well merited
dilatation of the vessels of the ears and fujtdi oadi. Convulsions close
the scene,
§ 87L Circulatiou.— The effect of the salt on the frog*s heart was
also studied in detail It seems that, under the influence of a soluble
salt of nickel, tlie heart beats more and more slowly, it becomes smaller
and paler^ and does not contract evenly throngbout tlie whole extent of
the ventricle ; but the rhythm of the ventricular and auricular con-
tractions is never lost.
It is probable that there is a vaso-raotor paralysis of the abdominal
vessels ; the blood -pressure falls, and the heart is not stimulated by the
blood itself as in its normal state. In support of this view, it is foimd
that, by either pressing on the abdomen or simply inverting the frog,
the heart swells up^ fills with blood, and for a time beatij well*
Nervous Syeteiii. — ^The toxic action is referable to the eeutral
nervous system, and not to that of peripheral motor nerve-endings or
motor nerve-fibres. It is probable that both nickel and cobalt |>aralyse
to some exttnit the cerebrum. The action on the nerve-centres is similar
to that of platimim or barium, and quite different from that of iron*
g 872. Action on Striped Huscle. — Neither nickel nor cobalt has
any eftect on tstriped muscle. In this they both differ from arsenic,
antimony, mercury, lead, and iron — all of which, in large doses, diminish
the work which healthy m\isc!e is cai>ablc of performing,
§87:1 Separation of Nickel or Cobalt from the Organic Matters
or Ttgeuea — It is ver^ necessary, if any case of poisoning should occur
by either or both of these metals^ to destroy completely the organic
matters. Both nickel and cobalt are thrown down, if in the form of
acetate, from a neutral solution by sulphuretted hydrogen; but the
precipitation does not take ]ilace in the presence of free mineral acid ;
hence, in the routine process of analysia, sulphuretted hydrogen is
passed into the acid liquid, and any precipitate filtered uff. The liquid
IS now made almost neutral hy potausic car])on»ite, and then potasstc
acetate added, and a current of sulphuretted hydrogen pasfn^d through
it The sulphides of cobalt and nickel, if both are present, will be
thrown down; under the same circnmstances zinc, if present, would
also be precipitated* Cobalt is separated from zinc by dissolving the
mixed sulphides in nitric acid, precipitating the carbonates of xinc and
cobalt hy potassic carbonate, collecting the carbonates, and, after wash-
ing, igniting them gently in a bull>tube in a current of dry hydrochloric
696 POISONS r Til Elk Kl^KECTS AND DETECTION, [| 874-876.
add ; volutilti s^iiic eh bride is fgrmed and dititib over, leaving cobalt
ohloride.
§874, To eat I mate cobalt^ siilphide of cobalt raay he dissolved in
nitric acid, and tlien precipitiLted by pure potash ; the precipitate
wanhed, dried, ignitedj and weighed; 100 parts of cobaltous oxide
(CogO^) equals! 7344 of metallic cobalt. Cobalt is separated from nickel
by a metliod easentiallj founded on one proposed by Liebig. The nitric
aoid Bolution of nickel and cobalt (wbieh must be free from ail other
metalsj save potassium or Bodimu) is nearly neutralised by potassic
carbonate atid mixed with an excess of hydrocyanic acid, and then with
pure caustic potash. The mixture is left exposed to the air in a sliallow
dish for some hours, a tripotaaMic cobalti cyanide (K^CoCy^} and a
nickelo-potassic cyanide (:JKCy» NiCy^) are in tliis way pro<luccd. If
this solution Is now l>oiled with a alight e3tce>ss of mercurio nitrate,
hydnated nickelous oxide is precipitatedf but potassic eolmlticynnide
remains hi solution, aud may be filtered off. On carefully neutralising
the alkaline iiltrate with nitric Etcid, and adding a solution of mcrcurous
nitrate, the cobalt may then be precipitated as a mercurous cobalti-
cyanide, which may be collected, washed » dried, decomposed by ignition,
and weighed as cobaltous oxide. After obtaining both nickel and cobalt
oxides, or either of them, they may be easily identified by the blowpipe.
The oxide of nickel gives, in the oxidising flame with boras, a yellowish -
red glass, becoming jmler as it cools ; the addition of a potassium salt
colours the bead blue. In the redueiiig llame the metal is reduced, and
can be seen as little greyish particles disseminated through the beatl.
Cobalt gives an intense blue colour to a bead of borax in the oxidising
flame.
IV.^PRECIPITATED BY AMMONIUM SULPHIPK,
Iron — Chromium — Thallium — Aluminium — Uranium*
1. IRON.
g 875* It was Orfila's opinion that all the salts of iron were poisonous^
if given iu suflicitJUt doses; but such salts lis the CiirlKjnate» the phos-
phatCj and a few others, possessing no local action, may be given in such
very large doses, without causing disturbance to the health, that the
statement must only be taken as applying to the more soluble iron
compounds. The two preparations of iron which have any forensic
importance are the perchlcride and the sulphate.
§87G. Ferric Chloride (Fe^Cl^^ 32 5). --Anhydrous ferric ohloride
will only he met with in the laboratory. As a product of p^iesing dry
1^77, ^7S,]
IROH.
697
oliluriiii' over rodbot iron, it Btiblitnpa in brown ^enlejs 18 v«ry deli-
quescent, and lusseft when tlirowu into water. There are two very
definite hjdnit^s^ue with 6 utomB of water, fonning largo, red, deli-
quescent orytitsls j and another with 12 of water, less dehque^centi und
oryBt&Uiiinig in orange stellate grouptt.
Tlie pharnmceutical preparationa in common use are : —
Stronger Solution of Perchlortde of Iron (Lii^uor Ferri Ferchlondi
Fortior), — An orange-brown liquid of specilio gravity 1*42, and conUiirj-
ing alx>ut 58 per cent, of ferric cidoridc.
TiBcture of Perddoride of Iron (Tmctura Ferri PercMoridi),
made by dilniing 1 part of the strong solution with 1 volume of
recti tied fi[nrit, and adciiiig distilled water to menBure 4.
Solution of Perchloride of Iron (Liquor Ferri Fercliloridi),^
Simplj 5 volumes of the strong' solution made up to 20 Uj the a<ldition
of water ; hence, of the e^ime 8treugth as the tineture*
§ 877, Effects of Ferric Chloride on Animala— A very elaliomte
aeries of reaearches on rabbits, doga, and eats was !uidert»kcu some
years ago by MM. Bt'rengtT-Prrraud and Porte* to elucidate the
general symptoms and ettt!ctii produced by ferrie chloride nnder viuying
conditions. First » a series of experiments showed that, when ferrie
chloride aolnliou wjts euelosed in gelatine capsules and given with the
food of the animal, it produced either no symptoms or but trifling
inconvenience, even when the dose e^tceeded 1 grm. per kilogrm. ;
jtnhydrous ferric chloride and the ferric chloride soluUon were directly
injected into the fttouiHtih, yet, when food was present, death did not
occur, and the effects soon subsided. In animals which were fasting,
quantities of the solution equal to '6 gmi, per kilogrm. mid above
caused death in from one hour to sixteen houm, the action lieing much
accclerateil by the aidition of alcohol — ^as, for example, in the case of
the tincture : the Bymptoms were mainly vomiting &ud diarrhcea, some-
times the vomiting was absent. In a few t^aaes the posterior extremities
were j>aralysed, and the pupils dilated ; the urjne waa scanty or quite
suppressed ; tlcath was preceded by convulsions.
§878, Effects on Man,— Ferchloride of iron in the form of tinc-
ture has been jxjpnlarly used in England, from its supposed abortive
property, and is siild under the name of 'Vsteel drops. *^ It has been
frequently taken by mistake for other dark liquifls ; and there is at
least one case on rt?cord in which it was proved to have been used for
the purpose of murder. The latter casef is peculiarly interesting frona
its great rarity; it occurred in Martinique in 1874-1876^ no less than
* ** ti^de mir rem|ioiftopiiamei3l }mr le {lerchlortire d« ht" piu* MU» B^rvngtr*
Fc-rraud at Porte/ Annal€x tfNfffune PubHqu*, 1879.
t Fully rctkortcHl in Bcrongor-FdriHad'i pi^icr, lee, eU^
698
POISONS: THEIR EFFECTTS AND DETECTION. [§ 879^880.
four persona being poisoned at diflercnt date**. All four were preaumed
to have had tra moral relations with a certain widow X — — , and to have
been poisoned bj her son. In three of the four cases, viz., Char ,
Duf , and I^b^ — — ^ the cause of death aeems pretty clear ; but the
fourthj Ab -, a case of strong suBpiciou, was not sufticientlj in-
vestigated. All three took the fatal doae in the evening, between eight
and nine o^clock — Lab the 27 th of December 1874, Duf the
22nd of February 187C, and Char on the Hth of May 1876.
They had all pasiied the day in tippling, and tliey all had eaten nothing
from midday, bo that the stomach would not, in any of the three, con-
tain any aolid mattem. The chloride waB given to them in a glass of
"punch," and there was strong evidence to &how' that the son of the
widow X adminiHtered it Char- died after about tliirteen
hours' illnesy, E>nf and Lab after sixty-five hours' illness ;
Ab lived from three to four days. Witli Char- — -* the symptoms
were very pronounced in an hour, and consisted eaaentiaJly of violent
colicky pain in the abdomen, and diarrhoja ; but there was no voiniting.
Duf had alao great pain in the abdomen and suppression of the
urine. Lal>-- — hail most vtoleiit alxlomiiiul pains ; he was constipated^
and the urinary secretion was arrested ; there was^ besides, painful
tenesmus. According to the experiments of Bi^renger-Furraud and
Porte J* the perchloride in the above cases was taken imder conditions
peculiarly favourable for the development of its toxic action, viz., on an
empty stomach and mixed with aloohoL
There have been several cases of recovery from large dosea of the
tincture, e.g^ that of an old man, aged 72, who had swallowed 85 ex.
(3 ozs.) of the tincture ] the tongue swelled, there were eroupy respira*
tion and feeble pulse, but he miide a good recovery. In other C}iaea,t
2S'3 CiC. (an ounce) and more have caused vomiting and irritation of
the urinary organs. The i^erchloride is not unfrequeiitly used to arrest
hemorrhage as a topical application to tl*e uterine cavity ^ — a practice
not free from danger, for it has before now induced violent infiammation
and death from peritonitis.
g 871). Elimination of Iron Chloride.— Most of the iron ia excreted
in the form of sulphide by the fieces, and colours them of a black hue ;
a smaller portion is excreted by the urine.
§880. Post-mortem Appearances. — In the experiments on animals
already referred to, the general changes noted were dryness, pallor, and
parchment-like appearance of the cavity of the mouth, the mucous mem-
brane being blackened by the contact of the liquid. The gullet was pale
• Bub. Mtd. Pr£S9, February HI, 184S*
t Fr&ifinekU J&umal, April 7 and 21, IM7, p. 180 j Bceftlso Taybr'a PrincipUM
mtd Pradi^ of M^Hcol Jurispnuimfef vol. i* p. 320, 2nd edition^
§ 881.]
699
and diy, not tuifre'idently covered with a blackish layer, The mucous
memhraiie of Ihc stomaeli svas geuemlly healthy throughout^ but, if the
dose wfts large and very concentrated, there might be one or more
hypersDmic spots ; otherwise, this did not occur- The toternal surface
of the intestines, similarly, showed no infiaranmtion, but was covered
with a brownish coating which dark^ined on exposure to the air. The
liver, in all tlie experiments, was large and gorged with black and fluid
blood ; there w^ere ecchymoses in the lungs, and venous congestion. The
kidneys were UBually hyfjeriemic^ atid contained little hemorrhages.
There was also general enceplialic engorgement, and in one experiment
intense congestion of the meninges was observed. Few opjjort unities
have presented themselves for pathological observationij relative to the
effects produced l>y ferric chloride on man. In a case related by Christi-
sun, in which a man swallowed 42"4 c.c, (li oz.) of the tincture^ anri
died in five weeks, there was found thickening and inflammation of the
pyloric end of the stomach.
The case of Char , already alluded to, is that in which the most
complete details of the autopsy are recorded, and they coincide very fairly
with those observed in animals; the tongue wns covere^J with a greenish
fnr, bordered at the edges with a black substance, described as being like
** mud" ; the lining membrane of the gullet was pale, Ijut also covered
with this dark "mud/* The stomach contained a greenish-black bijuid ;
the liver was large and congested ; the kidneys were swollen, congested,
and ecehymosed ; the cerebral membranes were gorged with blood, and
the whole brain bypercTmic.
,^ 881. Ferrona Sulphate, Cop[>eraSf or Green Vitriol, FeS0,7ti,0
= 152 + 12t> ; specific gravity, anhydrous, 3-138 ; crystals, 1*857 ; com-
position in 100 parts, FeO, 25'92; SD^ 28*77; HgO, 45-3-1— The salt
is in beautiful, tmnsparent, bluish - green, rhombcadal prisms, The
cryst^ds have an astringent, styptic taete, are insoluble in alcohol, but
dissolve in about 1*5 times their weight of water; the comniercial
article nearly always responds to th& tetts, both for ferrous and ferric
salts containing a little persalt. The medicinal dose of this salt is
usually given as from 0648 to *324 grnu (1 to 5 grains), but it has
been prescribed in cases requiring it in gramme ( 14'5 grains) doses with-
out injury. Sulphate of iron has many tecluiical applications^is em-
ployed by all shoemakers, and is in common use as a disinfectant, Tlw
salt has been employed for criminal purposes in France^ and in this
tiountry it i^ a popular abortive. In recorded casee the symptoms, m
well as the pathological appearances, have a striking r^emblance to
those produced by the chloride. There are usually colic, vomiting, and
purging ; but in one case (reported by Chevallier), in which a man gave
a large dose of sulphate of iron to bis wife, ther^ was neither vomiting
700 POISONS : THEIR KFFECTS AND DETECTION. [§ 882.
nor colic ; the woman lost her appetite, but slowly recovered. Probably
the action of ferrous sulphate, like that of the chloride, is profoundly
modified by the presence or absence of food in the stomach. Anything
like 28 '3 grms. (an ounce) of sulphate of iron must be considered a
dangerous dose, for, though recovery has taken place from this quantity,
the symptoms have been of a violent kind.
§ 882. Search for Iron Salts in the Contents of the Stomach, etc.
— Iron, being a natural component of the body, care must be taken not
to confound the iron of the blood or tissues with the " iron *' of a soluble
salt. Orfila attempted to distinguish between the two kinds of iron by
treating the contents of the stomach, the intestines, and even the tissues,
with cold acetic acid, and allowing them to digest in it for many hours
before filtering and testing for iron in the filtrate, and this is generally
the process which has been adopted. The acid filtrate is first treated
with sulphuretted hydrogen, which gives no precipitate with iron, and
then with sulphide of ammonium, which precipitates iron black. The
iron sulphide may be dissolved by a little hydrochloric acid and a drop
of nitric acid, and further identified by its forming Prussian blue when
tested by ferrocyanide of potash, or by the bulky precipitate of oxide,
when the acid liquid is alkalised by ammonia. In the case of Duf ,
the experts attempted to prove the existence of foreign iron in the liver
by taking 100 grms. of Duf 's liver and 100 grms. of the liver of a
non-poisoned person, and destroying each by nitro-muriatic acid, and
estimating in each acid solution the ferric oxide. Duf 's liver yielded
in 100 parts '08 mgrm. of ferric oxide, the normal liver -022— nearly
three times less than Duf 's.
To obtain iron from the urine, the fluid must be evaporated down to
a syrup in a platinum dish, a little nitric acid added, heated, and finally
completely carbonised. The residue is dissolved in hydrochloric acid.
Normal urine always contains an unweighable trace of iron ; and, there-
fore, any quantity, such as a mgrm. of ferric oxide, obtained by careful
precipitation of the hydrochloride acid solution out of 200 to 300 cc. of
urine, would be good evidence that a soluble salt of iron had been taken.
The hydrochloric acid solution is first precipitated by ammonia and
ammonic sulphide. The precipitate thus obtained will not be pure
iron sulphide, but mixed with the earth phosphates. It should l)e
redissolved in HCl, precipitated by sodic carbonate, then acidified by
acetic acid and sodic acetate added, and the solution well boiled ; the iron
will then be precipitated for the most part as oxide mixed with a little
phosphate of iron.
Since, as before mentioned, a great portion of the iron swallowed as a
soluble salt is converted into insoluble compounds and excreted by the
ficccs, it is, in any case where poisoning by iron is suspected, of more
§ 8S3-88S.]
CHROMIUM.
;oi
im{>ortaiiee to examine cheiiucnlly the fecea aud the whole len^rth of the
alimentary caiml^ thuu even the contents of the stomach. In partioular,
any black niaterial lying on the nmcons membmne may bo Biilphide of
iron mixed with mucus, etc,, and should he detached, die&olvedin a little
hydrochloric acid, and the usual tests applied.
In the erimitial oases alluded to, there were iron stains on certain linen
garments which acquired an importance, for, on dissolving by the aid of
nitric acid, tliey gave the reactions of chlorine and iron. Any stains
found should be out out, steeped in water, and boiled. If no iron is dis*
solved the ^taiu should then be treated with dilute nitric acid» and the
liquid tested with ferrocyauide of potash, etc* It need scarcely be
observed thnt iron-moutd is so common on shirts and any fabric capable
of being washed, that great care must be exercised in drawing conciliations
from insohible deposits of the oxide >
2. CHBOMIUM.
^SS3. The only salts of clmmiium of toiicological importance are the
neutral chromate of potash, the bichromate of potash, and the chromato
of lead.
Neutral Chromate of Fotash, CrOgK,/)^ 194-7, contiiining 56*7 per
cenL of it^ weight of chromic anhydride, CrO^.- — This salt is in the
form of citron-yellow rhombic crystals, easily Holuble in water^ l>ut
insoluble in alcohoL Its a^jueous solution is precipitated yellow by Itiatl
acetate or basic acetate ; the precipitate being insoluble in acetic acid.
If chromate of potasli in R*>lution ia tested with silvtT nitrate, the red
chromate of silver i» thrown down ; the precipitate is with diHiculty
soluble in dilute nitric acid,
g 884. Potassic Bichromate, Cr/V^K ^O ^ 295 2, containing 68-07 per
cent, of its weighLof chroniic anhydride, OrOj^. This salt is in heantiful
large, red^ transparent, four-sided tables ; it is anhydrous an*] fuses below
redness. At a higli temperature it is decomp<^ed into green oxide of
chromium and yellow chiijumte of potash* It is insoluble iu iilcohol, Imt
readily soluble in water. The solution gives the same precipitatea with
silver, \ei\jd^ and btirium as the neutral chromate. On digestinr; a solu-
tion of the bichromate with Hulphuric acid and alcohoE, the Boiution
hecouies green from the formation of chromic oxide.
§885. Neutral Lead Chromate, PbCVO^- 323-5, composition in 100
imrtSi Pbt>^ G8"94, CrOjj, 31 00.— Thia is technically known as " Oknmw
Yellma^^ and is obtained as a yellow precipitate whenever a solution of
pluml*ic acetate is added, cither to the solutions of potasaic chronuite or
bichn>mate ; by addinir chrome yellow to fused [Xftassic nitratei ** chrome
red " is formed ; it ljti>^ the compusition CrU^^FbO. Neutral lead
702
poisons: TJIEIE EFFECTS AND DETECTION, [ §886^888.
cbromaita is insoluble Iti acide, but may be dissolved bj potassie or fiodic
hydrates.
§886. Use in the Arts. — ^Potassic bichromate is extensively used in
the arts — in dyeing, cab co- printing, the manufacture of poreelaiuj and in
photography ; the neutral chromate baa been employed to a small extent
&8 a medicine I and is a common laboratory reagent ; lead chroamte is a
yaluable pigment.
1 887, Effects of some of the Chromium Gompoundg on Animal
Life, — In the cbromates of potasfi there in a combination o( two pgiiinu-
ous metals, so that it is net aurprising that Gmeliu found the cbloride
of chromium, CrCl^ less active tlian the neutral chromiite of pota&b ;
I'd grm. of the last, administered to a rabbit by tiie stomach, cauBed
death within two hours, while 3 grms. of cbromous chloride bad no
action. Sulx^ntaneous doses of *2 to "4 grm» of neutral chromate (accord-
ing to the experiments of E. Gergens* and Carl Posnert) ^^t with great
intensity on rabbits. Immediately after the injection the animals are
restless, and show marked dyspnoea ; death often takes place within a
few hours.
Diarrhcoa does not seem, as a rule, to follow when the salt ia admin-
istered by snbcutaneouB injection to animals ; but Gmelin's rabbits had
considerable diarrhoea ivhen l^D grm. was introduced ioto the stomach.
The same quantity, inject ed beneath the akin of a dog, caused loss of
appetite^ and, after mx diiys, there whb a dry exanthem on the hack, atid
the hair fell oJf in patches; there wa^, however, neither diarrba^a uor vomit-
ing. Bichromate of potash causes (iiccording to the researches of Pciikan)^
symptoms similar to those produced by arsenic or corrosive sublimate ; it
acts as a powerful irritant of tiie stomach and intestinal caniil, and may
even cause iutlammatioti ; on its absorption a series of sjmptoms are
produced, of which the most prominent are albuminuria, blgody urine,
and emaciation. From *06 to "36 grm. (l-5i grains) is fatal to rabluts
and dogs.
^888. Effects of some of the Ckromiiuii Salts ou Man — Bichro-
mate Disease. — In manufacttiring potassic bichromate, the workmen
exposed to the dust Imve suffered from a very peculiar train of ny mptoois,
known under the name of **biebromate disease," It w^as first descrit>ed
iu England by Sir B. W. Hichardson.Sj U api^ears that if the workmen
inspire the particles chieliy through the mouth, a bitter and disagreeable
taste is experienced, with an incretise of saliviw This increase of the
* At€h,f. t^mptsHitmfiL FaihoL u. I'hurfmthoL, M. vi., Hft. 1 and 2» § 148, 1675.
I Virt;litjw*M Arthivf, pit/X Anut,, IM. Ixxix.^ Iltl. 2, § 333, 18S0.
X BeUriiffe cwr ifetuML Mt'dieinf Toxikol. u. tharnmkQilifn^tmik^ WiiralHUg,
1S53.
*^ Br It. nnti Fur. Metl. Chirunj, Oeview, OaU l&flS. See J!il»n a jtiij^tf^r by thefmmv
vrriter, vtad bftfiire the &i«diciil Suciaty, re[hirtect In Uie Litturt, Miii\ih 11, 1892.
889.]
CHROMIUM.
703
buccal secretion get» rid of most of the poison, and m that ome but little
ill effect is experienced ; bnt those who keep the mouth cloaed and iuapire
by the noae, auffer from uu iiittiimma-tirm of the aeptum, which gmdiially
geta thhi, and ultimately ulcerated ; finally the whole of the septum tsiii
this way destroyed. It is stated that wben a workman has lost his tiaaal
»eptiim, he no longer auliere from mi&al irritation, and has a rertuirkahle
immunity from catarrh. The Uheuikml Works Committee of hKniiry
report ( 1 S93) that the manufacturo of bichromate of potasli or soda ia
prac tie ally hi the hands of three firms at Glasgow^ Rutherglen^ and Fal-
kirk, and that they visited all of thenii and found ** that ^ilmcj^t dl the
men working where dnst was prevalent^ more especially lietweeii the fur-
naces and the di&solvinj^ tanks^ had either perforation of the septum of
the nose, or had loet the septum altogether," Tlie hichromate also causes
painf id skin atlections— eruptions akin to ecxema or psoriasis ; also very
deep and intractable ulcerations. These the workers call " chrotno holes;"
These cutaneous maladies start from an ejcoriaticu ; so long as the skin
is not broken, there seems to be little local effect, if any. The ettects of
the bichromate are also seen in horses employed at the factories ; the
salt getting into a wound or crack in the leg, produces uleeratitm ■ horses
may even lose their hoofs.
g 8J^9, Acute poisouiug by the chromatea is rare. In the ten years
ending 1903, in L^ngLand and Wales, 14 accidetital and 2 suicidal deaths
are ascribed to preparations of chrtjmiuin. Kalek Ims, however, l»eeu
able to find in medical literature 17 cases, 6 of which were suicidal, 10
accidental, and in one the bichromate was used as an abortive. In a
case of poisoning by the ehromatc of potash (related by Maschka),* in
which a woman, aged 25» took for a suicidal purpose a piece of potaseic
chroma to, which she described as the size of a hn Eel -nut (it would pro-
Ijably he at leaat 6 grms, in weight), the chief symptoms were vomiting,
diarrhcea, patn in the stomach, and rapid collapHt^ ; death toi>k place
fourteen hours after swallowing the poison.
In poisoning by potassic bichromate, there may be much variety in
the symptoms, the more usiud being thone common to all irritant
poisous, i.e. vomiting, diarrhcea, and colhipse, with cramps in the limbs
and excessive thirst ; and the rarer affecting more especially the nervous
system, such aa narcosis, paralysis of tlie lower limbs, nn«\ dilatation of
the pupils ; occasitmally there is slight jaundice^
In a ease recorded by Dr, Macniven,t a nmo took a lump of bichro.
• /Vuj^i- Vm'Ufjahrixhr. /. 4^, pral^t milk., Bd. 131, i 37. 1877 ; Sohniidt*^
JtUtrk 1878, Bd. 17S, i 237. Scjy oku St^^hucliArdt in Miksolikt's Handhnrh, B*i il
p. 3.
t '*Oii ti ua^ uf PoiiMjaing witli Bichhiiiiiite of poUsh/' by Eii 0. Miiciiivca,
M.B., Lancet^ SepL 2S, ISSS.
704
POISONS: THEIR KFFEOTB AND PKTECTION,
[§ 890.
mate of potaab, eetiniated to be over 2 draebms (7^7 grms,). The
symptoms commenced in fifteen minutesj and consisted of lightnesa in
the head^ and a sensation of great heat in the body, which was fallowed
by a cold sweat ; in twenty minutes he vomited ; he then suffered from
great pain in the stomach, giddinesB, a^ecks hefore the eyes, a devouring
thirst, and there was loss of power over the legs* These symptom a,
again, were followed by severe rigors and great coldness of the ex-
tremities. On the patient^s admission to hospital, two hciurs after
t-ikiug the i^ipisou, it was noted that the piipils were diUted^ the face
pale and cold, and the pulse feeble^ He complained of intense
epigastric pain, and a feeling of depression ; there was some stupor ;
the stomach was emptied by emetics and by tlie stomach-pmnp, and
the patient treated with tepid emollient drinks, whilst subcutaneous
doses of sulphuric ether were administered. He made a good recovery.
In a ease recorded by Mr. Wilsonj"*^ a man, aged 64, was found dead
in his bed twelve hours after he had gone to rest, Durin*;: the niglit he
.was heard to snore loudly ; there were no signs of vomiting or purging,
and bichromate of potash was found in the stotpach.f
§ 890, Chromaie of lead has also caused death. In one case \ tlie
breathing of ehromate of lead dust seems to have been fatal ; and there
is also a double poisoning recorded by I)r, Lin8tow,g of two children,
aged three and a half and one and three-quarter years respectively, who
ate some yellow ornaments, || which were used to adorn a cake, and
which contained chrome yelbw (chromate of lead). The younger died
in two and the elder in five days. The symptoms were redness of the
face, duluess, and an inclination to sleep ; neither i-om plained of pain ;
the younger one haii a little diarrhceii, hut the elder neither sieknesH nor
purging,
lu Gui/s HiwpiUd Reporh for 1 897, Dr. Watson Smith records the
poisoning of a grocer, aged 31, by lead chromate sup|Kised to have been
taken in home-made wine which had been standing in a lead-glased
earthenware pin. The man became jainidiced ; the unnc was of a dark
colour, but gave no bile reaction. There was vomiting' and obstinate
constipation. The tongue showed blnish*black pigmentation along the
' Mrd, Oatftte, vol. ixxiii. 7S4.
f See ultMi canes recurdi^ liy Di', Al ^Luohlim^ Oimfotn Mfd^ Jttum, , Jaly 1881 ;
Hr, M'Crcirip, Hid., May 1881; Dr. R. A. Warwick, Lancet, Jan. 31,1880; afir)
Dr, Duuhar Walker, ihid., Sept. 27* 1879— n .^nmniary of nil of whteJi may l>e fl>uiid
in T>r« Mafituron^a jHHter, if*e, ctt.
t llthr hkiilitft^ Vrrgiffttng dutch Mitathinen dea SttiubeA tw* mil Chtvmiattmg
BM'0,rijdB gtfdrhleti Oame—Fierkljafirfarkr. /. gar. Mtd.^ 1877* Bd, xxvU. HTt
i. |i. 2$,
I Ihid., Bd, XX. 3. 60, 1874.
II Th«J orriaiueTits wprfl iniitati^iriFi of he^a t *?a*^h contained 'S7 K*"^' *^'""i tmgw-
caiith, *0042 grm* ueutrml lead tshromate.
§ 891 ]
CHROMIUM,
70s
left margin of the dorsum raaemblmg '^somewhat the appearance
af an ill-aliavea chin in a person of dark complexion/* The man
recovered^
g B91, Post-mortem Appearances.— We poaseaa some yery exact
researches * upon the pathological changes induced by subcutaneons
injections of sohitions of potossic bichromate on animals, and especially
on the changes which the kidneys undergo. If the animal is killed, or
dlea a few hours after the injection, there are appireutly no striking
appearances j but a closer microscopical examination shows considerable
changes. The epithelium of the tnbtili contortt exhibits a yellow
cloudiness, and the outline of the cells is irregular and jagged*
The glomeruli are moderately injected, and their capsules contain
an albuminous exudation ; the canaliculi are filled with round cells
imbedded in a Huid which, on heating, coagulates, and is therefore
albuminous or hbrinous — probably this is the lirat stage of the forma-
tion of fibrinous easts.
In the ciuie quoted of the woman who poisoned herself with [jotassio
ohromate, very striking changes were found in tho stomach and intes-
tines. The stomach contained above a litre of dark chocolate fluid of
alkaline reaction ; the mucous membrane, in the neighbourhood of the
cardiac and pyloric extremities, was swollen and red in sharply defined
patches ; portions of the epithelial layer were detached, the rest of the
mucous membrane was of a yellow- brown colotir, and the whole intestine,
from the duodenum to the sigmoid tiexure, was filled with a partly
bloody, partly treacly-looking fluid :, the mucous membrane, throughout
its entire extent, was swollen, with numerous extravasationij, and in
places there were losses of substance. Similar appearances to these have
been foimd in other instances ; the anomalous case recorded by Mr.
Wilson (ante) is an exception. In this instance a pint of inky^ turbid
liquid, which yielded to analysis potassio biohromate, was found in the
stomach ; but there were no marked changes anywhere, save a slight
redness of the cardiac end of the gullet. In Linstow^s two oases of
poisoning by leiwJ chroniate, there were found in both fatty degeneration
of the liver cells, and red points or patches of redness in the stomach
and intestines. In the elder boy the changes in the duodenum were
very iutenao, the mucous membrane was swollen and easily detache<l, in
the upper part strongly injected with blomi ; in one place there was a
perforation, and in aeveml places the membrane was eitremely thiti.
hi the younger boy the kidneys seem to have lieen normal, in the
elder congested and containing [.ius< Altliough it was clear that
the two children die*! from lead chromate, a chemical analysis gave
no result
• Q, Poaner, ^, eU.
706 POISONS : THEIB BFFBCTS AND DBTBCTION. [§ 892.
§ 892. Detection of the Chromates and Separation of the Salts
of Chromium from the Contents of the Stomach, etc. — If in the
methodical examination of an acid liquid, which has been already
filtered from any precipitate that may have been obtained by sulphur-
etted hydrogen, this liquid is made alkaline (the alkali only being
added in slight excess), and hydrated chromic oxide is thrown down
mixed, it may be, with other metals of the second class, the pre-
cipitate may then be fused with nitre and potassic carbonate, and will
yield potassic chromate, soluble in water, and recognised by the red
precipitate which it gives with silver nitrate, the yellow with lead
acetate, and the green colour produced by boiling with dilute
sulphuric acid and a little alcohol or sugar. If by treating a com-
plex liquid with ammonium hydrosulphide, sulphides of zinc, manga-
nese, and iron are thrown down mixed with chromic oxide, the same
principles apply. If a chromate is present in the contents of the
stomach, and the organic fluid is treated with hydrochloric acid and
potassic chlorate, chromic chloride is formed, and dissolving imparts a
green colour to the liquid — this in itself will be strong evidence of the
presence of a chromate, but it should be supplemented by throwing
down the oxide, and transforming it in the way detailed into potassic
chromate.
A general method of detecting and estimating both chromium and
barium in organic matters has been worked out by L. de Koningh.*
The substances are burned to an ash in a platinum dish. The ash is
weighed ; to the ash is added four times its weight of potassium sodium
carbonate and the same amount of potassium nitrate ; and the whole Is
fused for fifteen minutes. The fused mass is boiled with water and
filtered ; if chromium is present, the filtrate is of a more or less pro-
nounced yellow colour, but manganese may produce a green colour and
mask the yellow; this colour is removed by boiling with a little
alcohol. The liquid is concentrated down to 20 c.c, filtered into a
test-tube, and a colorimetric estimation made of the chromium present
by imitating the colour by a solution of potassium chromate of known
strength. To prove that the colour is really due to chromium, acetic
acid and lead acetate are added, when the yellow chromate of lead is
at once thrown down. (If lead was in the ash, a yellow precipitate
may appear on the addition of acetic acid.) To the portion of ash
insoluble in water strong hydrochloric acid is added, and to the acid
solution a large excess of calcium sulphate is added ; this precipitates
barium as sulphate free from lead sulphate, for, if the latter should
be present, it does not, under the circiunstances, come down, being
soluble in strong hydrochloric acid.
* Arch, Pharm, (8), xitvii. 944.
I S95-896.]
THALLIUM.
707
3, THALLITTM.
§ S9$, Thallinm wu dbeovat^d by Crookes in 1861. lis &bamic weiglitis 204 ;
B|>eoific gravity^ 11 '81 to 11*91 i m(^1 ting -pointy 290°. It is & h«Avy diamagnetio
metal f very similar to lead iu iU physical propertaaa. The nitrate and »n!pbate of
thallium are b»th soluble iu water ; the carbonate less so, requiring about 25 parts
of water Fur aolution ; while the chIond« is sparingly soluble, especially in hydro ^
chloric acid.
S %9i. EffectB.^Al! the ulta of thanium are pobotioiia. One of the earlier
experimentem on the; phjsiologioal action, Paii!et» fmind 1 grm. (If) '4 grains) of
thallium carbonate saffideut to kill & rabbit in a few houtB ; there were loss of mus-
cular ^wwer, trembling of the lirahM, and death opinai^ntly from aflphyxia* Lamy *
uaed thiiUium sulphate, and found that dogs weni saUvated, and suffered from
tTemhling of the limlm, follfiwed hy paralysis. Thy moat definite resulte were
obtained by Mamif^t who found that *04 to '06 grm. of a soliiMe thuUiuni suit,
iz^deted sabcutaneouNly or dimntly into the vein^i, and "b grm. adniiiiiHt43r(.<d through
the Ktomach of rabbits, cauite^l dimth. The actioii is cutnulatiTe^ and suinething
like that of mercary ; therv are red u ess and unwell ing of the mueous membrane of th^
Htomach, with mucous bloody discharges ; hj:emiu-rhag{^ may also occur from thr
lungs. Thallium i.^ eliminated through the urine, and is ako found id titc (vscch ; it
pMOffi. tntu the urine from three to five minut«a after itiJecHon i the {elimination is
slow, oft«u taking as long as three weeks. It has bean founrl in tlte milk, in the
tears, in the mucous membrane of the mouth, of the trachea, in the aocretion i>f the
gastric juucoua membrane, and in the ]vericardia! tluid ; and in tlieHe places, whether
the jjoison has been introduced by sulicutaneou.^ injection, or by any other channel.
It seems proliable that the reason uf itu bmng detected so resdily in all the secretions
is the minute quantity which can be dLseovere<:I by spectru^'opte analysis.
I 895, Separation of Thallium from Organic Fluids or Xitaues.— The ^Its of
thallium, if ab*M»rlted, vv+>uhi only Iw eitiucted in traces from the tissues by hydrtj-
chlnric acid, mi that, in any special search, the tissues are best destroyed hy eitht^r
sulpburiii or nitric aciil, or both. In Ihe ordinary metliod of analysis, when an acid
liijuid is iirst treated with sulphuretted hydrogen, and then made alkaline by
ammonia and anjmonio sulphkl^", thallium wonid lie thrown down with the manganese
and jmn of the blood, Frtun the mixed sulphides, tlmllmm may be se|iarated hy
oxidising and dissolving the f<ul[>hides with nitric acid, evjipcn-atiiig off the ejECt^ss of
acid, dissolving iu a very little hot water, and precipilating thallous chloride by
solution of common salt The eaw, however, with which ilialliuni may be separated
ffom ioliitiomi of ita aalta by gplvanism is so great as to rt^ndtr all other pivjce^us
ttongifMMiiiy t the tiest way^ therefore, t» to obtain a deposit of the miitiil on {ilatiuum
by a current from one or more colls, and then to examine tltedpiwsitsjiectreseopiejijly.
Thallium givi^e, wlien heated in a Bnnaen thime, a magnitieent green Hue, the eentre
of which corresponds with wave len;^fth 53**9 ; a second grocn line, tlie eentm of
which coincides with W.L, &€8| may also be <liHtinguished*
4, ALUMINIUM,
§ 896. Atuminium and its Salts. —A strong solution of acetate of
alumina lias irritaut properties^ niid liaa gi^en rise to uccideDta The
tartn alum, in a ohomteal setise^ is given to a clasa of bodiea of the
type of A1XS0|, Comrnou alum ii at tbe present time ammonia alum,
OWm. NaiV9, 1BS3.
f Qmin§er QtUKrL Nmhrichkn, Aug. U, No. 20,
7o8 POISONS : THEIR EFFECTS AND DETECTION. [§ 897.
NH^A1(S04)2 + 12H20; when made anhydrous by heat it is known by
the name of burnt alum, and possesses caustic properties.
§ 897. Action of Alum Salts.— Death or illness has hitherto only
taken place from the ingestion of large doses of alum or the acetate, and
the symptoms in these cases have been those of an irritant poison ; we
are, however, indebted to Paul Siem * for a research on the absorbed
substance, in which the local effects as far as possible have been
reduced.
Siem's research was made on frogs, cats, and dogs. For frogs he
employed a double salt, consisting of sodic and aluminic lactate, to which
he ascribed the formula Al2(CgH50g)3(C3H4Na03)3, equal to 15-2 per
cent, of AlgOg. Twenty to thirty mgrins., administered by subcutaneous
injection to frogs, caused death in from ten to twenty-four hours. After
the injection there was restlessness, and, ultimately, general paralysis of
the central nervous system. The circulation was not affected ; the heart
was the last to die.
For warm-blooded animals he used the double tartrate of sodium and
aluminium. Beginning with a small dose subcutaneously administered,
he gradually increased it, and found, under these circumstances, that
the lethal dose for rabbits was 0*3 grm. per kilo, of body weight ; for
dogs 0*25 grm., and for cats 0*25 to 0*28 grm. ; if, however, a single
dose was administerfed, then cats could be killed by 0*15 grm. per kilo.
The symptoms commenced ten to twelve hours after the injection of a
large dose, but with a medium dose the symptoms might be delayed for
from three to four days ; then there was loss of appetite, constipation,
emaciation, languor, and a disinclination to move. Vomiting and loss
of sensation to pain followed, the power of swallowing even saliva was
lost, and a condition supervened similar to bulbar paralysis. However
true this picture may be when large doses are given subcutaneously, it
does not follow that hydrate of alumina in small doses, given by the
mouth, mixed with food, produces any symptoms whatever.
Alum baking-powders, containing from 30 to 40 per cent, of alum
mixed with carbonate of soda, used to be found in commerce, and for a
long time many tons were sold yearly ; it is not usual at present to
meet with an alum baking-powder. When water is added to such
powders decomposition takes place, the result being sodic sulphate and
aluminic hydrate, carbonic acid being given off. Were the hydrate, in
small doses, capable of producing indigestion or disease of the central
nervous system, it seems astonishing that, considering the enormous
number of persons who have used alum baking-powders, there should
not be some definite evidence of its effect. The senior author and his
* Ueber die Wirkungen dea Aluminiums u. BerylHuma, Inaug, Diss.f Dorpat,
1886 ; Schmidt's Jahrbuch, vol. ccxi. 128.
§ S98, 899-]
ALUMINfUM.
709
fatuily for iiiuiidi^ tugtitiit^r uuctj used alum bakiikg-powders without uuy
Kipparoiit injury; and there is little doubt that ahimintt hydt^te passes
out of the By stem mainly by the bowel, without behig absjorbed to auy
great extent, lu a trial with regard to an alum baking-powder at
Pontypridd (1893), the proaecutiou advanced the theory, and supported
it by emhient scientific opinion, that aluniiuium hy^Irate was dissolved
by the hydrochloric acid of the gastric juice, formitig cbloride of
alumininnij »ome of which might be absorbed and enter the circulation ;
that wbich wa^ not absor1>cd in tbo Htomach passed on, and, meeting
the alkaline Huids of the intestines, was again separated as aluminium
hydrate, and as such absorbed.
If this does occur, still there is no direct evidence of ita toxic influ-
ence in the small quantitiea used in baking-priwder. It may be pointed
out, also, that with regard to tlie possible lethal elfbct of a uou-eorrosive
salt of alum, presuming that tlie lethal dotje for man m the same as that
for a cat, the amount of alumina to kill a 6 8-kilogram me man would
have to be equal to 1 7 grms,, or about 3 oza., of ammonia alum. This
important question e^in only be settled by careful feeding of animals
carried on for a long |>eriod of time.
5 898. PoBt-mortem Appearances. ^In the few cases in which
pci-sons hai?e been kilted by large dose*!! of alum or its salts there have
been found corrosion of the moulli, tbroiitt and stomach, and hyperemia
of the kidneys and intestine. In the atiimals experimented upon by
Paul *Siem, bypercemia of the intestine, fatty degeneration of the livefj
and hyaline degeneration of the kidneys wtTO the chief eluuiges noted.
g 899. Detection of Alumina.— In all operatioua for the detection
of alumina, glasy and pijrcelain vessels are to be avoided* I'he sub-
stances should W buruefl to an ;bsh in a platinum dish, the ash treated
with hydrocbtoric acid, the acid driven oH' by heat, and a lew drops of
nitric acid added, and dissolved in hydrochloric acid, and the solution
boiled and filtered. If organs of the body are operated upon^ iron and
phosphoric acid will be present in the ash ; this will, indeed, be the case
with most organic substances. The filtered solution is boiled^ and,
while boiling, poured into a strong solution of sodic hydrate contaiued
in & silver or platinum dish ; the iron will now separate as oxide, and
oan be filtered off. To the tilti-ate is added a little sodic phosphate ; it
is then feebly acidified with hydrochloric acid, and ammonia added just
sufficient to render it alkaline ; a light whitish cloud of alumina pho6r
phate, should alumiua l>e present, is thrown down, and can be collected,
thoroughly washed, dried, ignited, and weighed as alumiua phosphate.*
The ulnmina phosphate is then fused with sodio sulphate in a platinum
* One part of al. |jlioephiite k ^qm^ to 0^42 Alfla !i*73a aiumoaia mlum, ifcud
i*481 potash &lum.
" ml '^7
710 POISONS: THEIR EFFECTS AND DETECTION. [§ 9OO-9O2.
dish or crucible, and the fused mass treated with hot water ; the sodic
phosphate dissolves, aud the alumina oxide may be filtered off and
dissolved in a little hydrochloric acid or sulphuric acid.
A solution thus prepared has the following properties : —
Ammonium sulphide ; white precipitate of hydroxide.
Potash or soda ; white precipitate, soluble in excess.
Ammonia ; white precipitate, only slightly soluble in excess.
There is also a blowpipe-test : if a little of the hydroxide be collected,
moistened with cobalt nitrate, and heated on charcoal by the oxidising
flame, alumina, under these circumstances, becomes of a blue colour.
6. URANIUM.
§ 900. Uranium. — The salts of uranium are intensely i)oi8onous. The nitrate of
uranium is used in photography and the arts, and is a common reagent in chemical
laboratories.
According to Kowalewsky,* the acetate of uranium possesses an unusual power
of uniting with albumin ; the other soluble uranium salts act also in a similar way.
Hence concentrated solutions of uranium salts corrode the mucous membranes, trans-
forming, for example, the walls of the stomach into a dead uranic albuminate. If a
non-corrosive salt of uranium is injected subcutaneously, glycosuria is produced, with
fatty degeneration of the walls of Uie blood-vessels, and fatty changes in the kidneys,
liver, etc. The animal wastes and ultimately dies ; 0*5 to 2*0 mgrms. of UO3 per
kilogrm. will kill a cat, dog, or rabbit, if injected subcutaneously. The nitrate or
• acetate, when given by the mouth, produces gastro-enteritis and nephritis, with
haBmorrhages in the substance of the kidney. Uranium is not used in medicine.
§ 901. Detection and Estimation of Uranium.— Uranium forms uranous and
uranic salts. Both classes of salts are not precipitated by SH2, but are precipitablo
by ammonium sulphide, and, therefore, in toxicological analyses are likely to be met
with in conjunction with iron.
The sulphides of iron and uranium may bo dissolved in strong hydrochloric acid,
boiled to expel SH3, and the solution then oxidised with a little nitric acid ; the solu-
tion is now alkalised with ammonium carbonate, which precipitates the iron as oxide
and leaves the uranium in solution. On now acidifying with nitric acid in slight
excess, a solution of sodic phosphate will precipitate uranium phosphate as a white
precipitate, alkalies will give a yellow precipitate, alkaline carbonates a yellow pre-
cipitate soluble in excess. Barium carbonate also gives a precipitate, and is useful
in separations. Uranium oxide gives a green glass in the oxidising flame with borax
or with sodic mctaphosphate.
V. —ALKALINE EARTHS.
Barium.
§ 902. The soluble salts of barium are undoubtedly poisonous, and
are of frequent occurrence in the arts. The chloride of barium is used
in the staining of wool, the nitrate and the chlorate in the green fires of
* Zeiisehr,/. anal. Chemie, xxiv., 1886, p. 551.
§ 903-906,]
BAEIUM*
711
the pjrotechuiat, the oxide and the carbonate in t\ie maiiufacLurti uf
gla^B^ The uhroumte is used by artists under the oamo of ^* yellow
ultramarine," while the sulpbate, technically known as ** permanent
white/' is, on account of its weight and cheapness^ occasionally used as
an adulterant of white powdei-s and other substances. Barium snlphide,
under various uaniea, such hh Bottcher's depilatory, Thompson's hair
destroyer, Poudre epilatQire^ aud other names, is in commerce, and has
caused poisonous symptoms.*
§ 903. Chloride of Barium, BaCl22H^U = *208 + 3(3--anhydrous, Ba,
65*86 per cent; CI, 3ivl4 ; specific gravity, 3 "75 — is in commerce in the
form of white, four-sided, tabular crystals ; water dissolves about half its
weight at ordinary temperatures, tbree-fonrtha at 100". Its solution
gives a white precipitate with sulphuric acid^ quite insoluble in water
and nitric acid.
The sialt imparts a green hne to an otherwise colourless flame;
viewed by the spectroscope, green bands will be visible. We may
note that chloride of barium gives two different spectra — the one
at the moment of tlie Introduction of the salt, the other when the
tiubstance has been exposed for some time to a high temperature.
This is caused by a rapid Iohb of chlorine, so that the first spectrum
is due to liaClg, with a variable mixture of BaCl, the sacotid to
BaCl alone.
I 904, Baric Carbonate, BaCOa^ 1 97— specific gravity, 4'3 ; BaO,
77"69 |jer cent*: CO^, 2 2 "31 — in its native form termed Wttfierite, iu a
detise, heavy powder, insoluble in j:nire water^ hut disaolving in acetic,
nitric, and hydrochloric acids, the solution giving the reactiouii of
barium.
A rat-poisou may be met with composed of baric Ofirbonate, sugar,
and oatmeal, flavoured with a little oil of aniseed and caraway*
Ji 905, Sulphate of Barium, BaSO^— specific gravity, 4'59; BaO,
65'66 per cent. ; SO.^, 34"34 per cent, — is a pure white powder when
recently precipitated^ absolutely insoluble in water^ and practically
insoluble in cold dilute acids. It is quite unalterable in the air
at a red heat] on ignition with charcoal it may be converted almost
entirely into sulphide of barium, and by ignition with CaClj into
chloride.
g 906, Effects of the Soluble Salts of Barium on Aniinals.— One
of the early noticef^ of the poisonous characters of barium compounds
was by Jame^ Watt^t who found that Wttherite^ given to dogs, produced
* Bariuiti carbouatt^ And sulphate are usually I'lxumer&tDd as oocaiional adulter-
mts of br«ad« but there is no modeni authentic iiiHimiee of tbi£*
t Mtffwirti f/zAa Liitrajy timl Philomyhi&U Society 0/ Majtchewiert 17&0, vol iii
712 POISONS: THEIR EFFECTS AND DETECTION. [§ 906.
vomiting, diarrhoea, and death in a few hours. Sir Benj. Brodie *
administered barium chloride, and noticed its paralysing eflfect on the
heart. Orfila t made several experiments, and observed that 4 grms. of
the carbonate produced death in dogs in periods varying from one to
five hours; but in these experiments the gullet was tied. The later
investigators have been Gmelin, Onsum, Cyon, and Bohm.t Gmelin
found barium carbonate and barium chloride act in a very similar
manner; and, indeed, it is improbable that barium carbonate, as
carbonate, has any action, but, wheu swallowed, the hydrochloric and
other acids of the stomach form with it soluble compounds. J. Onsum
made eight experiments with both barium carbonate and chloride on
animals. The respiration was quickened and, at the same time, made
weak and shallow ; the heart's action was accelerated ; the animals
became restless; and there was great muscular prostration, with
paralytic symptoms ; convulsions did not occur in any one of the eight
animals. He found, on post-mortem examination, the right side of the
heart full of blood from backward engorgement ; he describes a plugging
of the small arteries with little fibrinous coagula, having an inorganic
nucleus, with constant hsemorrhagic extravasations. Onsum seems to
have held the theory that the baryta salts circulated in the blood,
and then formed insoluble compounds, which were arrested in the
lungs, causing minute emboli, just in the same way as if a finely-
divided solid were introduced directly into the circulation by the
jugular vein.
Onsum stands alone in this view. Cyon found no emboli in the
lungs, and refers the toxic efiect to a paralysing influence on the heart
and voluntary muscles, and also on the spinal chord. Cyon, to settle
the embolic theory, injected into the one jugular vein of a rabbit barium
chloride, and into the other sodic sulphate, but the small arteries and
capillaries of the lungs remained clear. Bohm, operating on frogs, found
a great similarity between the action of small doses of barium salts and
that of certain organic poisons, as, for example, cicu toxin; *012 to '02
grm. subcutaneously injected into frogs, acted as a heart-poison. So also
Blake § found the heart slowed, and concluded that barium chloride
had a direct action on the cardiac muscle, and also a toxic influence on
the nervous system. F. A. Falck, in experiments on rabbits, found a
great reduction of temperature after poisoning with barium chloride
(3' to 12-6'*).
♦ PhU, Trans,, 1812. t Traiti des Poisons, 8rd ed., t. i., Paris, 1826.
X Gmelin, C. G., Versiiche ilhcr die Wirkxingen des Baryts, Strontians, Chroma,
Molybddns, Wolframs, Tellurs u, s, to, auf den thierischcn Organismus, Tiibingen,
1824 ; Onsum, J., Virchow's Archiv, Bd. ii. 1868 ; Cyon, M., Archiv f. Anatomic,
Physioloffie, etc., 1866 ; Bohm, Archiv/, experiment. Pathol., Bd. iii. 1874.
§ Joum, of AnaL and Physiol., 2nd aeries, 1874.
I 907p 90SO
BARIUM.
713
§ 907, Effects of the Salts of B&rhim on Man.— There were alx>ut
fifteau cases of poisoning by barium salta on record by the ev\d of 1883
— three of which were suicidal, but moat of them were due to accident
or mistake ; one accidental death ia also recorded in the ten years ending
1903. In three caues, bariqm cbloritle wjis taken instead of Ulauber*g
saltfi ; in one, instead of Carl&bad salts ; in another, a mixture of barium
nitrate and sulphur, instead of pure sulphur ; in a sixth case, a mixture
of barintn iicetate and nispbeiTy syrnp, instead of sodic ethylsulphate ;
in a seventh, a chemist put a laiger dose than was ordered by the pre-
scription; and iu fotir cases barium carbonate had been mixed with
Hour^ and this fiour need in the making of pastry. Of the cases, 60 per
cent proved fatal.
Patal Dose.— The recorded cases of poisoning hiive not satis fa ctorily
settled the question as to the least fatal dose of the barium salts ! 6*5
grms. (about 100 griiins) of the chloride have destroyed the life of an
adult woman in fifteen hours ; 14 grms. (| oz.) of the nitrate of baryta
have killed a man in six and a half hours ; and the carbonate of baryta
has destroyed a person in the relatively small dose of 3 "8 gnns,
(60 grtfcins). On the other hand, certain Continental physicians have
preseribed barium chloride in large medicinal doses; for example^
Hrondi * and Lia franc t have gradually raised the dose of bjirium
chloride from 4 decigrams up to 3 grms. (48 grains) daily, giveu, of
course, in divided doses^ Pirondi hiniMelf took in a day T*7 grms, (119
grains) without had eflect.
§ 008. SymptotUB. — ^The local action of barium salta must be sharply
dii^tinguished from the action of the absorbed milts, Robert divides the
ajmptoms into seven groups :^
(1) Local, consisting iu tmi/ttttfe, nausea, salivatiou, vomiting, and
pain in the stomach. This group merges so much into the next as
hanily to admit of precise separation.
(2) Excitation of the alimentary canal, both of the nervous
and muscular apparatus ; hence vomiting, painful colic, and acute
diarrhoea* All these phenomena may be produced in animals by
subcutaneous injection, and, therefore, do not depend alone upon
local action,
(3) Excitation of the brain motor centres, which leads to Gonvulslons^
or may result in paralysis* About half the recorded cases of barium
poisoning in the human subject have been convulsed j the other lialf
paralysed. In one case mania resulted*
(4) Weakness or destruction of the power of muscular oontractiou ;
this produces in frogs, wfieu the muscular test movements are recorded
* Df lit Tumetir Btttnthf de Otiuntj ed. 2, Fariii, 1830.
t Qaz. M^iL ik Parijif 1335, Ku. U.
714 POISONS: THEIR EFFECTS AND DETECTION. [§ QOQ.
graphically, a veratrin-like convulsion curve. In the human subject the
effect is that of great muscular weakness.
(5) Digitalin-like influence on the heart and blood-vessels, showing
itself in great slowing of the pulse, pr»ecordial anxiety, and strong
beating of the heart (not only sensible to the patient, but which
can be heard and felt by the bystanders). The arteries are incom-
pressible and rigid, the blood-pressure strikingly raised. The blood-
vessels of old people do not stand the pressure, hence haemorrhages
in the lungs, stomach, and other organs. Frogs die with the heart
in systole.
(6) Catarrhal affection of the conjunctiva, the mucous membrane of
the respiratory tract, and the nose.
(7) Formation of insoluble baryta salts in the blood-vessels, accord-
ing to Onsum. This has not been observed in man^ and the fact is
disputed (see ante).
In Dr. Tidy's case,* in which a man, suffering from rheumatism, but
otherwise healthy, took a mixture of barium nitrate, flowers of sulphur^
and potassic chlorate, instead of sulphur, the symptoms were blisters on
the tongue, a burning pain in the gullet and stomach, with vomiting,
diarrhoea, convulsions, aphonia, and coldness of the extremities. A case,
copiously detailed by Seidel,t in which a pregnant woman, 28 years
old, took carbonate of baryta for the purpose of self-destruction, is in-
teresting. She probably took the poison some little time before six in
the evening ; she vomited and had great pain in the stomach, but slept
during the night without further sickness. The next morning, after
drinking some coffee, the sickness was renewed ; nevertheless, at 7 a.m.,
she repaired to her employment, which was distant an hour s walk ; she
probably suffered much on the way, for she did not arrive until 9 a.m.
The vomiting, accompanied by diarrhoea, continuing, she was sent to
bed at 2 p.m. She was very cold, and complained of great weakness ;
the vomiting now ceased. At 8 p.m. she shivered violently, could
scarcely swallow, and the respiration was oppressed. At 11 she
seemed a little improved; but at 3 a.m. she was found much worse,
breathing rapidly, but fully conscious ; at 4 a.m. she was again seen,
but found dead: she thus lived about thirty-four hours after taking
the fatal dose.
§ 909. Distribation of Barium in the Body.—Neumann has shown
that after repeated injection of insoluble barium sulphate into the veins
of rabbits, barium is to be found in the liver, kidneys, spleen, and
spinal cord, but not in the muscles, thymus, or brain. G. Linossier X
* Pharni. Journ., June 1868.
t Eu!enlHTg*8 Vierteljahrsschrifl f. ger. Med,, Bd. xxvii., § 218.
t Compt, rend, Soc. Biol, (8), iv. 122-123.
§9>o.9i']
BARIDM.
7'S
hiiu made a Bimilar series uf eiperimentH, but with th ecarbaiiate, and
this salt was injected into animals for a period of thirty days. All the
organs contained some bariuiii ; lungs, muscles, and the heart only oon-
taitied tracers ; the liver nither more ; the kidney s^ brain, and spinal cord
still more ; and, lastly, the bones a considerable quantity^ as much as
0"056 per cent.
§910, Post-mortem Appearanoefl.— The post-mortem appearances
are usually changes in the stomach and intestin«.l tract, but there are
only rarely traces of great infliimmation. It is true that in a case
recorded by Wach* perforation of the stomach was found ; but, since
there was old-standing disease of both liver and stomach, it is not clear
that this is to be attributed entirely to poison. In the case of suicide
just detailed^ the mneona niembratie of the stomach was much
eeohymosed ; over the whole were strewn little white grains, sticking
to the m aeon 8 membrane, and there were also ecchymoses in the
duodenum.
§911, The Separation of Barium Salts fi'om Organic Solids or
FIoidB, and their Identification, — In the usual course of examination
uf an unknown subitancej the matter will already have been extracted
by bydrochlortc iicid, and the solution successively treated with hydric
and am moil ic sulphides. The filtrate from any precipitate, after
being boiled, would in such a caae give a precipitate if treated with
sulphuric acid, should a salt of banum soluble in hydrochloric acid
be presents
If there, however, should be speeiai grounds to search for baryta in
particular, it is beat to extract the substances with pure boiling water, to
concentrnte the solntioUjand ther* add sulphurit; acid, collecting any pre-
cipitate which may form, if the latter is found to i)e sulphate uf baryta,
it must be derived from some soluble salt, such as the nitrate or the
chloride. The substances which have been exhausted with water are
now treated with hydrochlorlo aoid, and to the acid filtrate sulphuric
acid is added. If sulphate of baryta is thrown down, the baryta present
must have been a salt, insoluble in water, soluble in acids— probably the
carbonate. Lastly, the organic substances may be burned to an ash, the
ash fused with carbonate of soda, the maj^ when cool, dissolved in HCl,
and the solution precipitated with sulphuric acid. Any baryta now
obtained was present probably in the form of sulphate ; nevertheless^ if
obtained from the tissues, it would prove that a soluble salt bad been
administered, lor (so far as is known) sulphate of barium is not taken up
by the animal fluids, and is innocuoua.
The sniphate of barium is identilied as follows:^
(1) A part of the well washed precipitate is boiled with distilled
• IIenk«'» ZeOat^tiJlf. SUmi$arsn^nl%t 1835, Bd, ixx , Hft. 1, 1 1.
7l6 POISONS: THEIB KFTICTS AND DKTICTION. [§ 9II.
water, filtered, and to the filtrate a solution of chloride of barium added.
If there is no precipitate, the sulphate can be none other than baric
sulphate, for all the rest, without exception, are soluble enough to give
a slight cloud with baric chloride.
(2) The sulphate may be changed into sulphide by ignition on char-
coal, the sulphide treated with HCl, the solution evaporated to dryness,
and the resulting chloride examined spectroscopically ; or, the sulphide
may be miied with chloride of calcium, taken up on a loop of platinum
wire, heated strongly in the flame of a Bunsen burner, and the flame
examined by the spectroscope.
(3) A solution of the chloride of barium obtained from (2) gives
a yellow precipitate with neutral chromate of potash, insoluble in water,
but soluble in nitric acid.
APPENDIX.
Treatment by Antidotes or otherwise of Cases of Poisoning*.
§ 912. All medical men in practice are liable to be summoned hastily
to cases of poisoning. In such emergencies not a moment is to be lost,
for valuable lives have ere this been sacrificed simply from the delay
caused by searching for medicines and instruments, and visiting the
patient unprovided with suitable remedies. Hence it is far the safest
plan for every medical man to provide himself with an " antidote hoAj^^
which, to be complete, should be furnished with the following
requisites : —
I. Instruments: —
(1) A stomach pump or tube,* with proper mouth-gags.
(2) A hypodermic syringe.
(3) An ordinary bleeding lancet.
(4) A glass-syringe with suitable canula, which may, in case of
necessity, be used for transfusion.
(5) Bistoury, forceps, and tubes suitable for performing tracheotomy.
A small battery (interrupted current).
* The stomach-tube is simply a tube of india-rubber, from 6 to 8 feet in length,
one end of which should be a Httle stiff, and have a solid rounded extremity pierced
with two lateral oval holes— catheter-like ; but, on an emergency, any india-rubber
tube of a suitable length will do. It is used by passing the proper end gently down
the throat into the stomach ; if the {latient is insensible, or, as in some determined
suicides, obstinate, the jaws must be forcibly opened by the handle of a spoon, and
some solid substance placed between the teeth so as to give sufficient room for the
entry of the tube. If the tube is now passed in the median line well into the grasp
of the pharynx, it is actually drawn down into the stomach by the pharyngeal
muscles, so that the operator has, as it were, only to " pay out" a sufficient quantity
of the tubing. Holding the tube in a i)er))endicular position, it may then be filled
with water by means of a small funnel. When full, the end must be pinched and
brought down to the ground to deliver in a basin ; it will then act as a syphon, and
the contents of the stomach will be syphoned off. The tube is elevated again above
the body, and the stomach filled with water ; this syphoned off, and the process
repeated. Coffee, also, or antidotes may be conveniently introduced. If the recum-
bent position is necessary, the patient must, of course, be placed on a bed or table, in
order that there should be sufficient fall for the syphon.
7«y
7l8 POISONS: THKIR EFFECTS AND DETECTION. [§ 9 1 2.
II. Emetics: —
(1) StdphcUe of zinc.
(2) Apomorphine,
(3) Mustard,
(4) Ijpecacimnha,
The stdphcUe of zinc may either be carried in 30-grain powders or
in the ordinary solid crystalline state, together with a little measure
made out of a small pill-box which, when exactly full, is found to con-
tain from 25 to 30 grains.
A still more convenient form is that of the compressed tablets, sold
as a speciality by one or more firms. The same remarks apply to
ipecacuanha.
The apomorphine hydrocldorate should be in solution ; a suitable
stiength is 2 per cent. A few drops of this substance, injected hypo-
dermically, will cause vomiting in a few minutes.
Besides the above list, the bag should be funiished with a selection
of the so-called antidotes.
Antidotes : —
(a) CJiemicals neutralising the poison.
Acetic acid and calcined magnesia.
{h) Precipitants of alkaloids.
Tannin.— A solution of iodine in potassic iodide.
(c) Narcotics^ or anoedJieticSy for the treatment of the tetanic class.
Chloral --chloroform.
{d) Substances which act physiologically,
French oil of turpentine. — A solution of atropine sulphate for
hypodermic use (strength -8 per cent); hypodermic dose from 5 to 6
drops.
Solution of nitrate of pilocarpine (strength 5 per cent.); dose, 10
drops or more.
Muscarine. — A solution in water (strength 5 per cent); dose, 10
drops.
Morphine meconate in solution (strength 10 per cent.) ; dose, from
5 drops.
A solution of nitrate of str3rchnine (strength 2 per cent.) ; hypo-
dermic dose, from 2 to 3 drops.
Potassium Permanganate in crystals.
To these may be added a bottle of Wyeth's dialysed iron for use
in arsenic poisoning, a flask of brandy, some chloric ether, aromatic
spirits of ammonia, and some really good extract of coffee.
I 913]
APPENDIX : TBKATMEMT — ANTIDOTES.
719
TREATMENT.
§ 913, Aero, CARBOLia
Use the stomach tube or pump, unless there is great destruction of
the mucous membrane. Id the latter case^ excite vomitiug by injecting
subcutaneously from 5 to 6 dropn of the apomorphine solution ; or gi?e
an emetic of zinc sulphate, ipecacuaoha, or mustard^
The stomaeh m^j, hj the aid of the tube^ be washed ont with a
wei\k alkali oe solution of soda ; albimien nmy also be ^^ivon, and such
stimulants as br&ndj timl water^ chloric ether, and aromatic spirits of
ammonia.
It is important to apply warmth to the extremities.
Inject aubcutaneoualy From 2 to 3 drops of Ihe atropine hypodermic
solution*
Kitrite of amyl by inhalation is said to have been useiful
In desperate cases bLeeding, followed by transfusion, is to be con-
sidered.
Acids— MiNKRAt*, including Sulphuhio, XtTBio, Hydro€HIX>ric, Glacial
Acetic Agiun,
Stomach tube or pump, inadmissible.
Neutralise by calcined magnesia, linne^ chalk, i*r soda, but not with
potash, if there m choice.
If no neutralising agent can be immediately pnxjnred, then dilute
with plenty of water.
Other remedies are— oil, milk, white of eggs, giuel
tt is often recommended in such caaes to administer hypodermtcally
a little morphine.
ACONITB — ACONITIHS.
U.He fit uiice the stomach tube or pump, or give emetics of sulphate
of zinc, or hypodermic solution of apomorphine.
Keep the patient in the recumbent posture.
After the atomaoh baa been emptied, give atropine, either by hypo*
dermic injection or by the mouth, aay 4 drops of the IMS. solution ;
failing atropine, 20 drops of the tincture of belladoima. The dose may
be repeated more or less fre(|uently according to the condition of the
patient.
If there is great tendency to heart-syncope, tincture of digitalis in
J -drachm doses by the mouthy or in hypodermic doses of from 10 drops
upwards.
Apply a mustard pouUice to the pericardium; aid vomiting and
720 POISONS: THKIR EFFECTS AND DETECTION. [§913-
elimination of the poison by plenty of water, to which may be added
brandy or any form of alcohol.
Inhalations of nitrite of amyl are said to have been useful. If the
breathing stops, try artificial respiration.
Alcohol.
Empty the stomach by the tube or pump, and then wash it out with
warm coffee ; if the stomach-tube is not at hand, them empty the stomach
by hypodermic injection of 5 drops of apomorphine, or by a mustard
emetic, or sulphate of zinc. Keep the body very warm, but the cold
douche may be applied to the head.
Endeavours should be made to rouse the patient, if insensible, by
shaking, shouting at him, etc.
Inhalations of amyl nitrite are said to be useful.
Alkalies — Ammonia — Potash — Soda. — Stomach pump or tube not to
be used.
Vomiting nearly always present, or may be produced by administer-
ing plenty of lukewarm water , after which give dilute vinegar, or the
juice of lemons or oranges; olive oil, the white of eggs, barley-
water, arrowroot, and always plenty of water may be administered.
There may be oedema of the glottis, especially if ammonia has been
taken. In such a case, and death threatening from suffocation, perform
tracheotomy. In poisoning by ammonia, with croupous respiration,
keep the room warm, and fill it with steam by means of a bronchitis
kettle.
Relieve pain by small doses of morphine injected subcutaneously.
Ammonia. — See Alkalibs.
Antiarin. — See Digitalis.
Antimony — Tartar-Emetic — Antimonial Wine, etc.
Tlie stomach will generally have been emptied by vomiting. In those
rare cases in which this does not take place, use the stomach pump or
tube, or give hypodermic injection of apomorphine.
Follow this with doses of strong tea, or give half a drachm of tannin
or gallic acid in warm water.
Give also demulcent drinks, and stimulants in small doses, frequently
repeated.
Keep the patient very warm by hot blankets and wraps.
The interrupted galvanic current to the heart may be useful.
Apocynin. — See Digitalis.
§ 9t3^]
APPENDIX: TREATMBNT— ANTIDOTES.
721
AaaENia
Use the stoniach pump oi" tube, or empty -atotiiacli by emetics^ such
as hypodermio Hylutiou of apomorphina, or give mufitard or Bulpbate of
zinc. Tbe stomach should tfioD be washed out by large quantitiea of
water, moat cooveuieotly administered by the pump or tube.
If the tube or pump is not at hand, then administer iit once either
dialyeed iron, or the freably precipitated hydrated 03dde of iron,
obtaiued by precipitating the ordinary perch loride by lueans of
carbonate of soda or ammonia, avoiding excess of the latter, If the
operator has sufticient chemieal knowledge to precipitate the iron with
fair exaetnes^s, ao that there is no groat excels of ammonia, or of uodic
carbonate, then titration is unnecessary. In other caaea, filter through
a bandkcrchief-
Oil, mucUaginous drinks, the white of eggs, and, if fatntueas exiata,
small doses uf fitimulaiitB may all be given,
II the akin is oold, warmth must be applied to the body by means of
hot blankets, etc.
Pain may be relieved by morphme.
Atropine — Bbi.lauonna — Tinctukb or Belladonna.
Empty the stomach by means of the Btomach pump or tube.
Gi^e an enema of co£fee,
Administer half a gmm <>f pilocarpiBe nitrate ; or, if that is not at
hand, tnorpbllie or opium in Hoit-able dosea will act to a certain eittent
antagonistic to the p^jison.
A subcutaneous dose of muBcarine may be administered instead of
pilocarpine, Imt is not quite so good.
Hot water to the feet, alternate doncbes of cold and hot water are
found useful.
If the respiration seems likely to stop, artificial reBpiratlDn must be
practised*
Bellaoonna. — SeeAfEOPrnK,
Benz^enb.
If swallowed, then empty the stomaeh by pump or tube, or by the
hypodermic injection of apomorphine ; or give emetics, such as sine
sulphate, mustard, or IpecacnanhE.
If the vapour haa been inhakd^ this is nnnecesaary.
Plenty of fresh air.
A subcutaueons doHe of atropine, s.ay l-60th of a grain, or from 30
to 40 drops of belladonna tincture.
Alternate douches uf hnt and cold water to Uie ehest, artificial
722 POISONS: THEIR EFFECTS AND DETECTION. [§ 913.
respiration, if necessary. The heart to be maintained by mild inter-
rupted shocks of the battery over the region of the heart.
BiOHBOMATE OP P0TA8H. — See Chromium.
Bruoinb. — See Strychnine.
Calabar Bean— Physostiqminb.
Use stomach pump or tube, or emetics, such as sulphate of zinc,
mustard, or ipecacuanha; or, better still, hypodermic solution of
apomorphine.
Give hypodermic doses of l-60th grain atropine until the pupils
dilate. This treatment seeming to fail, chloral in 10-grain doses, every
quarter of an hour, has been recommended.
In certain cases strychnine has been used in hypodermic doses of
1-1 2th of a grain.
Stimulants and artificial respiration will probably be necessary in
some cases.
Oamphor.
Use stomach pump or tube, or empty the stomach by emetics.
Hypodermic injections of brandy, inhalations of ether, the alternate
hot and cold douche, warmth to the extremities by hot blankets, etc.,
seem to be the best methods of treatment.
Cantharides — Cantharidine.
Use stomach pump or tube, if the mucous membrane of the throat
is not inflamed ; or, administer hypodermic dose of apomorphine, or
give emetics— sulphate of zinc, mustard, or ipecacuanha.
Allay pain with morphine. Give plenty of water and demulcent
drinks.
Chloral.
Use stomach pump or tube, and, when the stomach is emptied,
introduce by the same means warm coffee, or give a hypodermic
injection of apomorphine, or administer emetics of sulphate of zinc,
or mustard, or ipecacuanha.
An enema of coffee will be useful.
Keep the limbs warm.
Administer hypodermically 2 or 3 drops of the solution of strychnine
at intervals of from fifteen to twenty minutes.
Rouse the patient by various means, such as shouting, shaking,
flapping the skin with a wet towel, etc.
Inhalations of amyl nitrite are recommended.
Artificial respiration may be necessary.
§ 9130
APPENDIX i TEEATMINT^ ANTIDOTES,
7n
Ceix>eatb op Potash,
Use the same treatment as for mtiBte of potash i^whie.h iBe^ p. 728}*
CuLORiDB OF ZiNa — ^See ZiNa
Chloroform— { Inhalmi),
Give plenty of fresh air, pull the tongue forward, and commence at
onae artificial respiration. If the heart has stopped, strike the chest
two or three times very hard over the region of the heart ; this has been
found occasionally to restore its beat. Apply the battery, but with a
weak current only ; one pole may be placed on the larynx, the other at
the pit of the Rtomach,
lubalatiotiB of nitrite of amyl are useful p The hot and cold douche
may also be used.
C iiLORopo R« — ( Swallowefi).
Empty the stomach by piunp or tube, or by emetics, such as 5 drops
of the hypodermic solution of apomorphine, or sulphate of zinc, or
mufitard.
Give an enema of hot coffee.
Administer large draughts of water, which may advantageously
cont&lu a little sodic carbonate in aohttion*
Attempt to rouse the pntient. Nitrite of amyl inhalations, and, if
necessary, artificial reispiration may bo U8ed.
Ckromatb of Potash, — Bee Ohromjitii.
Ghromio Acm» — See GuRoMiuM.
GhROMIUH — BlOlIROMATE OF PoTASU^ChHOIIATB OF POTASH — GhROMIU
Acii>.
Empty the stomach by pump or tube ; administer a suhoutancous
injection of apomorphine, or give sulphate of zinc, mustard, or
ipecacuanha as emetics. Follow up by administeriugi suspeuded iti
water, calcined magnesia, or carbonate of magnesia, or chalk.
Demulcent drinka, such as barley-water, etc.
CoocuLus iFDictrs.— See Piobotoxik.
CoLCHiGUM — Meadow SArFROX — 0>louicum Wfke, Tiwotore, etc.
Use stomach pump or tube, or ernpty the stomach by emetics, such
as sulphate of ^c, or mustard, or ipecacuanha ; or, better than all»
give a hypodermic injection of 4 or 5 drops of the solution of apo-
morphine.
Give taimiii or gallic add in ^-drachm dosf ^ or coffee.
724 POISONS: THKIR EFFECTS AND DKTBCTION. [§ 913.
Allay the pain in the bowels and purging by small doses of opiitm
or morplime.
Keep the extremities warm, apply hot fomentations to the abdomen ;
stimulants may be used, give plenty of water and demulcent drinks.
COLOCYNTH.
Treatment on the same lines as that for Goucuiomt.
CoNiuM — Hbmlogk.
Empty the stomach by the pump or tube, or give a hypodermic
injection of 4 or 5 drops of the solution of apomorpbine, or emetics of
sulphate of zinc, or mustard.
Keep up the temperature of the body by hot wraps.
Administer, as a drink, strong t^, tannin, gallic add, or any
harmless vegetable decoction containing tannin.
Stimulants may be administered.
If necessary^ use artificial respiration.
CoppBR— Salts op.
Empty stomach by pump or tube, and either inject by the same means
or administer white of egg in solution in water ; if no white of eggs can
be had, substitute milk ; give plenty of water and emollient drinks.
Pain may be allayed by opium or morphine.
Corrosive Sublimate — Pkrohloride of Mercury — Nitrate op
Mercury.
Empty the stomach by the tube or pump, and wash the organ out
with plenty of white of egg, dissolved in water or milk. If the stomach-
pump is not at hand, then give emetics, such as the solution of apomor-
pbine, hypodermically, in from 4- to 5-drop doses, or a zinc sulphate
emetic, or mustard, or ipecacuanha. Probably violent vomiting is
already present, then stomach-tube or emetics are unnecessary : but, in
any case, give plenty of albuminous fluids, such as white of egg in
water or milk. If neither of these is at hand, chop any fresh meat up
as finely as can be done in a short space of time, diffuse iu water, and
administer. Follow up with demulcent drinks, such as barley-water,
flour and water, etc.
Pain may be allayed with a little opium or morphine.
Stimulants are admissible, if necessary.
Croton Oil.
Empty stomach by means of tube or pump, or give emetics of
mustard or sulphate of zinc, or administer hypodermic injection of
apomorpbine.
§913.1
APPENDIX: TREATMENT — ANTIDOTES.
72s
Give 10 drops of laudanum every twenty minutes or half hour,
until the pain and purging are somewhiit abated, or else inject Bub-
outiineously small doses of morpliitie at intervalH.
Give plenty of demulcent drinks.
Two or three drops of essence of camphor in milk are useful.
Stimulants, such as brandy, ammonia, or chloric ether, are
admissible.
Cyti BINE. —See Laburnitm.
C DRARINB — WOOR A R I ^ — Ur A RI .
The poison is, of course, introduced by a wound : if any is likely to
be atill in the wound apply a ligature, suck the wound, and then wash
it with a slightly alkaline solution of potaestc permanganate.
Keep up the respiration artificially, give plenty of water and a
dose of spiriLs of nitre, apply warmth to the loins. By the^u me^Lns the
poison will be rapidly separated by the urine; and, if the patient can
only bo kept sdive by artificial respiration for a little time, he may
recover, for elimination is very rapid.
C VAN IDE OF PoTAsaiUM. — Sec Prusbic Acid*
DloiTALi^ Group of Heart Poison^ imltidinrj, besides the Digitalins,
Antiabin, Apocysiin, KerhNi OleanphiKi Evonymin, Thevktim,
SOILLAIN, SXEOPHANTmj and EltYTIlEOrtlLElN.
Empty the stomach by the tube or piunp, or adndiiistur a sub-
cutaneous dose (4 drops) of apomorphine, or give a tablespoonful of
mustard in water, or sulphate of zinc.
Follow up with strong te% or lialf a drachm of tannm, or gallic
acid in aqueous s4>lution.
A very small dose of acomttne tdtrate in solution (say L>20Qth of a
grain) may bo injected subcutaneoiisly and the effect watched ; if in a
little time it seems to do good, repeat the dose. On no account Jet the
patient ri^e from the recumbent posture, or he nmy faint to death,
Stimulants iu BumU doses may be given frequently by the mouth,
or, if there is vomiting, by the bowel.
ESGOT,
Use stomach pump or tube, or empty the stomach by a mustard
or sulphate of zinc emetic, or give a subcutaueous injection of apo-
morphina
Give a purgative, such as a drop of cxoton oil, and assbt its action
by plenty of warm drUiks.
726 POISONS: THKB EFFECTS AND DETECTION. [§ 913.
Tannin aud gallic acid have also been rccommeDded, but are
probably of but little use.
After the bowels have well acted, and the stomach has been emptied,
give small doses of opium at intervals.
Dr. Murrell recommends l-50th of a grain of nitro-glycerin every
fifteen minutes.
The recumbent positiou is necessary, and the circulation should be
maintained by warmth, and, if necessary, by friction.
Erythropulbin. — Sec Digitaus.
Ether. — The same treatment as with Chloroform.
EvoNYMiN. — See Digitalis.
tuNGi. — See Mushrooms.
Gelsemininb.
If seen soon after taking the dose, use the stomach pump or tube,
or give a tablespoonful of mustard.
Administer a small dose of atropine subcutaneously, or give by the
mouth tincture of belladonna in 20-drop doses.
Stimulants are admissible.
If necessary, use artificial respiration.
Rouse the patient by hot and cold douches.
Hemlock. — See Coniinb — Conium.
Henbane— Hyoscy AMINE. — The same treatment as for Atropine.
Hydrochloric Acid. — See Acids, Mineral,
Hydrocyanic Acid. — See Prussic Acid.
Hyoscyamine. — The same treatment as for Atropine.
Iodine.
Empty the stomach by pump or tube, or administer emetics, such as
the hypodermic solution of apomorphine, or give by the mouth mustard
or sulphate of zinc.
Give plenty of starch diffused in warm water, or in the form of a
dilute paste; or give any farinaceous substance whatever, such aa
arrowroot, boiled rice, or flour, or thin gruel.
Inhalations of amyl nitrite have been recommended.
Pain may be relieved by morphine or opium.
Jaborandi. — Treatment the same as Pilooarpinb.
S9'3]
AfPEKDLX: TKlATMEIfT — A^TmOTES,
72;
Labdbwum Skeds — CYTmiNB.
Eoiptj atomach by tube or pump, and wash it out with tea or coffee,
or give (as mi emetic) 11 liypodermJe dose of apomorpliiiiej or (by the
moutb) mustard or zinc Bulphate ; follow up thin treatment by au
enema^ or ii brisk purgative.
Stimulants may be ndmrniBtared ; the patieut may be rouaed by' the
hot or cold douchen.
Laubanitm. — See Morphike,
Lattrel Water. — See pRusaia Acm^
Lead^ Salts op.
Empty stomach by pump or tube, or administer subcutaueousty a dose
of apomorphine, 4 to 5 drops ; or give by the mouth a sulphate of zinc
or muBtard emetic. Follow up with half a dracbm of dilute sulphimc
add, or half an ounce of magnesic or sodic sulphate.
Blilk and albuminous fluids mtiy be giveu.
Allay pain with opium or morphine. Treat coltc with hot fometi*
tatious.
Meadow Saffron* — See Ck}L€mouM.
Mbhcury, Salts of. — See Corrobivk StTBLiMATi.
Monkshood. — See Acohiti*
MoRPHiKa^OpiUM — Laudanum and pfeparotitmi in which ih& Qnvu
ALKALoms pr&dominaie.
If taken by the moutb, give at once a solution of potassium per-
manganate and then empty the atomach ; but^ if taken by hypodermic
injection, both these would be useless. The atomach in opium-poisoning
iH best relieved by the pump or tube, and should then be well washed out
with hot coffee, leaving in the organ a pint or more. If the stomach
pump or tube is not at baud, a large subcutaneotis dose of apomorphine
(say 10 minims) may be given ^ or mustard or zinc sulphate ; but there
may be difficulty in obtaining vomiting from any emetic,
Attempt to rouse the patient by the battery, if at hand ; by flips with
a towel, and by shaking. In alt books will be found the usual direction
that you are to keep walking the patient about ; but this treatment is
questionable, and likely to favour the toxic action of morphine on the
heart.
Ammonia may be applied t4> the nostrils.
Hot coffee m*^ «'«o be introduced into the bowels by an enema
apparatus, or '"'be.
jT^t ?*:(a»'>?y?: THia DTim isif iswzwcnmL [§ 913.
Tzik ik,',^TiAZ^ coid aad boC doneke 10 sae haki » 2Q<jd, bos the bodj
.SguLI vr^'jp'.ZAZLarA'^ iuMs :f airo|iiK < ^^j l-^jth of a snin; mmj he
adminiawsriii. r»c<^i:rr-z «^ 'ioK rrecr cnnsj minaceay and vmsching the
If Qieccaurr, ^pcrh* artificiid rsfiimtion.
lr,hAhzirAa of mSzite of an^ kkre been iLsed.
yiuacAMi^t. — See MrsHSOjxs.
'Sll^HtUj^fM.^. MuSCARTir* PoiSf>5t>C5 FUXGI GcnOLALLT.
EriiptT ^touj-^L bv stomadi pomp or tube, or give a sabcutaneous
dose of i4Knii0frpfaiDe, or adminiati^r bj ibe moutb either nmstaid or
zJnc sulphate.
loject 2L& sooD as possible a sulicataneous dose of 2 to 4 drops of the
iTjlutioD of atropine : or, after the stomach has been emptied, gire
tiocture of belladoima everv balf-hour, in from 20- to 30-minim doses.
It is e*{UHWj important t^^ remove the remains of tbe fungi from the
luteKtiiiCH, aod for this purpose it is well to gire a dose of castor oil, and
to use an enema.
Stimnlanta maj be giyen. The body should be kept warm.
Neriin. — See Digitalis.
Nicc/ri-VE — Tobacco.
Unless the stomach has been already emptied bj vomiting, use
stomach pnmp or tube, or give an emetic of mustard and plenty of
water.
Inject sulx^utaneously a small dose of strychnme (say l-25th of a
grain of tho nitrate), or give half a drachm of tincture of nux vomica.
Stimulants, such as brandy, chloric ether, etc., may be given.
Keep the body warm, but the cold douche may be applied to the
head.
Tannin and vegetable infusions containing tannin may also be given^
but it is questionable if they are of much use, unless any remnants
remain in the stomach.
Keep the patient lying down for fear of fatal syncope.
Nitre — Nitrate of Potash.
Empty the stomach immediately by the pump or tube, or give a
subcutaneous dose of apomorphine (from 2 to 3 drops), or administer by
the mouth a tablespoonful of mustard, or a scruple of sulphate of zinc.
Dilute tho poison, and attempt to wash it out of the system by giving
plenty of water or mucilaginous drinks.
[§9I3- APPENDIX: TREATMENT — ANTIDOTES. 729
Apply hot fomentations to the loins, and keep the patient as warm
as possible.
Stimulants that are likely to increase the kidney congestion are to
be avoided.
Inhalations of nitrite of amyl have been recommended.
Nitric Acid. — See Acids, Minbrau
Nitro-Bbnzenb.
Empty the stomach at once by the stomach pump or tube, and wash
the organ out with plenty of warm water, to which advantageously a
little spirit may be added ; or give emetics, such as zinc sulphate or
mustard.
Administer stimulants, either by the stomach-tube, as an enema, or
by subcutaneous injection.
Keep up the respiration artificially, if necessary, and maintain the
heart's action by application of weak, interrupted shocks to the chest-
wall, by means of the battery.
Rouse the patient by the douche.
Atropine subcutaneously has been recommended.
Nitrous OxiDb Gas.
The treatment is the same essentially as for chloroform {which see).
Inhalations of oxygen may do good, but oxygen is very rarely at hand.
Nux Vomica. — See Strychnine.
Oleandrin. — See Digitalis.
Opium. — See Morphine.
OxAuc Acid — Binoxalate of Potash — Sodic Oxalate.
Unless the patient has already vomited freely, empty the stomach at
once by emetics of zinc sulphate or mustard ; or the stomach pump or
tube may, in most cases, be used. If the acid has been taken, neutral-
ise by chalk, lime-water, or, better, by saccharated lime-water ; but
on no account neutralise by carbonate of soda or any alkali, for the
alkaline oxalates are extremely poisonous.
Assist elimination by the kidneys by giving plenty of water ; apply
hot fomentations to the loins.
An enema may be given, if necessary, to empty the bowels well.
Phosphorus.
Empty the stmnaoh ^nd, at the same time, wash
the organ out with 1 been added a drachm of
730 POISONS: THEIK EFFECTS AND DETECTION. [§913-
French turpentine, or give emetics. The best emetic for phosphorus is
said to be sulphate of copper, 4 or 5 grains dissolved in water, and
given every ten minutes until vomiting is produced.
In default of sulphate of copper, then sulphate of zinc or mustard.
Give ^-drachm doses of turpentine, floating on water or on mucil-
age, every half-hour. Inhalations of turpentine vapour, much diluted,
are also of service. The American and Grerman turpentines are said to
be of no avail. Probably the turpentine will freely purge the patient ;
but, if not, the bowels should be opened by a suitable purgative, such,
for instance, as magnesic sulphate.
Physostigminb. — See Calabar Bean.
PiCROTOXIN — COCCULUS InDICUS.
Use stomach pump or tube, or empty stomach by usual emetics,
e,g. mustard, zinc sulphate, or apomorphine, subcutaneously.
Chloral, in doses of from 10 to 20* grains, may be given every half-
hour to allay or prevent tetanus, the effects being, of course, watched.
For the same purpose bromide of potassium has been recommended.
In severe cases, it may be combined with chloral, 1 drachm of the
bromide with 20 grains of chloral.
PiLOCARPINB.
The best treatment is a subcutaneous dose of atropine (say l-60th
of a grain) or tincture of belladonna by the mouth in 20-minim doses,
to be repeated every twenty minutes until the pupils dilate.
Potash. — See Alkalies.
Prussic Acid.*
Use stomach pump or tube, or, if not at hand, an emetic of mustard
or sulphate of zinc.
If the breathing has stopped, try artificial respiration and weak
shocks to the heart.
* J. Kossa, considering that potassium permanganate ought, theoretically, to act
as a chemical antidote to potassium cyanide, by checking the paralysis of the
respiratory centres, has performed some experiments. Babbits were shown to be
fatally affected in a few minutes by 0*01 grm. of the poison, but if, at the time of
administration, 0'5 grm. of permanganate dissolved in 50 c.c of water was also
introduced into the stomach, doses of cyanide up to 0*1 grm. failed to cause death*
Larger quantities (0*2 grm.) proved fatal under similar conditions, but the action of
the poison was much delayed. Successful experiments were also performed with
aqueous solutions of hydrocyanic acid containing 0*1 per cent. It is suggested,
therefore, that, in cases of cyanide poisoning, J to } litre of a 3 to 5 per cent,
solution of permanganate should be administered immediately {VroUch, through
Nouv, rem,t ix. 567).
§ QIJO APPENDIX: TREATMBNT^ — ANTIDOTES ^$1
l-60th of tt gmia of atropine subcutaneous ly ia recom mended to
assist the heart's action,
A i3(randy enema may be given, or brandy injected under the Bkin.
The body tuust be kept wamij but the uold doucbe may be advau-
tageou«ly applied to the bead.
Salts of Sorkjsl, — See Ozaiaq AoiDp
Savin*
If the patient haa not already emptied the stomach by repeated
vomiting, and the throat is not inflamed, ufse the stomach pmnp or
tube, and wiiah the organ out with water, or give auy one of the u&usd
emetics — such as mustard, Bulphate of zinc, or ipecacuanha.
If tho bowelfi have not acted well, give a doae of castor oil ; allay
paiu with Bmall do^ee of morphine^
Soillajn: — See Dioitaus. /
8nAKEW, lilTK OF.
8uck the wound, and apply au alkaline solution of permanganate
of potash.
In severe cases of cobra poiaouing nxid other extremely venoraons
Buake^ death threatening, the only likely means of saving hfe would
be bleeding at one arm and transfusing blocHl by the other.
Ammonia may be given by the month, and also smelt.
In cobra puit^ontng and venoms which kill mainly through the
reepiration^ the breathing must be kept up arti^cially ; and, should
there be signs of the heart failings weak, interrupted galvauic shocks
may be applied to the walls of the chest.
Lacerda'fi plan of injecting permanganate of potash under the skin
is not only useless but even mischievous, for it takes up time which
might be more valuably employed.
Soda Cactstic— See Alkalisb.
Solan IKE — Solanum DuLCAMAaA — BrrrKa Sweet — Woody NfaHT-
8HADB. — The same treatment as for AthuPIKk (which ^ee).
8T£UJiONiuu.— The same treatment as for ATttortNic.
Stbophantin.— See Digitalis.
StryohnIxN'k^Bbucinb— Ndx Vomica.
Empty the stomach as quickly as possible by an etnetic of mustard
or zinc sulphate, or by a hypodermiu solution of apomorphiue (4 drops).
732 POISONS: THEIR EFFECTS AND DETECTION. [§ 913.
The stomach pump or tube inadmissible : for, if tetanus is present,
it cannot be applied ; or, if absent, it is likely to excite a spasm.
Place patient at once under chloroform or ether, and keep up a
gentle narcosis for several hours, if necessary.
Darken the room, stifle all noise; if in a town, and opportunity
permit, have straw or peat placed at once before the house to deaden
noise.
If the spasms threaten the respiration, artificial respiration is
absolutely necessary; and, to facilitate this, it would be justifiable,
in a dangerous case, to perform tracheotomy — of course under
chloroform.
Chloral may be given in place of chloroform, but the latter is best ;
the dose of chloral should be, at least, half a drachm, and if no effect is
produced in half an hour, then doses of 20 grains should be given at
intervals of a quarter of an hour.
If neither chloroform n«r chloral is at hand, the juice from a
recently-smoked pipe may be diffused in a little water and a few drops
injected subcutaneously, and the eflect watched. If there is a marked
improvement the treatment may be persevered in.
Bromide of potassium in combination with chloral has been recom-
mended.
Nitrite of amyl inhalations are said to be of use.
Curarine in a subcutaneous dose of one-third of a grain b antagonistic
so far that it paralyses the voluntary muscles.
Sulphuric Acid. — See Acids, Mineral.
Tartar Emetic— See Antimony.
Tartaric Aciu. — The same treatment as for Oxalic Acid {which see),
Thbvbtin. — See Digitalis.
Tobacco. — See Nicotine.
Turpentine.
Empty stomach by tube or pump, or administer the usual emetics,
such as mustard, or sulphate of zinc, or ipecacuanha, or give hypoder-
mically 3 or 4 drops of the solution of apomorphine.
If purging is not already present, empty the bowel by enema; give
plenty of water and demulcent drinks to aid elimination by kidneys.
Apply hot fomentations to the loins.
Allay pain with opium or morphine.
§91^]
APPfi;NDIX: DOMSSTIC EEMEDXSg.
733
Empty thd stomach hy the tube or pump^ or giv^ any one of tlie
uaual emetieu, &uch as muBtard, or zinc sulphate, or ipe€acuanlia.
Keep the patient lying down,
StimulEiits may be administered.
Ad enema of hot coffee has been recommended.
Keep the body warm with wraps, hot blankets, etc.
White Precipitate. — The same treatment as for CoBiiosiviB Sublimate,
Wasps, Bkis, Ho uNB-ra— Sting of.
An oniOE immediately applied to the part stnng is a favourite
popular remedy j but ammama is better.
Extract the sting, if it remains in the wound,
liive BtioiulaiitBj if necessary.
The only salt likely to cause poisonous symptoms is the chloride
which is used in the arts, and is the actiye principle of Bumett*a dis-
infecting Kuid*
Stomach pump or tube inadmiBaible. Give plenty of water, in
which carbonate of soda is dissolved ; or, if that is not nt hand,
carbonate of potash.
Eggs and milk ghould also be giveD.
Solutioua of tamiin, strong tea, and the Uke, alaoi to some extent,
neutralise the poison.
The pain in the abdomen is to be allayed in the uftual way— by
hot fomentations^ and small frequent doses of morphine or opium.
DOMESTIC READY REMEDIES FOR POISONINa
1 914, Large bonseholds, more especially those in which no one
possesses any special medical knowledge, would do well to furnish an
ANTiDoTR cuPBOASP, for use in cases of emergency. This cupboard may
contain : —
(1) The MMipU AntvMe^ which consists of saturated solution of
sulphate of iron 100 parts, water SOO, magnesia 88, nnimal charcoal 44
parts. It is beet to have the animal charuonl and magnesia mixed
together in the dry state and kept in a well-corked l)ottle ; when required
for use, the saturated solution of sulphate of iron is mixed with eight
times its bulk of water, and the mixture of charcoal and mivgnesia added
with couRtant stirring. The multiple antidote may \ye given in wine^
llasfiful duties^ frequently repeated, in poisoning by arienic, zinc, opium,
734 P0I80K8: THKIE KFFICTS AND DKTBLTION. [§ 914.
digitalis, mercury, or strychnine ; it is of 00 use in phosi^oniB poiaooing,
or in poisoning by the caustic alkalies or sntimony.
(2) Calcined Magnetui, for use in poisoning by adds.
(3) French Turpentine^ for poisoning by phosphorus.
(4) Powdered ipecacuanha in a well-corked bottle ; the bottle con-
taining a small pill-box which is cut down, so that when full it contains
30 grains — the proper dose as an emetic. A similar small supply of
sulphate of zinc may also be provided.
(5) A tin of mustard.
(6) A bottle of vinegar.
If, then, provided with such a supply, any member is known to
have taken poison, and yet the precise poison is not known, give a
sulphate of zinc or ipecacuanha emetic, and follow it up by the mul-
tiple antidote, which is in itself not poisonous.
If Phosphorus has been taken, then give the French turfleiituie as
directed under Phosphorus (p. 730).
If Acids, neutralise by the calcined magnesia (see Acids, Mineral,
p. 719).
If Alkalies, neutralise with vinegar (see Alkalies, p. 720).
INDEX.
Abel and Crawford, on epinephrin,
505.
,, and Field's test for bismuth in
copper, 655.
Abrus precatorins, 478.
Abrus, The toxalbuniin of, 478.
Acetaldehvde, 170.
Acetaniliae, 90.
Acetic acid, 116.
Aceto nitrile, 223.
Acetyl gronp, 41.
,, morphine, 805.
Acetylphenylhydrazine, 40.
Achscharumow, Action of aconitine on
birds, 869.
Acidity due to acid salts, 106.
Acids and alkalies, 81.
Acids, Internal effects of, 88.
„ Mineral. See Hydrochloric cund,
Sulphuric acidf etc.
„ „ Hilger's test for, 94.
„ „ Tests for, 105.
,, „ Treatment in cases of
poisoning by, (App.)
719.
,, „ Treatment of poisoning
by, 89.
Aconite, Derivation of name, 4.
„ extract, 360.
„ Fatal dose of, for cats, 366.
, , group of alkaloids, 860-377.
„ liniment (linimentum aconiti),
860.
,, ointment, 360.
,, pharmaceutical preparations,
360.
,, tincture, 360.
,, Treatment in cases of poisoning
by, (App.) 719.
Aconitine, 250, 265, 269, 360, 861, 362.
,, Action on birds, 869.
,, ,, mammals, 869.
„ man, 370-376.
,, Effects of, on animals, 366,
367.
,, Melting and subliming tem-
peratures, 260.
„ Physiological action of, 375.
, , Poet-mortem appearances after
poisoniiiff bv ft?^.
„ Ptopv
Aconitine, Separation of, from stomach,
etc., 376.
,, Statistics of poisoning by,
370.
„ Tests for, 368.
,, Treatment in cases of poison*
ingby, (App.) 719.
Aconi tines, 361.
,, Fatal dose of, 365.
Aconitum napellus, 360.
AcquaToffiina, 11.
Adenine, 263.
Adler, Effects of picric acid, 471.
Adonidin, 448.
Adonis vemalis, 440.
Adrenalin. See Epinephrin,
^thyl-urethane, 37.
Agaricus pantherinus, 480.
„ phalloides, 429.
„ ,, Post-mortem appear-
ances after poison-
ing by, 430.
„ ruber, 430.
Agarythrine, 430.
Agrostemma-sapotoxin, 450.
Anrens on the decomposition of cevadine,
404.
Albers on dose of coniine, 271.
Alcohol, Amylic See Amyl Alcohol,
Ethylic, 142.
„ „ Criminal or accidental
poisoning by, 142.
,, ,, Excretion of, 146.
Fatal dose of, 144.
,, ,, in brain, 146.
,, ,, in chloroform. Detec-
tion of, 152.
„ „ Post-mortem appear-
ancesafter poisoning
by, 145.
,, ,, Statistics of poisoning
by, 142.
„ ,, Symptoms of poisoning
by, 144.
,, ,, Toxicological detection
of, 147.
,, Treatment in cases of poisoning
by, (App.) 720.
Alcohols, 142-149.
,, Identification of, 147.
Aldehyde group, 41.
785
736
INDEX.
Alexander VI., Death of, 7.
All Ahmed's treasures of the desert, 619.
Alkalies and acids, 81.
Alkalies, Detection of, 126.
Caustic, 122-127.
,, Effects on animal and vegetable
life, 124.
,, Estimation of, 127.
,, Local action on skin, etc., 124.
,, Museum specimens illustrating
poisoning by, 126.
,, Post-mortem appearances after
Jtoisoning by, 125.
ts of the, Toxicological de-
tection of, 127-133.
, , Symptoms of poisoninc by, 1 25.
,, Treatment in cases of poison-
.„ , .. ingby, (App.)720.
Alkaloids, 248-431.
,, Colour tests for, 251.
,, containing oxyeen, 263.
,, „ metnoxyl groups,
264.
,, „ nitrogen, 264.
,, Discovery of, 16.
„ Estimation of, 264.
„ General tests for, 248.
,, Identification of, 257.
,, Identification of, by organic
analysis, 263.
,, Melting-points of, 262.
„ Purification of, 268.
,, Separation of, from organic
matter, 252-257.
„ Sublimation of, 258-262.
Alkyls replacing hydrogen, 35.
Allantoin, 39.
Allen, A. H., Assay of carbolic acid
powders, 193.
on lead in drinking
water, 630.
on bromine test for
carbolic acid, 187.
on distinction between
naphthas, 136.
on tne composition of
vermin-killers, 332.
Alloxantin, 39.
Almen, on the physiological action of
oxalic acid, 539.
Alumina, Detection of, 709.
Aluminium, 707-710.
Alum salts. Action of, 708.
,, Post-mortem ap{>earance8 in
poisons by, 709.
Amanita muscaria, 426.
Amarin, 40.
Amblard, on the action of morphine,
303.
Amido-phenols, 34, 35.
Amines, 510.
Ammonia, 116-122.
,, Action on human beings and
animals, 119.
Anmionia, Chronic poisoning by, 119.
,, Estimation of, 12i2.
„ Fatal dose of, 120.
,, in solution, Action on plants,
119.
„ OflBcinal preparations of, 117.
,, poisoning, Museum specimens
by, 121.
, , Post-mortem appearances after
poisoning by, 121.
,, Properties of, 116.
„ Spectroscopic appearance of
blood in poisoning by, 120.
,, Separation from organic
matters, etc., 121.
,, Statistics of poisoning by,
118.
,, Symptoms in poisoning by,
118.
, , Treatment in cases of poisoning
by(App.),720.
„ Uses of, 117.
,, vapour. Poisoning by, 118.
Ammonise liquor fortior, 117.
,, carbonati, 117.
Ammonic cyanide, 221.
Ammonium salts, Neutral, 128-184.
,, ,, Toxicological detection
of, 134.
Amphibia, Poisonous, 483-486.
Amygdalin, 204.
Amylal, 87.
Amyl alcohol, 148.
,, Detection of, 148.
Amyl nitrite, 148.
,, ,, Post-mortem appearances
after poisoning by,
149.
Ansesthetics. See Chhroform^ Chloral^
etc.
„ Minor, 170.
Anderseck, on a case of poisoning by
mercuric chloride ointment, 676.
Anderson, H. T., on the alkaloid of
aconite plants, 361.
Androctonus funestus, 486.
Androctonus occitanus, 486.
Aniline, 250, 284, 285.
„ Detection of, 286.
„ Fatol dose of, 285.
,, Properties of, 284.
,, Spectrum of colour reactions,
58.
„ Symptoms and effects of
poisoning by, 284.
Animal toxmes, 607-529.
„ „ Isolation of, 507-510.
Anson, Hon. Mrs., poisoned by laudanum,
307.
Antiarin, Effects of, 445.
,, Separation of, 445,
,, Treatment in case of poisoning
by, (App.)720.
Antidotes, (App.) 718.
^^^^^H INDEX. ^^^H
^^^H AntLinonial wtne^ Traatmcat in cmm of
Arsenic, Elimination of, 577. ^^^^^|
^^H iioisonlDg bj CApp), 720.
Eatimation of, 591. ^^^^H
^^^H Antlmaiyium ui^iti pun 6ca turn, 602.
^^^H ADtimonmi'^ttea hydnigeOj 614. Bee
by electrolyeia, ^^^^|
^^^M
Imbibition of, aft^r dvath, 537. ^^^^|
^^H StiMn£, filB,
in beer, 571 ^^^^^|
^^^H Antimony^ 600-615.
in glycerin, 5S5. ^^^^H
in hydrochloric acid, Ofl. ^^^^^|
^^^H^ Alloys cootKining, 604.
^^^H ehtoride, EtfecUof, 610.
in organic matter, 585. ^^^^^|
^^^^B ,, Chronic poiaonmg by, 607,
in the arta, 552. ^^^^^|
, , Compound used in pyrotech ny
In trrxl action of, 561. ^^^^^|
Cijn twining, 604.
in wall papers, 564, 500. ^^^^H
„ Detection of, hi orgnni^*
ii)dide^ 551. ^^^^^|
matter. 611.
( itraenion !j an hydride), Projiertlee ^^^^H
„ Dose of, 605.
^^^1
,, Elimination uf, filO.
Ltiw rclatinj; Ui, ^57, ^^^^^|
„ KatinitLtiou of, 614.
LrxMilisatiao' of, in the iKKiy, ^^^^H
,, modicinos, chiefly veterinary,
^^^H
603.
Met&llic, Proiiertie^ of, 546. ^^^H
„ MctaHic, 600.
Mirrors of, 5Sa. ^^^M
,j MiiToi-s of, 583,
Pljarmaceutical preparationa of, ^^^^^|
„ oxide, Ellccta of, ou amiunK
^^^H
606,
Pby^iological action of, 576. ^^^^|
1, Patent ftnd qUAck pills eon-
Pigments con tainiug, 555* ^^^^^|
tidning, 603,
j.H>isoniug, Ab^nce of symptoms ^^^^^|
f, FbnTTnaoeutical pre|iarfrtious
^^^^H
of, 602.
Antidotes for, 577. ^^^^^|
„ PigmeutH containing, 605.
by external applica- ^^^^^|
„ Poat - mortem appearancea
^^^H
ftfter poiaoning by, 600.
Forms of, 564-569. ^^^H
^^^ ,, Sulphide or, 600.
Microscopical appear- ^^^^^|
^^^H , , Treatment in Gaum of jfoiaon-
ances of liver ^^^^^|
^H ingby,(App.)7*20.
^^^H
^^^ AutH, 491.
MuHcum pre{)arationa ^^^^|
■ Aplyaia, a
inuHtrative of, 573, ^^^^^
H Apocodeiue, 29^,
Fost-mort^^m appej&r- ^^^^^|
H A|KK>yuin, 449,
u tioe^ of, 572 , 5 73 . ^^^^H
^K , ^ Trm tmejit 1 n cases of {JOiBouing
Quack nostrums containing, 554. ^^^^H
■ by, (App.)720.
Rat and fly ^loisons containinf^, ^^^^^|
■ Apocynum cauiiablnam on»bam, 4i9.
H Afiollodoruifi S.
^^^H
Sheep-dipfi containing. 555. ^^^^^|
B AjjomorpiiinOj 298, 323,
Slow poisoning by, 56S. ^^^^^|
™ „ Tefltfor, 329.
Soaps containing, 555. ^^^^^|
„ Dose of, mi.
Solubility of, 547. ^^^H
Aqua Laum-oeraai, 203,
Bt&tistica of poisoning by, 556, ^^^^^|
Aquetta de Fenjgiaj 11.
sulphide, 551, 579. ^^^^H
Aftki, T,, on the phyniological action of
terivulpttide, ICstiniiAtioD by ^^^^^|
arsenic, fi76.
iodine, ^^^^|
Arotsns, RHTecta of lead on the nervous
Estimation aa ^^^^^|
sYFiteni, 626.
Aribine, 263,
niagnesmn ar* ^^^^^^|
^^^^1
AriiQld*? case uf prussic acid poison ing^
Estimation i^ ^^^^H
'J07.
ai^i'nomolyb - ^^^^^|
Arai-uiatea, 553, 579.
am * ^^^^^1
■ Ai^Qto, 547-600.
monia, 598. ^^^^^|
^^^^ chloride, 551,
Estimation aa ^^^^^|
^^^^L ,, compounda naed in pyroteehny^
metallic arsea- ^^^^H
^^H
^^^H
^^H Detection of, 577.
Precipitation of, ^^^^^|
^^H Doaea of, 557,
^^^H
^^^1 eaters, 5S0.
Treatment of poisoning by, ^^^^^|
^^^H £ffeetaofjOnaniQaikK55S,
(App.)72L ^^H
^^H man, 560, 564-560.
Veterinary medicines contain- ^^^^^|
^^1 p1anta,558.
^^^M
■
^^^H
738
INDEX.
Arsenioos acid. See Arsenic,
Arsenites. 579.
Arsen-methyl chloride, 36.
Arseniuretted hydrogen, 648. See Arsiiu.
Arum maculatum, 481.
Arsine, 548.
,, Etfects of, on animals and man,
549.
,, in the arts, 549.
Aselline, 528.
Asiatic knowledge of poisons, 4.
Aspidium Filix mas, 481.
Aspidosamine, 353.
Aspidospermatine, 358.
AspidoBpermine, 353.
Assamin, 450.
Astier, L., The active principles of
Lathy rus sativus, 480.
Atkinson's infant preserver, 293.
Atropa belladonna, 378.
Atropamine, 378, 396.
Atropine, 250, 264, 265, 377, 378.
, , Accidental and criminal poison-
ing by, 385.
,, Action on animals, 886.
„ „ the iris, 384.
man, 887.
,, Constitution of, 880.
, , Diagnosis of poisoning by , 390.
„ Fatal dose of, 386.
„ Melting and subliming temper-
atures, 261.
,, Physiological action of, 389.'
„ Post-mortem appearances after
poisoning by, 390.
„ Properties of, 381.
,, Separation of, from organic
matter, 391.
,, Statistics of poisoning by, 384.
„ Tests for, 881-884.
, , Treatment of poisoning by, 390
(App.), 721.
Atroscine, 396.
Attains Phylometer, 2.
Aatars(J.) antidote for prussic acid, 213.
Baker on ereot epidemic, 461.
Bamberger, Urine in sulphuric acid
poisoning, 95.
Banded Krsit ( Bungarus fasciatus), 503.
Baptisia tinctoria, 398.
Bardach's (B.) method of separating
mercury, 689.
Barium, 710-716.
„ carbonate, 711.
,, chloride, 711.
„ Distribution of, in the body,
714.
,, Effects of salts of, on animals,
711.
„ „ „ on man, 713.
, , Fatal dose of salts of, 713.
,, Post-mortem appearances in
poisoning by, 715.
Barium, Separation and detection of,
715.
„ sulphate, 711.
,, Symptoms in poisoning by salts
of, 713.
Barker on thiB action of strychnine, 338.
Barrier on the nervous form of arsenic
poisoning, 568.
Barth on the poisonous nature of sodic
nitrate, 129.
Bartholow, Antidote for physostigmine,
412.
Basic method for destroying organic
matter, 53.
Bauman and Kast on relation between
narcotic power and ethyl groups, 171.
Baumann, E. , on excretion of carbolic
acid, 184.
,, ,, separation of animal
tozines from urine,
510.
„ „ separation of guani-
dine from urine,
521.
Baum, H., and Seeliger, R., on copper
oleate, 634.
Bazt on the effects of papaverine, 322.
,, ,, thebaine, 822.
B6coeur*s arsenical soap, 556.
Beef, Poisoning by, 530.
Beer, Arsenic in, 571.
„ Poison of, 491.
Behren's method for identifying alkaloids,
257.
Belgian commission on ii:jurious effects
of hydrochloric acid on vegetation,
100.
Belladonna, Pharmaceutical preparations
of, 880.
„ alkaloid — discs (lamelln
atropine), 880.
,, ,, solution of at-
ropine aol-
pnate, 880.
I, „ ointment, 880.
,, leaves— juice (suocus bella-
donna), 880.
,, ,, tincture, 880.
„ root — alcoholic extract, 880.
„ ,, liniment, 380.
,, ,, ointment, 380.
„ „ plaster, 380.
,, Treatment of poisoning by,
(App.) 721.
Belladonnine, 378, 396.
Bembo on nitric acid poisoning, 111.
Bennet on effects of coniine on man, 271.
Benz-aconine, Fatal dose of, for cats, 806.
Benzene, 138.
,, Detection and separation of,
138.
,, Treatment in poisoning by,
(App.) 721.
Benzoic acid. Test for, 865.
^^^^r ^^^^^^V ^^H
^^^H Beaa^Iine, 135*
Bird, Dr. Golding, A cas<i of ae&nitin« ^^^^H
^^H h&mo nitnk, 223.
])oisoningt 372. ^^^^H
^^^H BeiiKOpiirpurin test for luineTal acid, 105.
Bishop Stortford cAsm of food poisoning, ^^^^^|
^^^1 Bensayl'iu^oDiEe, B04.
^^^H
^^^H J, chloride method for isolntiDg
Bi^mutli, 652-657. ^^^H
^^^^ft fttiimal toxiiieei, S09,
citrate aolutton, 653. ^^^^^M
^^^^H ecgonioot 34, 356.
Estimation of, 655, 656. ^^^^|
^^^^r morphine. 305.
elcfitrolj'tically, ^^^^^|
^f Bfiti^y! uitTib, 223.
^^^H
H BerbeHne, 250, 265.
Extraction and detection of, ^^^^H
^^^H
^^L on the [H^isonous elt'^ta of ferrio
in the arts, 653, ^^^^|
^^H chloride. ^97.
lozengea, 652, ^^^^^M
^^^1 BerKf^roti and Hole, L. L., on copjier in
MBdicinaJ doses. 653. ^^^^^H
^^H the Mmmi body, 640.
nitrate, 652, 653. ^^^^^H
^^^H B«rtiftrd, Ckndc, hydrochloric add In
o%ide, 653, ^^^^^|
^^^H g«»tno j uie^, e tc. , 6d.
oleate, 653. ^^^^|
^^^^B ,p on the etf«!tB of
peroxide, 652. ^^^^^|
^^^^1 codeine, 318.
,f [iharmaoeatical preparations, ^^^^^|
^^^^H oil the effects of
^^^H
^^^^1 narcetne, 320.
potassium iodide, 240. ^^^^H
Fropertiea of, 652. ^^^^1
^^^H an th« poiaonous
^^^^1 action of mercuric
^pn ration of, 654. ^^^^^|
anb^]at«, 653, ^^^^|
^^^1 cyanide, 222,
^^^^H on tlie eHectfl of
snluodide, 653, ^^^^H
^^^V ji«tmvenne, 321.
fiulphide, 652. ^^^H
^f BemaUlc on the poisonons etfecta of
Tests for, 655. ^^^^^1
■ Bernhardt on olfects of 03^, 173.
Toxic etrecta of, 653. ^^^H
Bismnthic |)ota^ic iodide reagent, 249. ^^^^H
^M Ikrntroirfj method of deteitting lead in
Bisulphide of carbon, Be« Uarb<m ^^^^^|
H dri n km g water, 631,
■ B^rthelot'a bomb, &2.
bisulphidr. ^^^^^M
Bitter almonds, Post-mortem appearancea ^^^^^|
^^^^ Bertnmd, 0,, on arsenic, 52,
after pot Boning by, 220. ^^^^H
^^^^L on bufonin^ 485.
Black bryony, 461 ^^^^1
^^^^1 on cstimiiLinn of ur^onic,
Black drop, 292. ^^^H
^^H
Hhiir'a gout pills, 424. ^^^^|
Hlanchard^ Tb« poison of the soorpion. ^^^^^|
^^^^P on ailioo-tungBtic yalta of
^^^ alkaloids, 251,
^^^1
H^ Berzelioit, Test for arsemr, 578, 580-584.
Blaa, A ca«e of [lois^^ning by white h^h- ^^^^^|
^H Bednou'a estimation of alcohol hi chloro-
bore, 407. ^^^H
H form, 153,
Blondlot and Beniard, Hydrochloric acid ^^^^H
■ Betaine, 522, 523.
in gastric juice, 99. ^^^^^|
and Duaart on thu deti^ction of ^^^^H
^m BettclbeJm on a«qnelfl3 aiter phoaphortis
^M poisoning, 232.
phospboriia, 243. ^^^^^H
^M Bcjtold, Antidote for physoatigmiue, 112,
M., on the Marsh- Hi^r^^eliua ^^^^H
^M Biacetylaconitine, Fatal rlose of, for cat*;,
t4^t, ^^^H
■ 360.
Blood and bluod-sitainti, Examination of, ^^^^^H
H Bibliffgr^phy ufchief works on toxicology,
^^^M
■
cor^itif^^les^ 65. ^^^^H
^m Bibra and Schuchardt on the blood in
human and animal, biulogtual test, ^^^^H
H pho«[>hon]E pujfioniiigi 235.
^^H
^M Bichromate diaease> 702,
Sodium and potassium in, 66. ^^^^^|
^1 Bidder on excretion of ciirare, 420,
Spectroscopic appearances of, 60, ^^^^H
in sulphuric acid [Xiiiioning^ 90. ^^^^^|
■ Bikhaoonitine, 362, 363.
^M „ Phy Biological eiteots of,
Blo^tield on the compoaittnn of nux ^^^^^|
■ 360.
vomica, 329. ^^^^^H
^m Billroth im deatb under ihhmiftjrm^ 159.
Blue pill, 663. ^^^H
Blyth\ ( A. W. } delinition of poistUL, 23. ^^^H
H Binnendijk on excretion uf cjirboHe acid,
■ 185.
Boc&rm^, Count, 273, ^^^^H
^L Binx on action of oHloroforin on man,
Biicklisch, Methylguanidiue, 521. ^^^^H
^^K
Bocklifi(3h'B apparatus, 508. ^^^^|
Boerhaave^a odontalgio essence^ 293. ^^^^H
^^^^1 », on the phytdological ai^^oii of
^^^■^ at*eaic, 576,
Boehm and Wartmaun on the action of ^^^^^|
^m Biological test for human IiUhkI^ 66.
aiuouitina, 375. ^^^^H
740
INDEX.
Bogoslowsky on chronic poisoning by
nitrate of silver, 660.
Bobm on contraction of the gullet in
alkali |>oisoning, 125.
, , on the action of aconitine on frog's
heart, 367.
„ ,, effects of barium salts on
animals, 712
,, ,, influence of digitalis on the
heart, 442.
„ ,, isolation of cicu toxin, 472.
„ „ mental effects of chloroform,
159.
Bois on the fatal dose of strychnine, 835.
Boisbaudran on the spectrum of phos-
phorus, 244.
Boletus satanas, or luridus (Lenz), 431.
Bollinger, 0., on sequelte after phos-
phorus poisoning, 232.
Bonaparte as a poisoner, 8.
Bonaparte's ( Prmce Lucion) viperin, 504.
Bondzynski's method of separating mer-
cury, 683.
Borchers, Physiological action of taxine,
416.
Bossey, Poisoning by water hemlock, 474.
Bostrom, The effects of the common
morelle, 431.
Bothus afer, 486.
Bott on the composition of opium, 286.
Bottard on the poison of Synanceia
braohio, 487.
Bottcher's depilatory, 711.
Bouchardat on the excretion of mor-
phine, 313.
Bouchart1at*s case of poisoning by phos-
phorus ya{K)ur, 233.
Boufanti, T., effects of cantharides, 495.
Boullay discovers picrotoxin, 466.
Boussingault, 82.
Bradbury on the effects of papaverine, 322.
Braconnot, Hydrochloric acid in gastric
juice, 99.
Braine, C, on the antiseptic action of
HON, 214.
Brampton, Baron, on the Palmer case,
333.
Brasch, 0., on spectroscopy of poisons, 57.
Braun's method of estimating HCl in
stomach, 107.
Braimer, The estimation of arsenic, 597.
Brawn, Poisoning by, 530.
Brenner on effects of breathing phos-
phine, 286.
Bneger on ethyl idenodiamine in putrid
haddock, 514.
„ methylguanidine, 521.
„ mydaleine, 520.
„ mydratoxine, 526.
„ neurine, 523.
„ peptotoxine, 524.
,, saprine, 522.
,, the isolation of neuridine,
515.
I Brieger's mytilotoxine, 627.
I ,, process for the isolation of
animal toxines, 507, 510.
,, process for isolating muscarine.
429.
, , * * spasmotoxine, " 525.
Brighton green, 644.
Brinvilliers, Madame de, 11.
Brittanicus, Death of, by poison, 6.
: Brodie, Sir Benj. , on the effects of barium
saltson animals, 712.
II 11 on the effects of arsenic,
' 561, 567, 574.
Bromine, 187.
,, tost for coijper, 651.
Brouardel and L'Hote on a case of
potassic chlorate poisoninir.
131. *
, , on a ptomaine like veratrine.
408.
Brown, A case of chloral jwiscming, 165.
Brown (Crum) and Fraser on the effects
of thebaine,
323.
II M on toxicity, 35.
Browne, Crichton, Physiological action of
picrotoxin, 468.
Brucine, 250, 264, 265, 349-352.
,, Fatal dose of, 351.
„ in strychnine. Detection of, 381.
,, Melting and subliming tempera-
tures, 261.
„ nitrate, fatal dose for rabbits.
351.
,, Physiological action of, 360.
„ Properties of, 399.
„ Quantitative estimation of, 348.
,, Spectrum of colour reactions.
58.
„ Tests for, 351.
,, Treatment in poisoning by.
(App.) 731.
. Ili*s Ik)
mercury, 682.
Brugnatelli*s (E.) method of detecting
Brunner, A., on the effects of phosphorus,
Brunnich, J. C, on deaths amongst
cattle from dhurrin, 204.
Brunswick green, 644.
Brunton, L., on the influence of digitalis
on the heart, 442, 443.
I^uchanan on dose of ether, 1 50.
Buchner, A case of chronic poisoning by
chloroform, 159.
Buchner*s (C. A.) case of nitric, acid
poisoning. 111.
Buchner, M. L. A., on the solubility of
arsenious acid, 547.
Buchwald, Poisoning by Agaricns ruber.
431.
Buckheim on the active principle of
mezereon, 456.
Budd, C, on a cose of colchicine poison-
ing, 425.
^^^^^^H^^^^^^^^^^^H
^^^^ ^H
^^^H Llufonin, 4b5.
Cantharida^
^^^1
^^H Buti>talin, 485.
It
Effects on animals, 493. ^^^H
^^^^B Bufo vidgaris, 434.
ti
man, 494, ^^^B
^^^H BuHyocatpnine, 359.
n
Fatal do^e of, 493. ^H
^^^1 Burk&rt, A cam of chbrofonn poiscming,
^^^1 Burnett's dlHinfectaut fluid, 687.
}i
Phanaaceutical preparations ^^|
of, 493. ^H
Post - mortem apj^eamncce ^^H
after poisoning oy, 495, ^^^^H
}»
^^^H Bt^ssclier, Dr. Albert, Oftwa of Jbcomtinjb
^^^^B poisonings 372,
11
Teste for, 495-407. ^^^B
^^^1 Butykmine, 523,
tf
Treatment in poisoning bj, ^^^^H
^^H Butykl, 37.
(Am) 722. ^M
t Meltmg and subliming ^^^^H
^^^H Butjl chloral hydrate, 37.
^^^1 Butjlcbloral, 16B,
^^^^P ByusBeu, A.^ on the vlLmiuatiou of
i*
Properties of, 492. ^^^H
merourj, 67I>*
tt
Separation of, AM. ^^^^H
Gantharis vo^icatoria, 491. ^^|
-
Capjuarelli^
The fioison of tbc water ^^1
CADAVKRtNK, 51fi*
Ralamand
pr, 484. ^M
Gadmiuni, 615.
Ca}MiicirTn si^s, 379. ^^M
„ FatAl du«$a of, 615,
Carbolic acid, 174. ^fl
„ In tbo arts, 615.
ji
Ev^timation of, 187, 191, ^H
1, Mcdicin&l prep&ratious of, 615.
^M
„ oiidc, 615,
tt
ExBmination of urincj for, ^H
1, Separation and deletion of,
^H
616,
ff
excreted by the skin, 185. ^^^
^^^_ „ sulphide, 615.
It
Fatal dose for animab, 1 79. ^H
^^H CalTeinG, 40, 41.
Fata] dose of, 178. ^H
^^^H ,, Spectinmoroobur r^jk^tdons, 58*
it
Internal administration^ ^^M
^^^^H Cahn on hydric sulphide poiuoning, 79.
Poisonous elfccts of, 182, ^^M
^^^H (Xbonra on fltrychnino, 3^7.
11
PhiirmacotKeia ^lutiou of, ^^|
^^^H Caitlol and Lirou'i ex|wiimet)tB witli
^B
^^^H antimony oxide on cats, 606, 610.
i%
Physiological action of, ^^M
^^^^1 Calabar boan^ Trealmeut in poisoning by,
^H
^H (App0722,
If
paiHonoUB elfecte on animals, ^^|
^^^B Cabbannt^t 409,
^B
^^^^1 Oalmette, A., The poisonous action of
Jf
poisonous elTeets on lisb, ^H
^^^H cobra*s blood, 500.
176. ^B
^^^H Calmetle'^ cobra antitoxin, 502.
tt
[(oisonouB eflects on frogs, ^^H
^^H Calomel, 662, 665.
^B
^^^H Calvert's carbolic acid iHiwder, 176,
Jf
poUKinoiia efTeots on in- ^^H
^^^^1 CambieT^ Isolition of an album ose from
*i
fusoria, 178,. ^^H
^^^H the locust tree. 431,
II
{loi^noas effects on warm^ ^^^^M
^^^H CamptiolU Dr. , Lead poisoning from wliie,
blooded animals, 179. ^^^H
^^H
n
powden, 191, 192. ^^^B
Po^t' mortem api»arances ^^B
^^^H Qampbenc, 139.
11
^^^^L^^ Ouiiphor, 141,
after i»ois<init)^ by, 136. ^^|
^^^^^^^L Goiui>ou£id linimetit of, 117.
i»
prepsratiouB, Pnvy Council ^^M
^^^^^^B tincture of, 141,
order relating ta, 176. ^^M
^^^^H
* t
Properties of, 175. ^^M
^^^^^^H linlmeat, 141.
it
Separation of, from organic ^^|
^^^^^^1 Minimtiin fatal dose of, 142,
matters, 100. ^H
^^^^^^H PhairmaeeutirAl preparations
If
soa|ie, 176, 193. ^B
^^^^^H
tf
StatisUca as to poisoning ^^M
^^^^^^^H Pofit-niortcm ap^^earances after
by. 176. ^B
^^^^^^H {loisquing by, 142.
It
8ym]itoma in man of ^^H
^^^^^^H Enhin i'a ess«iiee of, 141,
poisoning by, 130. ^H
^^^^^^H Sttparatioii of, from oon tents of
^,
Tests for, 1S7, 188, ^H
^^^^^■i stemach. 1^2.
It
Treatment in cascis of ^^|
^^^^B Spintof,
poisoning by, (App.) ^H
^^^^^^H Symptoms of poisonlni^ by,
^B
^^^^B
,.
Usee of, 176. ^B
^^^^^^H Tr«atQietit in poisoning by,
^^^H (App.)722.
^^^^^H waipr, 141.
*»
Urine in tioisonitig by, ^^M
cna, Linking of, il« ^^^^^|
Carbon ato
742
INDEX.
Carbon bisulpliide, 172-174.
,, ,, Detection and separa-
tion of, 174.
Poisoning by, 172.
,, ,, poisoning (chronic),
173.
,, ,, Post-mortem appear-
ances after poison-
ing by, 174.
,, ,, Properties of, 172.
Carbon monoxide, 68-76.
, , , , Blood in poisoning by,
62.
,, ,, Detection of, 75, 76.
,, ,, Estimation of, 76.
,, ,, haBmoglobin, 61, 62.
,, ,, Mass poisoning by,
72.
,, ,, Penetration of, 74.
,, ,, Post-mortem appear-
ances after i>oisoning
by. 71.
,, ,, Properties of, 68.
,, ,, Symptoms of jK)ison-
ing by, 69.
Carbon sulphide. See Carbon bund-
phicfe.
Carbon tetrachloride, 170.
Carboxyl group, 41.
Carlisle cases of food poisoning, 520.
Carriere's case of prussic acidpoisoning,
207.
Carson on antimony sulphide, 61 2.
Cash, J. T., on the fatal dose of aconitine,
366.
, , Physiological eflects of inda-
conitine, 369.
CaHjier, A case of hydrochloric acid
poisoning, 103.
Cases of sulphuric acid poison-
ing, 96.
Family poisoned by veratrum,
408.
nitro-benzenc as a poison, 193.
on the acute form of arsenic
I>oisoning, 565.
on arrest of putrefaction after
poisoning by acids, 90.
on the detection of HCN after
death, 220.
on the inflammatory effects of
arsenic, 575.
on post-mortem appearances
after poisoning by alcohol,
145.
on the post-mortem appearances
after poisoning by colchicine,
425.
on post-mortem examination in
HCN poisoning, 214.
Cass, W. C, on morphine taking, 311.
Casson, F., on the composition of aconite
extract, 360.
Castor-oil seeds, The toxalbumin of, 478.
Catalytic ))oiiion8, Loew's, 41.
Cataplasma conii, 270.
Caventou on bmcine, 349.
Cedrenes, 139.
Cephalopoda, Action of poisons on, 44.
Cerbera odallam, 447.
Cevadilline, 401.
Cevadine, 401, 402, 404.
Cbadderton case of food poisoning, 530,
531.
'*Chandoo,"311.
Chapman, A. C, and Law, H. D., The
estimation of arsenic, 594.
Chapman, A. C, and Law, H. D., on the
insensitivencss of zinc, 581.
Chapman, The, poisoning case, 608.
Charles IV. as a |K)isoner, 8.
Chastaing, P., on the solubility of
morphine, 296.
Cheiraiithin, 449.
Chelidonin si)octrum of colour reactions,
58.
Chenot iK>isoned by carbon monoxide, 69.
Chevallier, Action of fluids on zinc, 688.
Chover, A case of opium poisoning, 309.
Chevers, Dr., An Indian case of atropine
poisoning, 387.
,, on a case of aconite iK)ison-
ing, 371.
,, on atropine |K)iHoning, 386.
Children, Hydrocliloric acid in gastric
juice, 99.
Chilognathen, 208.
Chittenden on the localisation of arsenic
in the body, 586.
Chloral, 161-170.
Chloral cyanhydrino, 223.
Chloral hydrate, 37, 161.
,, ,, Chronic poisoning by,
167.
,, ,, Detection of, 162.
,, ,, Estimation of, 162.
,, ,, Excretion of, 168.
,, „ Fatal dose of, 165.
,, ,, Poisonous effects of, on
animals, 163.
,, ,, Poisonous effects of, on
man, 164.
,, ,, Properties of, 161.
,, ,, Se]>aration of, from
organic matter, 168.
,, ,, Statistics of poisoning
by, 162.
,, ,, Symptoms of poisoninj;
by, 166.
„ Tests for, 169.
,, ,, Treatment in poisoning
by, 166,722(App.).
Chlorate of potash, Treatment in poison-
ing by, (App.) 723.
Chlorcodeine, 305.
Chlorine, 76-78.
„ Detection of free, 77.
,, Estimation of, 78.
INUKX,
Chlorlnv, F<ist- mortem App«aniiioeti aft^r
poisrjiiing hy\ 77*
,, Pmpertiea of, 78.
f , Symptoms of poiaoniikg hj, 77*
Chlorodyne, 293.
ChlorofonD, l&l-16h
,i Detectiut) ^ad eetim&tian of,
160, IflL
Detection of imuttrities in.
Fat*! doM of, 155,
General olTfleta of liquid,
154.
Hydenbad Comttxisiion w-
safttclies on, 15S.
Local action of, 153.
MAuufacturfl of, 153.
Metliylnt«d, 162.
Poisoning bj liquid, 1!!KI.
Poat - mortem aiipearauces
Alter poLsotiliig Dy, 159.
Properties of, 16L
StttU^ticji of poisoning hy
litjuid, 153.
guicid«.{ and crimiciftl pois-
oning by, 167.
Symjitoms of poiaoniiig bj
liquid, 1&5.
Treatmoot in poisomng hv
(App.), 7t;3.
vapour, I6e»
,, Chrotik {lobotiijig
by, 169.
„ F»tid dose of, 159.
„ Physiologioa] effvcts
of, 167.
i» ti Poat morteni Kp-
f»earancca after
polAoulog by, 169.
1. M Symptoms of
fKiisotitiig by, 153.
Cbloro^^tmethylttic, 545,
Cbodomisky, K,, on llie itolubility of
atvenious acid, 54B.
Choline, 41, 522.
„ group, 522.
Cbristison, A cae« of ammoDui poiiioning,
120.
A case of cytiaine poison-
lug, 409.
A ca8« of DiGotiiie poboning,
Effect of digitalis on m^Uf
487.
,, oxalic acid on ani-
makp 636.
, , osalie add on man,
588.
,, phjaofftigmine on
man, 412.
Miaiuiuui letbal dose of tiu]*
phuricutitdf 86«
on jMiat-mortfiiti apjiottivnccd
amr lead poiaonuig, 682,
Chri&tisou on tlie fatal dos« of strycb<'
iiin«, 335,
,, on tbe non -fatal dose of sugar
of lead, S33,
Ghiome r«d, 619*
>, yellow, 619,
Chitimium. 701^706.
^j coraiKJunds, Effect* of, 702,
,, Detection of, 706.
,, Post - mortem app«arances
after poisooing by, 705*
„ Sepftratioti of, 706.
„ Statistics of pdaoniug by,
703,
,, Trsainitftnt in poisoning by,
(App0 723,
Chry BO- toxin, 458,
Otcut»t 3.
,, virosii, 471,
Cicutoxin, 471.
^, Dlfecta on animals, 472*
„ SeparaUon of, from organic
matter, 478.
Cinchonidine, 265,
CincbouiDe, 250» 265,
Cinnabar. See Atcrcjtric ftiiifthide,
Cinnamomiim eamphora, 141,
CiDn&myl cocalae, 356,
Clapton, Dr., on cbronic j^ioiaoiuug by
copper, 648*
Clark, John, ou E«inscb^s test, 685,
Clarke, F. G,, on etfeots of veronal,
172.
Oausmanu on arsenic taken oa food,
567.
Claviceiie purporea, 456.
Clemen s JMilution, 653.
CieofKitra's asp (Naja haje), 503.
Cloetta, Max, on digitomn, 432.
Clopea thnsaa, 488,
„ reneuoea, 488*
Cokl-gaa, poisoning by, CS.
Coal-tar crea4K>t6. See Carbolic add.
Cobalt and nickel, 603-696.
,, „ Eiitiination of, 696.
,t t» Poifloninjj by, Aetion
on circulation, 695.
^, ff Poisoning by, Action
on nervous system,
695,
,, „ Poisoning hr, Aotton
on stn^ied mtiiele^
695*
M t» Poisoning by. Symp-
toms 01, 694*
,, „ Separation and dd*
taction of, 695.
Cobra di capellu, Tl)** p*>iaoii of the, 408.
„ poison antitoxin, h02.
„ ,, FJfects on animals, 500*
„ ,, M m^n, 501.
,, „ Fatal dose of, 500.
Qooa aakalotda, 866-^59*
744
INDEX.
,, KMtiruAtion of, 368.
F*Ul dose of, 359.
„ hydr.PchLirate, 357.
, , .Melting and subliming tempen-
tures, 260.
,, pharmaceatica] preparations,
357.
,, Post-mortem ap|iearancvs after
poisoning by, 359.
, , Projierties of, '35<J.
„ iSe]Aration of, 357.
„ Srmptomft of poisoning by, 358.
„ Te«t« for, 357.
Cocculus indicas (Indian berry, Levant
uut;, 465-469.
Codanine, 286.
Codeine, 250, 261, 266, 286.
,, Constitution of, 298.
EtfecUof, 318.
,, nitrate. Fatal dose for rabbits,
351.
,, Properties of, 317.
,, 8i»ectnim of colour reaction, 58.
Colchicine, 250, 421-426.
,, Effects on animals, 423.
,, ,, man, 424.
„ extraction of, 421.
Fatal dose of, 423.
,, Patent and quack medicines
containing, 423.
,, Pharmaceutical preparations
of, 422.
,, Post - mortem appearances
after poisoning by, 425.
,, Pro{)ertie8 and constitution
of, 422.
,, Seiwration of, from organic
matters, 425.
,, Statistics of ])oisoning by,
424.
„ Tests for, 422.
,, Treatment in- i>oi8oning by,
(A pp.) 723.
Colchicum autumnale, 421.
„ wine, 423.
Coleman, W., A case of trional i)oisoning,
171.
Collas, Dr., on poisoning by the goby,
489.
Collidine, 40. i
Collie on the spectroscope, 57.
Collie, J. N., Estimation of cocaine, 358.
Colocynth, Treatment in i)oisoning by,
(App.)724.
Cologne yellow, 619.
Oolophene hydrocarbons, 139.
Coltmann, Poisoning by locust - tree
leaves, 481.
ColubridflB vononosif, 498, 503.
Conessino, 263.
Confectio opii, 291.
Congo red test for mineral acid, 105.
Conhydrinc, 266, 269.
' Coniceine. 263, 266, 269.
I Conicemes, 268.
Conierbe and Orfila, Arsenic in bones,
> 588.
j Coninck, O. de. An alkaloid from the
cuttle tish, 524.
Cx»niine, 250. 263. 264, 265, 266-272.
„ Constitution of, 268.
„ Effects on anintals, 270.
,, Effects on man, 271.
Paul dose of, 271.
,, Pharmaceutical preparations of,
269.
„ Physiological action of, 271.
,, Post-mortem appearances after
poisoning by, 271.
„ Pro(iertie8 of, 266.
,, Sejiaration of, from organic
matter, 272.
,, Statistics of poisoning by, 270.
„ Tests for, 267.
,, Treatment in poisoning by,
(App.) 724.
Cfiuium maculatum, 266.
Convallamarin, 440.
Conyrine, 268.
Coote, Barrington, A case of poisoning
by antimony chloride, 611.
Copper, 637-652.
„ carbonate, 648.
,, Chronic poisoning by, 648.
„ Deaths from, 29.
„ Detection of, 650, 651.
„ Effect of salts of, on animals,
644.
,, Electrolysis of salts of, 650.
,, Estimation of, 650.
,, in the animal and vegetable
kingdom, 640.
,, in the arts, 643.
,, Icguminate, 645.
,, Medicinal dose of, 644.
,, nitrate, 643.
,, oleate, 639.
,, oxide, 637.
,, phyllocyanate, 642.
,, pi^ents, 644.
,, poisoning, Statistics of, 647.
„ Post-mortem appearances in cases
of poisoning by, 648.
„ Proi)ertie8 of metallic, 687.
,, salts. Toxic dose of, 646.
,, Scijaration of, 650.
„ Solubility of, in various fluids,
638.
„ 8uba(»tate, 648.
,, subchloride, 648.
,, sulphate, 643.
,, sulphide, 637.
„ tartrate, 644.
„ Treatment of poisoning by,
(App) 724.
,, Volumetric process for
tion of, 651.
^^v ^^^^^^v ^^^1
Cupper*s» 69&.
Outtle tifih, A py ridi nu a] kaloid from , 5 24. ^^^^H
Cop})«ntig of rcgDUl]lf!»f 641,
Cyanide, Pataa^ic, E^lmmtiun of, 220. ^^^^H
GoqueTet, Dr»^ on the aervaua form of
PoiEoniagby, 215. ^^^H
St-atlatica ofpoifioning ^^^^^B
AFseatc poisouing, &68,
CoriamjTtin, i09.
^^H
Goriaria SarmontOiSttj C. arborea, and C.
TeatJtfor, 315. ^^^^B
Tutu, 46a
Cyanidea, Double, 22L ^^^H
Cornutin, 45S, 46&.
In v^^ble kingdom, 203. ^^^^^H
Oorrigau on chronic potsonlng by copper,
. ti Separation of, from organic ^^^^^B
64».
matter, 217. ^^^H
Curru&ive aublimnte, 664, 660, 675.
Sodic and ammonie, 22 L ^^^^H
Oorybulbine, 350.
CyanmetlieeEnoglobin. 214, ^^^^^B
Corycavamine^ 359.
Cyanogen chloride, 222 ^^^^H
Cory came, 3&9,
iodide, 222. ^^^^B
Corydnline, 35&.
Cyanurio acid, 222, ^^^^H
Gorydalb cava, 3B9»
Cyclamin, 450. ^^^^H
Cory dine, 359.
Cymogene, 135. ^^^^^B
norytitb«riDe, 3£p9.
Cyon on the efTecta of barium !salt» on ^^^^^B
CottoD wads, 470,
animaK 712. ^^^^^B
Coulloii oil the aotioD of hydrocyanic lu^nl
on thf^ physiological action of ^^^^^B
on iidogt 210.
oxalic a<:id, 539. ^^^^^B
Conty, M*, on the tki^tum of curare^ 420,
Cytistne, 398-401. ^^^H
Cox^s mot hod uf esti mating nicotluc in
Elfecta on animak, 400. ^^^^H
ti>biwjco, 2?4.
Effects on man, 400. ^^^^M
Cmwfbrd on epiueiihriu, 505,
ProiH]rtica of. 399, ^^^^B
Cr»ia.in, Thotnua Neill^ the poisotiori 333.
Teiits for, 399, ^^^^^B
Creaaob^, 189.
Cytisns labnTnum, 398. ^^^^^|
„ Carholio acid in, Teat fori 189,
^^^^^H
Creaol, Commerci&t, 183*
^^^^^^
,, Exu mi nation of mine for, 190.
D^^KIK, H. D., Epinephrin, 505. ^^^^H
t, Eicretiouof, 184,
Dal by V carminative, 292. ^^^^^B
CreaolB, 34, 174, 176, 177. 179, 188.
Da Silva's teat tor physoatigmine, 410. ^^^^H
„ Fatal dose to aninmk* 179,
Datnra atba, 379. ^^^H
Greaylic acid, 8«e CrtmL
atrox, 379. ^^^H
Orimitial Gotiaolldation Act, 1861, p.
r&atuoaa, 379. ^^^^B
Crofit on the poiHonoua properlie^ of
Daturitie, 373. ^^^H
amy] alcobolj 148.
Omta iiiae (pit vipere), 498,
Datnr& atramonum, 379, 393. ^^^H
Davidson, Dr. , A cams of ergot poison tng, ^^^^^|
CrotoTi oil, 476,
. ^^^M
^. ,, Dose of, 477.
Nonfatal doRe of carbolic ^^^^^B
^^m EMuctaof, 477.
^^^H
^^^^K Pcist- mortem upfjoarancefi lifter
Duridaon's cancer remedy, 554. ^^^^^B
^^^^B |>oisoning by, 477.
Dav^ie, Margaret, Execntion of, 9. ^^^^^B
^^^H jf Semrotion and idontiJicaiiou
Darison, H,, on the etTecta of fool'j^ ^^^^H
^^M
pareloy, 473. ^^^^B
Davy, Dr. Edmund, on the arsenic ^^^^H
^^ (App.) 724.
&l^rb«d by plants, 558. ^^^^H
■ Crotot) U^'Hum, 473.
Debray's eixi>erlment on ^iraenious anhy- ^^^^^B
dride, &47. ^^^M
■ Cryptopine, 256, 323.
H Cupnius chloride, Prepai^tion of, 75.
Delednorei, A, M., on a ptomaine like ^^^^^B
H Cuprum ainminatttm, 643,
veratrine, 403, ^^^^H
■ Cnrare alkaloidEi, 41 8-420.
Delpech on elf eels of CS^ 1 73. ^^^H
■ „ Commercial, 418,
Delphintne, 250, 266. ^^^H
■ „ Elimination of, 420.
Melting and subliming ^^^^^B
H ,, PhTHiologic&l effects of, 419,
tt-MipratQrD9, 262. ^^^^^B
■ Gurarine, 263, 266, 418,
Delphinoidine, 266. ^^^^B
■ „ Separation of 420*
Spectrum of oolcmr ^^^^H
^B ti Treatment in fioiaoning by,
reactions, 58, ^^^^^B
■ (A pp.) 725.
De Martiny on the etfects of santonin, ^^^^H
^B Gnrei on the eM'ect^ of wtlver nitrate on
^^^H
H ikutroaU, 659.
De Pauw poisoned by digitalin, 443. ^^^^H
^1 Ouaoohygrin^, 356.
Dorrid, 418. ^^^^B
^B Cuiili man's miithod for 5c9par»tLng
Desgrauges on t Kiis^jning by the external ^^^^H
application oi arsenic, 563, ^^^^^H
^1 Btrychninei 343.
746
INDIX.
DentBch, A case of sulphuric add
poisoning, 84.
De Valanguis' solutio solventes minenlis,
563.
De Vry on antiarin, 445.
Dhurrin, 204.
Diacetin, 37.
Diacetyl morphine, 305.
Diamines, 514.
Diaphoretic antimony, 604.
Diazobenzol. See Tyrotoxicon.
Dibenzoyl mor(»hine, 305.
Diethylamine, 518.
Diethylamino-aceto nitrites, 223.
Diethylamino-])henyl-aceto nitrile, 223.
Diethyleuediamine, 511, 519.
Diethyl-malonyl carbamide, 172.
Dietbyl-sulphon -methane, 37.
Digitalacrin, 434.
Digitaleretin, 434.
Digitaletin, 433.
DigiUlein, 432, 434.
DigiUliu, 432.
,, Action of, on common blow-
fly, 442.
Fatal dose of, 435.
,, Pharmaceutical preparations
of, 434.
,, S|)cctrum of colour reactions,
58.
Digitalins, Action of, on frog's heart,
442, 444.
,, Physiological action of, 439-
442.
,, Post-mortem appearances
after poisoning by, 443.
,, Separation of, from animal
matter, 444.
,, Tests for, 439.
Digitalis, effects on man, 436-439.
,, group, 431-445.
,, group of heart iK)isons, Treat-
ment on poisoning by, ( App. )
725.
,, preparations, Maximum doses
of, 436.
purpurea (foxglove), 431.
,, Statistics of poisoning by, 436.
Digitin, 434.
Digitogenin, 432.
Digitonin, 432, 450.
Digitoxin, 433.
,, Estimation of, 433.
,, Sei)aration of, from organic
matters, 433.
Dihydrolutidine, 528.
Dillak'rger's auto - experiments with
coniinc, 271.
Dimethylamine, 513.
Dimethyl - sulphon, dimethyl -methane,
37.
Dinitro-benzoate, Prei)aration of, 147.
Dinitro - benzoates, Melting • points of,
148.
Dinitro-benzol, 198.
„ Detection of, 201.
„ Effect of, on blood, 200.
Fatal dose of, 199.
,, Influence on the sight,
200.
„ Poisonous effects of, 199.
,, Properties of, 198.
Tests for, 199.
Dioecorides, 3.
„ Effects of lead on the nervous
system, 626.
Diphenyl-carbazide test for copper, 651.
Diphenyl diethyl sul phone ethane, 171.
Disinfectants, 191.
Disinfecting powders, 176.
Distillation in vacuum, 49.
Dobbio and Lauder, Constitution of cory-
daline, 360.
Dolbeau on the ansesthesis of a sleeping
person, 157.
Dolium galea, 82.
Domestic remedies for poisoning, 733.
Donovan's solution of arsenic, 553.
Dott on physiological action of morphine,
305.
Dott's method of assaying opium, 288.
„ tests for purity of chloroform, 168.
Douzard's method of assaying opium, 289.
Dover powder, 291.
Dragendorff* on blood-stains, 64, 66.
,, on cantharides, 496.
,, on digitalin, 435.
,, on the colour reactions of
strychnine, 347.
,, on the composition of nox
vomica, 829, 330, 381.
,, on the constituents of eriFot,
457.
, , on the detection of HON long
after death, 220.
, , on thedetection of strychnine.
345.
, , on the excretion of curare, 420.
, , on the excretion of morphine,
313.
,, on the extraction of que-
bracho alkaloids, 863.
, , on the separation of cuiarine,
420.
, , on the separation of gelsemine,
356.
,, on the separation of physos-
tigmine, 412.
, , on the separation of solanine,
398.
,, on the solubility of strych-
nine, 327.
,, on the treatment of dried
blood, 59.
DragendortTs experiments on cats with
coniine, 270.
,, process for separating alka-
loids, 264.
^^^i^^^^v ^^^1
H Dri^ndorff'& irea^eD t fV>r oX kdoids^ 25 1 .
Elliotti FaUl doee of oobra poison, 500. ^^^^|
^m ,, ^Iflrocry^tallin, ib&»
PoiBon of fi«a'^nake, 498. ^^H
■ Duboia RusBelliL, 504.'
^1 Dtibciii^ia Hopwoodiit 233.
Envetine, 250, 266. ^H
■ DuJios' pniKsic acid, 203.
Emplastruin pluuihis 61S. ^^H
^H Dulcajniannj 45Q,
iodidi, 613. ^^^^^H
^1 Hani^^n, Dr^ a t^am nt hydrochloric acid
Engi(!] on excretion of carbolic aeid, 186. ^^^^^^H
^M liomomiig, 103.
■ DutJitan, W. R., and Cash, J. T., oti the
Engclhardt on aniline |>oieomng, 2^4. ^^^^^^^H
Kn^ravefA* acid^ 109, ^^^^^^^^H
^m ,, fatal do^j of aconitine,
Kiibydrina bengalensU, Poison of, 496. ^^^^^^^|
Enhydrfna valokadien, 49S. ^^^^H
■ 366.
^^L „ and Cafihj Physifjlogical
Ept i n^ d kde tna, 4 9(>. ^^^^H
^^^^^^^^L «lipctis of iiiilacoui-
fipiiiepbrin, 505. ^^^^^|
^^^^^H
Physiological action of, 506. ^^^^^^
^^^^^^H M ud T. A t)d ertiou H (Ji I ry ,
Erbf W,, ](ctiun of epin^phrin, fi06. ^^^^H
^^^^^^^H thi^ 11.1 keloids of
E rd nm n u'h ruagcn t, 4 22. ^^^^^^
^^^^^^^H acynltc pliititaf 3^1,
Ergot of rye, 156 - 4 6 5, ^^^^1
^^^^^^^H aud Hpnry^ ou pniBBtc
Active con^tituenta of, 456, ^^^^H
^^^^^^^H acid yielding glti-
^^^H
^^^^^H co^dea,
Detection of, in flour, 460, ^^^^H
^^^^^^^P on the oom]>oaition of
Dose of, 460. ^^^^^1
^^^^^^^ aconitttift gold chlor-
Pharmaceutical preparations ^^^^^H
m ide, 365.
^^^H
^M Diinstati, PR^f.f on the estiTtiatiou ot
Phystulogical action of, 463, ^^^^H
■^ tartar Qtneiic, 601.
Separation of active princi- ^^^^H
^^^^ f, on the melting -jioint or
plos of, froni organic ^^^^^|
^^^^L acoDititief Mh.
matters, 465. ^^^^|
^^^^f 4 J on the solubiliiy of
Symptoms of acute poison- ^^^^^|
^^^^ aeonitiiie, 363.
iiig by, 463. ^^^^H
^^ Du|»r^ on co|jj>er in the human liver,
Treatnient in jKiisoning by, ^^^^^|
^^^
(Am) 725. ^^H
^^^B ,, on excretion of alcohol, 146.
Er|(otintnii, 457. ^^^^^|
^^^^r ^, on sepaFatioLi of acouitine from
Ergotis^TOj Gonvulaive fonn of^ 461. ^^^^^^|
^F «otjtentfi of the Htoma<iht 376,
Gaugri^nous form of^ 462. ^^^^^|
H Dui^y on alcohol in ili^ brain^ 146.
EryUirocytc«. 43. ^^^H
H Durd uft f Action of aconi tb^i on tho heart,
Eryibmplddn, 440, 449. ^^^H
■ aea.
Erythrupldufum guineeuse, 449. ^^^^^|
^M Ousart on the detection of ^boBpboni^i
EsBrlne. See PhtjaoHifpniHc, ^^^^H
■ 243.
Esmr on the pbysiologica) actiuu of ^^^^^|
■ Dutch Pink, a 1 a.
^H DwoTzaV^B au to ■ e X jierimeutfl with coniin c%
an^enic, 576. ^^^^^|
^^^H
■ 271.
OB an ans&athetic, 150. ^^^^^|
H Dybskowsky on solubility of phoB[ihonj«
Kataldoi^uuf, 150. ^^^^|
■ iu blood, 236.
Poisonous properties of^ J i9, ^^^^^M
■ Dyer's acid, 109.
Frojwr tiers of, 149. ^^^^H
„ Separation of^ fit^ni org^ie flaida, ^^^^H
^M Eabtfijeld and Aston on tutin, 469.
^^^H
■ E»u de Javetlo, 124.
, , Treatment i n poisoniiig by , ( App. ) ^^^^H
^M Eberty on the action of ergot, 463^
^^H
■ Ecboliiie, i57.
Ethiopaof antimony, 604. ^^^^H
^M Ee^oniQej 357.
■ Et.hu]in, 449.
Mthykmine, 41, 513. ^^^H
EtfaylenediaminCj 511. ^^^^1
^1 Ecimim ar^cnic&k, &09.
Etbylie ether. B^ Ethet, ^^^H
■ KA blood, 469.
Ethylidenediamine, &14. ^^^^^|
^m Kgyptian knowledge of poi^us, 2.
H Ehrfieh on |Kii^oning by cocaine, 359.
Ethyl sulphide as a poiaon, 33« ^^^^H
Eucaine, 356. ^^^^H
H EkpLhiL', 503.
Euchlorine test far carbolic acid, 188. ^^^^^H
■ Elap GomlUnus, 503.
Eulen berg on chronic poisoning by anti- ^^^^^^
^M EUenberger and liofmeiater on the excto-
mony, 607. ^^^^^|
^^ tion of hi}»|)uric a^eid in lead
on chronic poboniug by QB^f ^^^^^M
^^^m poisoning, 629.
^^^M
^^^^P f , &nd Uofmeister on the local -
on thedodeofootmne, 372» ^^^^H
^^^"^ bstioti of load, 624.
on the ejects of bansene ^^^^^|
^K Klliuger, Efleots of cantharidesi 493*
va[»ouf, 138. ^^^^1
748
INDEX.
Euleuberg on the etl'eclH of lead poison-
iug, 627.
, on the effects of mercurial
vapour on animals, 670.
on the effects of phosphine, 235.
on the fatal dose of strychnine,
335.
on the i>oisonous effects of
hydrocliloric acid, 101.
on the poisonous effects of
petroleum, 186.
on the poisonous properties of
amyl alcohol, 148.
on the vapour of ammonic
cyanide, 221.
Eulenberg's experiments on animals with
creasote, 189.
experiments on pigeons with
ai-senic, 559.
experiments on jiigeons with
oxalic acid, 537.
experiments with methyl
cyanide, 222.
ex])eriments with phosphorus
vapour, 233, 234.
Euonymin, 447.
Euonymotoxin, 440.
Euonymus atropurpurcus, 447.
Extractum physostigmatis, 411.
Eykmann on the poison of Illicium
religiosum, 470.
Faber, Cows poisoned by vei-atrum, 408.
Fabris, L., A case of poisoning with
strychnine and atropine, 383.
Fagge on the action of digitalin on the
frog's heart, 442.
Falck, C. Ph., and Victor, L., Local action
of sulphuric acid, 85.
Falck, F. A., on ammonia poisoning,
118.
,, on cases of poisoning
by Agaricus phal-
loides, 429.
,, on criminal cases of
alkali poisoning, 124.
,, on deaths from atropine,
390.
,, on poisoning by cicuta,
472.
, , on poisoning by cytisine,
400.
,, on poisoning by san-
tonin, 453.
,, on poisoning by yew,
416.
,, on the effects of barium
salts on animals, 712.
,, on the eifect of copjKjr
salts on animals, 644.
,, on the effects of silver
nitrate on animals, 659.
,, on the effects of tartar
emetic, 606.
Falck, F. A., on the fatal dose of
atropine for rabbits,
886.
on the fi&tal dose of
brucine, 350.
on fatal dose of chloro-
form, 155.
on the effec^ of codeine,
819.
on the fatal dose of
picrotoxin, 467.
on the fatal dose of
strychnine, 334.
on the poisonous effects
of chloral hydrate,
163.
Falck's statistics as to rapidity of death
from carbolic acid,
183.
„ ,, of carbolic acid poison-
ine. 177.
,, ,, of chloroform poisoning,
153.
,, ,, of colchicine poisoning,
424.
,, „ of coniine poisoning,
270.
,, ,, of cyanide poisoning,
206.
,, ,, of mercuric chloride
poisoning, 675.
,, ,, of phosphorus poison-
ing, 228.
,, ,, of sulphuric acid
poisoning, 83.
False angustura bark, 826.
Faust, E. S. , on the poison of the cobra,
499.
,, on the poison of the
salamander, 483, 484.
,, on the poison of the toad,
484.
Fa voile, M., Test for hydrochloric acid,
105.
Felletar on blood-stains, 64.
,, on poisoning by hellebore, 447.
Ferrari on poisoning by hellebore root,
446.
Ferric chloride, 187, 697, 698.
Ferrous sulphate, 699.
Field, Test for bismuth in copper, 655.
Filho's caustic, 123.
Fischer, A base like muscarine, 428.
Fish, Action of metals on, 42.
„ Poisonous, 487-489.
Fitzwalter, Maud, poisoning of, 8.
Fleming's tincture of aconite, 861, 366.
Fleury's method of assaying opium, 289.
Frohde's reagent for alkaloids, 251.
Flourens on action of chloroform, 168.
Flowers of antimony, 604.
FlUckiger on the colour reactions of
strychnine, 346.
„ on the tests for atropine, 8H8.
IKDKX.
749
FlUcldger'a teat for brtidnft, 352,
,, ,, carbolic acid id
fi ,, cocaiue^ 357*
,. ,r ooniiae, 2@S,
WtBtm Bpiiit of amiDonM^ 117,
ToderS, Poifioning by arwaicaJ enemAta,
583.
Foora paiii!«y (^thuBA cynapium), 473.
Food poisoning, 629-£32»
,, Statij^ttcs of, 531.
Fonnal cy anhyd tin e^ 2^3.
Fomuildoxmie tefit; for cop]^)er, 651.
Fomwuek, J., Bea«wichefloiigaine&*pigE,
62.
,, on the apectnim of blood,
ea
FoqgiiieSj M. , the poisoning of, 27S.
Fowler's .«!olution^ 552,
Fmenkelj E., and Reiche, P., on efTecto
uf »u1|ihunc Bcid on Iciilney^ 91.
Franclfi on pnisaio acid in cossaTra Toot,
205.
Fmnkforter on the constitutjoti of
narcelne, SIfl.
FTxi.^er uii HUntpLiantiiiT 447.
,, the M'tion of atrojiin*?, 387,
, , tb6 ell«GCA of thehaitiv, 323.
,, the fatal do»e of cobra jKjiHon,
500.
„ tcijticity, 35.
Fraaer and Bartholow^ Antidote for
phyaoatigmine, 412.
tf and Elliott, Poiaon of sea-snnke^
493.
Fr^rea Come** can<?er paate^ 654.
Freaeniue and HLziU un tbt^ detection of
ai-Henic, 59 0<
,^ on ordinary phosphoriaa in red
phosulioms, 225,
Freund and Friedman n on tho melting-
{xHiii of methylentt dicyfiaiiiei
$90.
,f and Frankforier on the conati-
tution of nAT^iuo, 319.
Fngu*poiBon, 187*
Futigi, Poisonous, 42Q, 429, 430, 43L
Furat on the jKiiionotaB properties of
amy I alcohol, 148,
Galippe, Etfeots of t'antharidpsi, 493*
Garcia, Rate of format ion of diamines,
514.
Garacd, W,, and Collie, J. N., Ealimataon
of cocJiinej 358*
Oaaea, Foisonom^, 88-80.
Gasolene, 135.
Gantier, A., and Claosmonn, on araenie
taken in food, 587.
,, on destmotion of organic
matter, 68.
,, Teat for CO, 78.
,» The sejiaratioii of Ktsinio^
£94.
Gautier*fl process for the isolation of
animal toxine^^ 507.
Gay on the detection of stTychntne, 3&5,
Gehlen poisoned by arslne, 549.
Gelseniine, 3^3,
Fatal do90 of, 354.
,, Se^iaratiou of, from organic
matter, 35 5»
I, Physiological action of, 354,
355,
„ Treatment in fKiisomtjg by,
(App.)72fl.
Gielaeminmef 353.
Udgcmium acm^Xirvirens, 353. i
Geppert on carbon monoxide, 7 L '
,, on the action of prn^ic acid on
tb« blood, 209.
GeTgens^ E,, and Posner, C, on the effecU
of chromium on animals. 702.
Gergers and Bamnann on the ^jiuhttiun
of giianidine from urine, 521.
German aanaage poisoning, 532.
,, poisoning, Post-mortem
appearance after, 5:+2.
Geschcidlen on the physiological nntion
of morphine, 305,
Geysii^ra and carbon monoxide, 88.
Gipsies, Kuowledg? of poisons possM*«?tf>d
by, 5.
Giraud, Dr. H., on Datura doliri urn, 388,
Glass of antimony, 604.
Glauber, Pre para lion of hydrochloric
acid, 97.
Glenard on arsenic in bjdr<»chlorie nc\f\,
98.
Glncosidos, 131-453,
Gm^liii, L., Hydrocbloric atjid in gaatric
juice, 0&.
, , on the effects of bannm salts
on animals, 712.
,, on the ell'^ite of ohromtnm
oii animAls, 702.
Omelin*a experiments on nickel sulphate,
698,
Gnoflcopinef 286.
Goliy, Poisfiuing hy^ 489.
Qodetfroy, Dr. K., onmlioo-tungstic aeid.
250.
Godfm'a eordial, 292.
Gold clilonde reagent, 249,
Gbldschmiedt un the constitution of
papayerine, 32 L
Goodart, G, F., on the microi^copjcul
appearances of the liver aft«^r phug-
pnoma jroisoning, 239.
Gomp-Besaue£ on the araeiiic abaorbed
by plantji, 558.
Qottto on the libemtion of dietbylarsine
by Mucur mucedtj, 564.
Goulard *a balsam ^ 619.
wat^r, 618.
Graudoan-s test for digit*Un, 134.
(traudval and lAJonx*s pruoess for
se^iaratijig alkaloids, 257*
750
INDEX.
Grasset and Amblard on the action of
morphine, 803.
Grate on the composition of nux vomica,
331.
Greek knowledge of poisons, 2.
Green verditer, 644.
Grehant (N.) and Martin's (E.) experi-
ments on opium smoke, 311.
Grehant, N., on carbon monoxide in
blood, 63.
GreshofTs amygdalin like glucoside, 204.
Griepenkerl on ergot epidemics, 461.
Grimm on the effects of santonin, 455.
Grinrod's remedy for spasms, 292.
Gnindmann on the composition of nox
vomica, 329.
Guaiacmn test for blood, 65.
Guanidine, 520.
Goareschi and Mosso's hydrocollidine,
528.
Guilbert on the nervoos form of arsenic
poisoning, 567.
Guinard on the action of morphine on
goats and cats, 304.
Gunn's (Alexander) method of detecting
and estimating oxalic acid, 543.
Gunther on alkaloids in Belladonna
plant, 878.
GUnzburg's test for mineral acid, 105.
Gussemo s experiments on animals witli
lead, 622.
Gutzeit test for arsenic, 579.
Guy, Dr., on a case of prussic acid poison-
ing, 212.
, , on the chromate test for strych
nine, 346.
, , on the fatal dose of strychnine,
336.
,, on the microscopical appear-
ance of strychnine, 327.
Guy's(Dr. ) method of subliming alkaloids,
258.
Gynocardin, 204.
Gypsophila-8aiK)toxin, 450.
Haaoen, a case of sulphuric acid poison-
ing, 84.
Hackford, J. E., Lead electrodes, 594.
Hsematin, 60, 61, 63.
Hsematoporphyrin, 61, 62.
Hflemochromogen, 60, 61.
Hsmoglobin, 60, 61.
Hager*s test for phosphorus, 245.
Hahneman's soluble mercury, 666.
Haidlen on morphine in blood, 314.
Hair dyes, 658
Hall, Marshal, on a death from smoking,
280.
Hamodryad (Naja bungarus), 503.
Hamberg on the localisation of arsenic in
the body, 586.
Hamlet and Plowright, Oxalic acid in
fungi, 583.
Harland, R. H., on carbomtte of lead,
618.
Harley, J., on the action of aconitine,
369.
„ on the effects of fool's
parsley, 473.
Hamack, Isolation of a base like mus-
carine, 428.
,, on the effect of copper salts on
animals, 644.
Hamack's experiments on animals with
lead, 622.
Hamack and Witkowsky's calabarine.
409.
Hamack and Witkowsky, Effect of
physostigmine on animals, 41 1.
Hartmann, J., Solubility of phosphorus
in water, 224.
Harvey's statistics on arsenic poisoning,
573.
Hassal, Dr. R., A case of poisoning by
Bumett's fluid, 691.
Haufl* on the liver in phosphorus poison-
ing, 238.
Haywood, Mr., i)oisoned by nitric acid
vapour, 110.
Heart of cold-blooded animals, Effect of
poisons on, 45.
Heart poisons, 439-440.
Hebrew knowledge of poisons, 5.
Hecker on tarantism, 491.
Hehner, 0. , Auto-experiments on potas-
sic chlorate, 132.
Hehner's method for purifying wine,
580.
Heinrich, Effects of can tharides, 494.
Heinrich's auto-experiments with coniiiie,
271.
Heisler on jaundice in phosphorus i>oisou-
ing, 230.
Hellebore root, Poisoning by, 446.
Helleboretin, 446.
Helleboriu, 446.
Helleborus foetidus, 446.
,, uiger (the Christmas rose),
446.
,, viridis, 446.
Helmholtz on the effects of santonin,
454.
Heloderma, Poison of, 485
,, horrid um, 485.
,, suspectum, 486.
Helwig on deaths from smoking, 280.
Helwig's method of subliming aJkaloids,
258.
Hemlock. See Coniint.
Hempel's method for detecting CO, 76.
Henderson's (Dr.) experiments with
phosphine, 236.
Henry VlIL, 12.
Hermann, L., on opium taking, 311.
,, on the action of ei^t, 464.
,, Physiological action of
oxalic add, 539.
^^^^^ ^^^H
H HeiMher, Biological test for human
Hufeland on the efl'aeta of tantaolti, 4fi4, ^^^^H
Hufuer and Helmholtz on the o€ecta of ^^^^H
■ blood, 66.
santonin, 454. ^^^^^|
^B Hertwiir an iioisonrng bv ohtoriue, 77^
^m Horzuand Mtjyer, Method for dttormin-
H ing^ -methyl gfoiajWr 264.
Hogo, P., on the effects of arsenic on ^^^^^|
mammals, 560, 576. ^^^^^|
on the post mortem appear^ ^^^^^|
^1 HeaWi laolatioQ of phymiatigmiiiei 4Q9,
ances in araetiic poiBon, ^^^^^|
^^^^ I^^ciKj 0,, melting-point of coeaioe
^^K h jdrochl orate ,ZBT.
^^H
Hunt, Reidj qu the fatal dose of nitnlea, ^^^^H
^^^B „ on thfl quebracho alkaloids,
^^^H
^^" 353.
on the fatal df>se of [lotaseic ^^^^^|
■ HeiseV {0. ) atroacine, 306.
xanthog^imte, 174 ^^^^^|
H Haubel on the loc&lisalion uf ]&ni, 634.
Hurt^ a case of tjixine poisoning, 417. ^^^^^|
H Hflubd^i experimeuts on animals with
Husband on a coae of rosli followtng ^^^^|
■ lead, 622.
chh>rdl, 167. ^^^H
H Hounefeld^^ turpentine solatlon, 65,
Huiiemnnn on ergot epidemics, 461, ^^^^^|
H HeUBipger on ergot eptiiemic, 461 .
Huiiemann^a ciu^iefi of digitalis jKiisoning, ^^^^^|
H Hexam&thjlone diamiue, 519.
^^^H
^V HUdebmnd on pQiBoning 1>j tobaoiCO
deGnition of poison, 22. ^^^^^|
HuB^s, Magnus, a caae of poisoning by ^^^^^|
■ through the skin, 280,
H^ Hilger, A , , a nd M ark en s , VV\ , pu ri fica ti on
phosphi^rus vapour, 5E33, ^^^^^|
Hvdrozin iv^^ a bo vent for blood, 61. ^^^^^|
^^^^ of crude Holanine^ 3B6,
^^^H f, and Markens, W«, on soUtne-
Hydfazine sulphate teat for copper, 651. ^^^^^|
^^V ine, 393.
Hjdrie i^ulphide, 76-80. ^^^H
Hilger on the Bolubility of oupper in
Ohronic poiaoning bj^ ^^^^H
soaji, 639.
^^^M
HilgerN tt'st for mineral acids, &4,
Detection of, SO. ^^^H
Hind's sweating ball, 604.
post - mortem appear- ^^^^H
Hinsborg and Ti*eupel, 35.
ances after poinoning ^^^^|
Hintz on the df^te<!tion of arHeuic, 590.
^^H
Hirne on elimination of potaaaic chlorate,
Properties of, 78, ^^^M
133.
Symptomsi of poisoning ^^^^H
Hirt on the Abeorptiou of meroury by
^^H
the skin, 672.
Hjdric sulphocranide, 322, ^^^^|
Hydrobenxamioe, 40. ^^^^^|
Hoffman on a mm of poifioning by
chloroform, 156.
Hydrocarbons, 1S5. ^^^^|
Htjifmjinn'm (A. W. v.) ^* piiieraziDe,"
Hydrochloric acid, 97-1 OS. ^^^H
620,
Action on cloth, etc., ^^^^^|
Hofmaii, Actio n of curare, 420,
^^^H
Hofraau's t^t for CSg, 174.
Detection and e^tima* ^^^^^|
Hog cholera, Toxin^a of, 638,
Holland on the eleclfolytie method of
of, 105, ^^^H
Estimation of^ 106. ^^^^|
ae^iOTating lead, 636,
Holmes on the action of ergot, 463.
Fatal dose of, 99, ^^^H
lufluenoeof, on vege- ^^^^H
Homatpopino, 3&4.
Homolle ^ di gitalin^ 435,
tation, 100. ^^^^H
in gastric juice, 99. ^^^^H
Hopkins, F, G,, on the effects of phosh
Law as to quantity ^^^^^^|
phoruB poifloning, 234.
Hoppe-Seyler on the phyaiolo^cal action
air, etc , 100. ^^^^H
poisoning, Mnsetim ^^^^^|
^^^H of carbolic acid, 1 85.
fipeoimens, 104. ^^^^^|
^^^H on th« ne^iiiration of car-
Poisonous eJIecU of, ^^^^^M
^^^" bolic acid from orgatiic
^^^H
M matter, 190.
Poison Oils effects ol ^^^^^^
H Bfippe*8ejler^a formtiln for h^ipatu),
solution of, 102. ^^^^1
■ 64.
anoda alter poison- ^^^^H
H Hot«, L. L., on copper in the human
■ body, 640.
ing by, 103* ^^^^|
H Hot tot's aconitinOf poisoning by, 374,
Propertiea of, 97. ^^^^|
H HuUEton, Dr.^ on Ifxd m driuldng
PunGcation of, from ^^^^^|
■ waterB, 630,
arsenic, ^^^^|
H Howard, J. , a horse poiaoned by tiicotine,
Statistics of poisoning ^^^^^|
■ 273.
by. ^^^H
^H Hiiber, A. ^ on polaououa effecta of dlmtro^
Hydruoollidine, 53 S. ^^^^|
■ beniol, 190, 200.
Hydioootanune« 2d$, 316, ^^^H
^^^^^^H
^^l^^H^B
752
INDEX.
Hydrocotarnine nitrate, Fatal dose for
rabbits, 851.
Hydrocyanic acid, 202-221.
Accidental and crimi-
nal poisoning by,
207.
Action of, on lower
organisms, 209.
and cyanides, Action
on living organisms,
208.
Chronic poisoning by,
213.
Commercial, 203.
Estimation of, 220.
Fatal dose of, 208,223.
Impurities in, 202.
in oil of bitter
almonds, 203.
in the vegetable king-
dom, 203-206.
Length of time after
death, it can be
detected, 219.
Medicinal prepara-
tions of, 202.
Poisoning by, 203.
Post-mortem a])pear-
ances after poison-
ing by, 214.
Properties of, 202.
Separation of, from
organic matter, 217.
Statistics of poisoning
by, 206.
Symptoms of poison-
ing by, in animals,
209.
Symptoms of poison-
ing by> in man, 211.
Tests for, 215.
Hydropotassic oxalate, 535.
Hygrine, 866.
Hymenodictine, 263.
Hyoscine, 377, 395.
Hyoscyamine, 250, 266, 377, 391.
Dose of, 395.
Effects of, 395.
Melting and subliming
temperatures, 261.
Pharmaceutical prepara-
tions of, 398.
Proi)erties of. 393.
Separation of, from organic
matter, 395.
Tests for, 382, 383.
Treatment in poisoning
by, (App.) 726.
Hyoscyamus albus, 392, 393.
muticus, 393.
niger, 391, 392.
Hypaphorine, 348.
Hypaphorus subumbrans, 348.
Hypochlorite test, 187.
Hypoquebrachine, 353.
Hyaroxylamine method of separating
mercury, 683.
Ibsrn on the detection of strychnine, 345.
Icthyismus gastricos, 489.
Ictrogen, 479.
lUioium religiosum. The poison of, 470.
Imido groups. Action of, 40, 41.
Indaconitine, 361, 368.
„ Physiological effects of,
369.
Indicators for titration of alkaloids, 264.
Inde, 447.
Infusoria, Action of poisons on, 43.
Inoko on lugu-poison, 487.
Insects, Action of poisons on, 44.
Iodic acid test for morphine, 300.
Iodine in hydriodic acid (reagent), 248.
,, in potassic iodide (reagent), 249.
,, Treatment in poisoning by,
(App.) 726.
Iodised parethoxyphenyl succinimide,
249.
Ipecacuanha and morphine lozenges, 291.
,, Compound powder of, 291.
Iris, Effect of poisons on, 48.
Iron, 696-701.
,, chloride, 696.
, , Detection and estimation of salts of,
700.
„ Effect of chloride of, on animals,
697.
,, Effect of chloride of, on man, 697.
,, Elimination of chloride of, 698.
,, Pharmaceutical preparations of,
697.
,, Post-mortem appearances after
poisoning by salts of, 698.
, , Dinitrosulphide preparation of, 1 52.
Isaconitine, 364.
Isambert and Hime on elimination of
l)ota8£(ic chlorate, 132.
Iso-amylamine, 514.
Iso-amyl ester nitrite, 148.
Isocorybulbine, 859.
Jaborandi, Treatment in poisoning by,
(App.) 726.
Jacobi, Dr. , on cases of potassic chlorate
poisoning, 131
„ on the active principles of
eigot, 458.
Jacobi's apparatus, 46.
Jaksch on benzopurpurin as a test for
mineral acid, 105.
, , Hydrochloric acid in gastric j nice,
100
Jaksoh's method of estimating HCl in
stomach, 107.
Janecke*s (E.) method of separating
mercury, 684.
Jannasch's (Paul) method of separating
mercury, 683.
jApaJdonitiDep 3^1, 3fi2«
Kippenberg(^r*9 iodine process for purifi- ^^^^H
Jftvelle watef, 124,
cation of jft1ka1oid», 253, ^^^^H
Jeaun«r8 test for CJ][i{»er, 63 8>
procB^ for aeparating ^^^^H
Jelfer-B j>uri(icaUon of Uydrochbrio acid,
alkaloids, 252, 255. ^^^H
58a,
Kirby. Case of |»oisoning hy arsenical ^^^^|
Joqiiiiity, 478. •
^^H
Jemjoe, 260, 402, 404.
Kirachgasser on the symptoms of poison- ^^^^H
,j Sii«ctruiu of colour reaations, 5i<
J obit itm Hesse iaoUte physoatigmine,
ing by arsenical waJl-pa|iers, 509. ^^^^H
Kitasato and Weyl on the separalioii of ^^^^|
409.
tetanine, 525. ^^^^|
JohnBfAij G., Casea of c&mplior tMiEtoaing.
KleiD, Dr., on tlie cauacr of food [loiflou- ^^^^H
UL
ing, 531. ^^M
Jowett, H. A. a, E]>iiici4mn, 505.
KloewBti or Ctiapman case of antimony ^^^^H
Jub{:^ir» statiBtu-a of nitrO'bett£eiie |ji>i^)i-
pojjsoning, 608. ^^^^H
h\g, 193.
Kober^ Detection of ergot in Hour, 460. ^^^^|
.h]jiitjUi» on action of chlDFoform on
Kohert on carbon monoxide itoiaoning, ^^^^^H
pkiiU, 157:
^^H
Juuy, l>et(!ction of merciir? in ttnnej 684.
.hirgeijs, A., on the »>lub»Uty of ncojiJ*
on cyanogen iodide, 222. ^^^^|
on {jeatlifi from lupin seeds, 47^. ^^^^H
on the (colour of olood it) HCN ^^^^|
tine, 36JJ.
poiivoningt 214, ^^^^H
Kaiilhauh^m pi lias ic taldf 203,
etfect of ''^hnapSf" 9Z ^^^^H
eirectsof^'pbanin,*'42d. ^^^H
Kfippeler on di<u.thH under chloroform
vajKJur^ 15&.
cllects of sphaovlic acid ^^^^H
Kara-Knrtf 'JMiCj (Latbrodf!€t€« higubris)^
and eornutin on nni* ^^^^|
490.
mats, ^^^H
Kiiring on the coinjwftition of nux
poison of spiders, 490. ^^^^H
vomica, 331.
symptoms of iioisoning ^^^^H
by barium safla, 713. ^^^^H
ICaritschoijer on chmnie HCN |Hjisoniiig,
214.
t^KXalbumin of c»stor-otl ^^^^|
Ka^ner^ G.^ Solanlne in dLsea^
seeds, 478. ^^^1
potatoes, Zm.
and Kfisan<^ron the phyMiolugical ^^^^|
KaHl, Relation between nan^otic power
action of oxalic acid, 539, 510. ^^^^H
and numbt^r of ethyl groU|M}, 171.
and Eiisancr^s t^i^penmentu on ^^^^H
aniniab with oxalic acid, 536. ^^^^H
Kiitiix>, Th*?, 491.
Kauzmaun on thu excretion of morphine,
^obert^s classification of poisons, 24. ^^^^H
313.
c«irnntin, 458. ^^^^|
K^lk^r on the rt'JLctions of cornntiit, A(i9.
dctiiittion of poifion, 23. ^^^^|
t43st fur HCH, 217. ^^^H
Keller^s method of estunating brnuine
and stryohiiint;^ 349>
Kuhler on the action of ergot, 46 4p ^^^^H
,, ,, ofeBtitniitingdigitojtinj
Kol!«r*s prnssic add, 203. ^^^^H
^K
Kombe, 447. ^^^M
^^^1 of f?5timating nicotine
Kou<.4da tree, 326. ^^^H
^^H in tobacm, 273.
Koppe, Dr., poison i^d by digi toxin, 433. ^^^^H
, Be jiamtion of m u»«arine , 4 28. ^^^^|
^^^H tifnux vomica analysis.
^ 330,
KoppeV experimentjfi on dlgitoxin, 435. ^^^^H
Kt'lynack antj Kirby on the iiyiaptonis
Koplwachaar's method of ostimating car- ^^^^|
bolic acid, 192. ^^^^^1
from drlnkinf^ arHenicul boer^ 571.
Krirmua niinetan ^OL
Koviillamaru), 449. ^^^H
Keroaine, 136.
Kowalewsky on the combination of ^^^^|
Kili&nij 11., on anlmriii^ 4^5.
albumin with uraninm^ 710, ^^^^H
„ on digitonin, 432.
Ktaatzer on Ciciman ^ansage |ioijfoning, ^^^^|
,T Formula ufdigit/jxiu, 433.
^^H
Kitig on opium stnoking. 3l*i.
King*9 yellow, &55.
Knft. See StebeH. ^^H
Knit (Enngnnis c«nil«t]B], SOS. ^^^H
Kino^ Compound powder of, 200.
Kmtter, Dr., on excrotion of strychnint^, ^^^^|
Kionka, Ezjierinienta on carbon mon*
^^H
oxid^ 7!.
K Tockiitj Physiologiral aetiou of n ieoti ne , ^^^^|
Kipjienberger on lodieatoTS for titration
^^H
^m of alkaloida, 261
Kromhob, A ciii« of jmisoniug by the ^^^^|
^^^H ,, on tiie decotii position of
Ci>mini»n morelle, 431, ^^^^H
^^^H ctiloroform, 1^9*
Kru^rr on ars^nious acid, 547. ^^^^|
Knflorath OT1 the i^leetrnlvf^iH of eoppr ^^^^|
^^^M „ ou the* fiolnbiltty of alka-
^^^^^ lo&ds, 255.
m]U, 6r»]. ^^^1
^^^M
754
INDEX.
Kusa-UBU, 377.
Russner, Eifects of sodio oxalate on
animals, 536, 539, 540.
Kiister on a case of carbolic acid poison-
ing, 183.
,, on sensitiveness of animals to
carbolic acid, 183.
Laburnum. See Cytisine.
, , seeds, Treatment in poison-
ing by, (App.)727.
Ladenburg on alkaloids in belladonna
and datura plants, 378.
Ladenburg*s hyoscine, 395.
,, preparation of coniine, 266.
Lajoux method of separating alkaloids,
257.
Lallemand, Perrin, and Duroy on alcohol
in the brain, 146.
Lamy on the effects of thallium salts,
707.
Lamson, Henry, the poisoner, 374.
Lancereaux on chronic poisoning by
copper, 649.
LanoBDerg on the excretion of morphine,
313.
Lane, R. W., and Carson, C. M., on the
solubility of antimony sulphide, 612.
Lancaard, A., on the poison of Illicium
religiosum, 470.
Langsdorf, Dr., on the effects of Amanita
muscaria, 427.
Lanthopine, 286.
Lassar, 0., Observations on nitric acid
vapour, 110.
Lathyrus cicera, 480.
,, clymenum, 480.
,, sativus, 480.
Laudanine, 286, 324.
, , nitrate, Fatal dose for rabbits,
351.
Laudanum, 290.
,, Treatment in poisoning by,
(App.)727.
Laudanidine, 286, 324.
Laudanosine, 286, 324.
Lauder, Formula for corydaline, 360.
Laurocerasin, 205.
Law on salts which facilitate separation
of arsenic, 581.
,, H. D., Electrolytic cathodes for
separation of arsenic, 594.
Laws relating to poisons, 20-22.
Lead, 616-637.
acetate, 617, 618.
and opium pills, 290.
as a poison, 620.
basic acetate, 633.
carbonate, 618.
,, Dose of, 634.
Chloride of, 617.
chromate, 625, 701.
,, Case of poisoning by,
704.
Lead, Chronic poisoning by, 625.
„ Deaths from, 620.
,, Detection and estimation of, 635.
,, EfTects of, on animals, 622.
„ „ man, 623.
,, ,1 ,, nervous system, 623.
,, Electrolytic method of seuaratiiif,
636.
,, Elimination of, 633.
,, encephalopathy, 626.
„ Fatal dose of, 633.
,, glazes, 621.
,, in American overland cloth, 621.
,, in foods, 621.
,, in glass, 621.
,, iodide, 618.
,, Localisation of, 684.
„ „ in the brain, 627.
,, nitrate, 619.
,, oxides, 616.
,, Peroxide test for, 635.
,, Pharmaceutical preparations of,
618.
,, Physiological action of, 632.
,, pigments, 619.
,, plaster, 618.
,, poisoning among white lead em-
ploy&, 620.
,, „ from water, 629.
,, „ Influence on pregnancy,
625.
,, ,, Post-mortem appear-
ances in, 632.
,, ,, Statistics relative to,
620.
„ „ Treatment of, 634.
,, pyrolignite, 619.
,, Salts of, Ti'eatment in poisoning
by, (App.)722.
,, sulphate, 617.
,, sulphite, 617.
Lebert and Wyss on the urine in phos-
phorus poisoning, 234.
Ledoyen's disinfecting fluid, 619.
Lees, Isolation of gynocardin, 204.
Lefort on the excretion of morphine,
313.
Leerip on the localisation of lead, 634.
Lehmann on hydric sulphide poisoning,
79.
, , on hydrochloric acid in gastric
juice, 99,
,, on poisoning by chlorine, 77.
,, on the excretion of solpharic
acid, 95.
, , on the quantity of laurocerasin
in the service tree, 205.
lichmann's experiments on the solubility
of copper, 638, 689.
,, experiments on the toxic
effects of copper, 645.
Leiblinger on a case of mercurial
poisoning through the skin, 672.
Lemaistre on poisoning by digitalin, 435.
^^^p ^^^H
^M L&nmnmfs odontalgic essamoe, 292.
Lippert on R«insch's test for arsenic, ^^^^1
^M Lenuberger, Penetration of carbon moD-
^^H
^H oxid«^ g&s LQto tliG body, 75.
Liquor amn}oni^^, 117. ^^^^^|
^M Ij^ Emery, Nii^olas, 14.
ammonu ai^nitis, 552. ^^^^H
^1 Leiititi on poisoning by »abadilla powder,
utienicalia, 5{i2. ^^^H
■ 407.
arsenii et bjdrargyri iodidi, 653. ^^^^H
natri carbolici, 176. ^^^^^1
^B Leo ftnd Uttelmann's distinction between
^M tmd& and acid salta^ 106,
plumbi HubaoetattSf 018. ^^^^H
^H Lerach on the ettect of digitalis mi man ^
„ potoBsat, 122. ^^^^H
■
pota^^ elferveseens, 123^ ^^^^^|
^m Lc'sfranc un the fatal dose of banuni saltan
,, sodm, ^^^H
■ 713.
Lloyd, J. W., on Urn solnbUity of ^^^M
^^^^ L<ssa*iT on tbo action of hydruehloric acil
morphine Aolte, 297. ^^^^H
^^^^L on skin, 102.
Lloyd's test for morphine, 300. ^^^^H
^^^^1 y^ ontheeom)Hivi?actionofftu]phuric
Lob«l, L., on the mininuim dose of ^^^^^|
^^H acid, 83.
phosphorns, 229. ^^^^^^
^^^^P ,, on the pathological changes caused
Locke on Iho physiological action of ^^^^^|
^^^™^ by oicalic acid, 64L
^M Letkefayf Dr., A caae of nitro-beQiene
oxalic acid, 539. ^^^^H
Locus tUp &, ^^^^^1
^M poisoning, 134.
Locust tree, 481. ^^^M
^m Leticin in pho^phojus |>oiionin0, 245.
Ltien on poat -mortem appeamnces after ^^^^H
^M Levenatein on strychnine m cliloml
l^d poisoning, 032. ^^^^H
^M pciisonlngt 106.
Loew's theory as to poisons, 39. ^^^^^|
^M Lewea* Btlrer cream ^ $19.
LoQwy on poisoning by mercunc chloride ^ ^^^^^|
^M Lewiu on tbe toxic do&e of oopjier, €47.
^^^^1
^M t3 ^^ jaundice in phofiphoms
Lolliot on the eU'ecte of arsenic on a dog, ^^^^|
^M poisoniDg, 2S0«
^^H
^M Lowy on the effects of lead poisoning,
Lomlianl, H. C, A oaso of sulphuric ^^M
■ 627.
acid poboningj B4. ^^^^M
^B Leyden, Fatty liver after phosphorufi
Lotusin, 204. ^^^H
^H poisoning, 233.
Lowe, Cbarlc^, on tbe assay tif ctnde ^^^^^|
^H Leyden, E., and Mniin, P., Urine In
carbolic acil J p 191 » ^^^^|
^1 ^nlpbufir acid puisuning, 9&«
LubiuMky on tht^ di^te^tton of bismuth, ^^|
^M L'Hote, Poisonous effects of jKitAsaic
^^^M
H cblitrate, 13L
Ludwig on the localisatiou of arsenic In ^^^^H
^B Liebort's cosmHii^ue infallible, SIS,
tbe body, 580. ^^^H
^M Li ('big and Wohler on the hydrotysts of
Lndwig and de Try ou audarin, 445. ^^^^H
^1 amymlaliti, 204.
^M Liebreck on the blood tn phosphorus
Luilwig'M method of separating mercttry, ^^^^^|
^^^H
^m poiflODingf 235,
LuH, Method of extracting Ihe remtrum ^^^^^|
^M Liebreicb on the poisonous c-tfectfl of
alkatuids, 401. ^^^H
■ ebloral, 164.
,^ properties of jervine, 404. ^^^^^|
^M Liefsch's (U W,) eiperimeuts with
t, properties of rubi-jervine, 405. ^^^^^1
^M tnrpeDtino, 140.
Lupininis 479. ^^^^^|
^M hbith on the compel tion of mix vomica,
Lupinidine, 263. ^^^^^|
■ aso.
Lupins, 479. ^^^^H
■ Life-tests, 45-48.
Lupinna luteus, 272. ^^^^|
■ Ling, A, R., atid Kcndle, T., on the
Lutidtnc as an antidote for strye1inin«, ^^^^^|
H purification of hydrocbloHo acid, 5S1.
^^^H
^1 Linii4 on a case of potanning by niiL^zei^on ,
Lyct)sa tarantula, i^Q. ^^^^H
■ 4ae.
LyLta as^ieru, 492< ^^^^1
^M Linosaier^ G., on the distribution of
^^^^^^
H barium in the body, 714*
^^^^^^
^^^^ Linstow, Dr*, on a case of |*<49oning by
^^^K chromate of lead^ 704 ^
M*Apam on tbe dotcotion of strychnines, ^^^^H
^^^H
^^V
H'Conkey p. Reg., A case of aconite ^^^^^|
^^^^ ,1 on the eH'ects of santonin,
|Hji Boning, 370. ^^^^^^|
]kliiedoti^airs disinfecting pi>wdeTi 17^. ^^^^^|
H 455.
^M Liouvillc on the poisonous elfects of
Macb on chronic poisoning by copper, ^^^^^|
^M curare, 419.
^^^H
^^^^ , , on tb 0 |x)st- niortc in a ppeaiancea
Man^agan, Dr., and Rutter, J. T., on ^^^H
^^^^L in silver nitrat«r jioisouing.
^rmnic eaters, 561. ^^^^H
^^B
MacMnnn on blood in dinitrodfenseu ^^^^^H
^^^^ Lipwitz^a test for pboephorue, 245.
ptnaoning, 201. ^^^^H
756
INDEX.
Macniven, E. 0., on a case of poiBoning
by bichromate of potash, 703.
Macphairs cases of carbolic add poison-
ing, 180.
Macredy on a case of strychnine-laudanum
duplex poisoning, 336.
Madagascar ordeal poison, 449.
Magefhaes, Test for cytisine, 399.
Magendie on the action of hydrocyanic
acid on a dog, 210.
,, on the effects of phosphorus,
229.
Male Fern, 481.
Malmignette (Lathrodectes tredecim-
guttatus), 490.
Malpur^o*s test for nitro-benzene, 198.
Mandelic nitrile, 223.
Mandelin's reagent for alkaloids, 251.
Man^iga, 447.
Manjot, Dr., on symptoms of chloral
poisoning, 166.
Mannheim, Poisoninc by cocaine, 358, 359.
Mannko]>f and Schultzen on excretion of
sulphates, 95.
,, on a sequel of sulphuric acid
poisoning, 89.
„ on urine in sulphuric acid
poisoning, 95.
Manouvriez, Dr. , Case of potassic chlorate
poisoning, 182.
Marchand, F., Experiments on animals
with potassic chlorate, 130.
Markens, W., Purification of solaniue,
396.
Marking-inks, 659.
Marme-Borchers, Physiological action of
taxine, 416.
Marme, W., isolates taxine, 416.
,, on i)otass - bismuth iodide
as a precipitant, 448.
„ on the effect of cytisine on
animals, 400.
,, on the effects of thallium
salts, 707.
Marm^*s experiments with cadmium on
animals, 615.
,, reagent for alkaloids, 251.
Marsh and Marsh-Berzelius test for
arsenic, 580-584.
Martin, Experiments on opium smoke,
811.
,, on a case of chronic poisoning
by ether, 150.
Martineau on ttie subacute form of
arsenic poisoning, 566.
Mascarcl on ])hosphorus poisoning, 237.
Maschka on a case of acute poisoning by
copper sulphate, 647, 648.
,, on a case of |)oisoning by
morphine, 807.
, , on a case of i)oisoning by Nerium
oleander, 449.
,, on phosphorus |K)iHoning, 241.
,, on the effects of " phallin," 429.
Maschka's case of alcoholic poiaoniog,
144.
, , case of bitter almonds poiaon-
ing, 220.
„ case showing caution neoes-
saiy in judging sulphuric
acid spots, 87.
Mason, W. P., on a doubtful cmse of
arsenic poisoning, 588.
Matches, 226.
Matzkewitsch on the diatribution of
zinc in the body, 692.
Maybrick case, 569.
Mayer, Poisonous effects of oxalic com-
pounds, 545.
Mayer, J. L., on Lloyd's test for
morphine, 300.
Mayer s reagent for alkaloids, 264.
Mays on the physiological action of
brucine, 850.
Meadow saffron, 421.
Meconic acid, 286, 824.
„ Physiological action of,
825.
,, Separation of, 326.
Meconidine, 286.
Mecouine, 324.
Medicus, L. , and Kober, on the detection
of ergot, 460.
Meihuizin on the action of digitalin on
frog's heart, 443.
„ on the physiological action of
morphine, 305.
Meili on poisonous effects of phenol and
cresols, 179.
Meillere, G., on the localisation of lead,
634.
Melanthin, 450.
Melitta vencuosa, 488.
Mclsons on the detection of nicotine,
282.
Menard on the blood in phosphorus
poisoning, 235.
Mendius* reaction for producing cada-
verine, 517.
Menegazzi, P. G. , on recovery of carbolic
acid, 190.
Menispermine, 465.
Merck on codeine in opium, 317.
„ on hyoscine, 395.
,, on pseudo-hyoscyamine isolated
by, 396.
,, on the solubility of strychnine,
327.
Mercurial lotion, 664, 665.
„ ointment, 663-665.
„ suj)po8itories, 663.
,, tremor, 673.
Mcn^uric chloride, 664, 676.
„ cyanide, 667, 681.
„ ethyl chloride, 664.
I ,, methide, 674.
I ., potass-iodide, 249, 686.
I „ salts, TesU for, 681.
^^^^^^^^ ^H^P ^^H
ftlcruuric 8dltii, Volumetric efttiTfiAUoa of^
Metaphetiyletiediamlne, 510. ^^^^|
68&,
Kothivntoglobin, f)0, 61. ^^^^|
Metheoe dichloridc, 170. ^^^H
1 1
auiuhido, 667^ i
l^tercumufi acfit&te, 664,
MethoLodiJLne, 805. ^H
**
chloride, 662.
Metlioxyl ^oups. Determination of, 263. ^H
It
saltB, 681.
Methylamme, 513. ^M
If
„ Testa for, esi.
Methyl -aniline viokt test for mineral ^H
It
,f Volumetric e^miitlt»n
acid, 106. ^^^^|
of, 696.
bnicine, 34. ^^^^h
Memiry, 662^680, i
chloride, 170. ^^^H
11
Absoq>tioTi of, by tlie skm^ 672.
and cn&lk, 663.
Meihylconiine, 263, 269. ^^^^|
Methyl cyanide, 222, ^^^H
i^^^^^h
and quinine^ 667.
cyanide, 221, 667, 677.
M ethyl guamidiue^ 521, ^^^^H
^^^^^1
Mcthyliuorphiniethide, 299. ^^^^^
^^^^^H
,, Teals for, 680.
Methyl morphol, 299. ^^^H
]>cath8 from, 669.
pbcinol. See CTe^jL ^^^^|
^^^^^1
D^tcotion of, in orginulc »uh*
i^tryehnine, 34. ^^^^H
«t4nce«, 631, 683.
iirethane, 37. ^^^^|
^^^^^1
EliininAtion of, 67 £^.
Methylene dicytielne, 399, ^^^^1
'^^^^1
Estimatitin of, 685.
Meyer, filimination of methyl groupi, ^^^^H
i^^^^^P
Green iodido of, 666.
^^H
^^^^^1
in the arts, 667.
on ergot epidetnic^, 461. ^^^^H
^^^^^H
in vcteriimiy modicino, 669,
OD narcotica^ 37. ^^^H
Uniiucri^ 663.
on the actton of fltryoUnine on ^^^^M
^^^^^V
Loealiijfttioii oi; 679,
blood presauTO, 341. ^^^^H
Mcdiciual Atid fatal dose of 8f)Xt&
Meyer, Dn Oarl, })oieoii<^ by aeotiHtne ; ^^^^^
of, 66f).
Poflt-moriem apppAranct?a, 376. ^^^^H
^■^^_
Medicinftl [ireparfttionEi of, 662.
Meyer, H., on the conulttntion of can- ^^^^H
Iharidin, 492. ^^^H
^^^^^^B
Mu^om prepamtions illustra-
tiTC of cases of poificming by,
Meyer and Stein feld on the toxio eflocts ^^^^H
678.
of b ifimnth , 653 . ^^^H
^^^^^^H
nitrates, 666, 667.
Me£€reum, The Daphne, 456. ^^^^|
, t Fktiiological cli an ges i n
Midwt, M. Cb., Exix-Timentaon Mi, 42. ^^^H
Cftses of iioisonhig by.
Micro- riii|]inictrr\ 65. ^^^^H
676, 679.
M il n Q £<1 wanls on t he action of morphine ^^^^|
^^^^^^H
„ Foisonotte iMtton of.
on the Felidiv, aOi. ^^^M
676.
Mitiemi blue, 56B. ^^^H
^^^^^^H
oleftto, m^.
Mirt4>^ D. , Exp^nmentis on CO, 76. ^^^^H
^^^^^H
Patient and quack medicines
MitfiolicrUch*fi discovery of nitfo^tienEcue, ^^^^H
containing^ 668.
^^H
^^^^H
iwrclilonde, 664, 676,
process for the detection ^^^^H
^^^^^1 f 1
pUsUf, 66a.
of phosphofua, 241. ^^^^H
^^^^^H
tKiiiioning.StutiHUci^ijf, 669 » 675.
ro»t*niorlcin ainioarancea in
M older, E., Test for bmi^oic acid, ^m. ^^^H
l^^^^^l
Mohr, The eaLtmation of arson ic^ 698, ^^^^H
caaeu of poi^utiing by ^ 677.
MoisHan, H., on the comitoiiitioti of ^^^^|
^^^^^^1
Potftssic iodide migcnt, 219.
* * c h a i^doo " smoke , 311. ^^^^H
^^^^^M
Red iodide of, 665.
Monac(5tin, 37- ^^^^H
^^^^^^1
,j oxide of, 664
Monkshonrl or wolfsliane, 360. ^^^^^
^^^^^^1
Sp^tamtion of, 6 S3.
aUDclilorlde, Ointment of, 66fi.
Morellc, The common, 431. ^^^^H
^^^^^1
Morgagni on |K>i«uning by bollebore root, ^^^^H
^^^^^1
,. Hll 0^ 666.
^^^H
^^^^^1
sulphate, 666.
Morgan on ntortality from cblx>L\ifurni ^^^^^H
^^^^^^1
suli»!iidB, 662, 666,
vapour, 156. ^^^^H
Mor|mia. See Mt^rphinf. ^^^^1
^^^^^^B
Id^^utilicatioti of, 682.
'^^^^^P
Hutpbo-cyanide, 668.
Morphine, 2&0, 264, 266, 266. 236. ^^^1
^^^^^^1
TeaU for, 680.
acetate, 297. ^^^H
^^^^^^^P
Treatment of poisoning by, 677,
Aetion qji animak, 303. ^^^^|
(App.)729,
man, 306-300, ^^^H
^B I'l
Tapoor, Elfectit of, 670-673,
Contititution of, 298. ^^^^1
■ Menc,
A f^m of ohronie eldurofonn
dcrivativeji, Pliyablogical ao^ ^^^^|
■ Metttldehyd^ 170.
tion of, 305. ^^^^H
iXiBeof, 294. ^^^1
■ Mt^t^h,
Detection of. I>5»
Excretion of, 313. ^^^^H
^t Mt^iuijtimonic tKtid, 601.
hydroebloialv, 297. ^^^H
758
INDEX.
Morphine lozenges, 291.
,, mcconate, 297.
,, Melting and sablimiug tem-
peratures, 260.
„ Physiological action of, 304.
,, iK>i8oning, Treatment in, SI 2.
,, Post-mortem appearances after
poisoning by, 312.
„ Proi)ertica of, 296.
„ salts, Solubility of, 298.
,, S(.>])aration of, from animal
tissues, etc., 313, 314.
,, Spectrum of colour reactions,
58.
,, sulphuric acid, 305.
,, suppositories, 291.
„ tartrates, 297.
„ Teste for, 300-303.
,, Treatment in poisoning by,
(App.)727.
Morphol, 299.
Moqiholine, 299.
Mosso, Isolation of CioHi^N, 528.
Mountain or mineral green, 644.
Mucor i)hymocetes, 5.
Muir, Patterson, on the estimation of
bismuth, 656.
Mulder on codeine in opium, 317.
Mulliken on pre])aration of dinitro-
benzoate, 147.
Multiple antidote, 733.
Munk and Leyden on the liver in phos-
phorus i)oisoning, 238.
Munk ana Sip|)cll on the effecte of crypto
pine, 323.
Munn, P., on the urine in sulphuric acid
poisoning, 95.
Mursena helena, 487.
Murrell, Physiological effi-cto of gelse-
mine, 354.
Muscarine, 266, 426, 430, 522.
,, Detection of, 429.
,, Effecte on man, 428.
,, Properties of, 428.
Mushrooms, Treatment in poisoning by,
(App.)728.
Mussels, Poisoning by, 488, 526
Mydaleine, 520.
Mydatoxine, 526.
Mydriasis, Toxic, 48.
Mylabris cichorei, Cantharidin in, 492.
,, punctum, „ 492.
,, pustulate, „ 492.
Myosis, Toxic, 48.
Mytilotoxine, 527.
Naoelvoobt, J. B., Teste for physostig-
mine, 410.
Naphtha, Coal-ter, 186, 138.
,, Mineral, 135, 136.
,, Petroleum, 135, 136.
Shale, 136.
Naphthylamines as poisons, 34.
Narceine, Effecte of, 320.
,, Melting and subliming tem-
peratures, 261.
, , Properties and constitation of,
319.
„ Teste for, 820.
Narcotics, 86, 37.
„ Minor, 170.
Narcotine, 250, 264, 265, 266, 286.
„ Constitution of, 816,
Effecte of, 817.
,, Melting and subliming tem-
peratures, 261.
,, Properties of, 315.
,, S})ectrum of colour reactions,
58.
„ Teste for, 816.
Nasse, 0., on the blood in phosphorus
poisoning, 235.
,, on the physiological action of
nicotine, 282.
Nativelle's digitalin, 435.
Nemssia cosmenteria, 489.
Nerianthin, 448.
Neriin, 448.
Nerium odoruni, 440.
,, oleander, Poisoning by, 440, 449.
Nenist balance, 684.
Neumann on blood, 66.
,, on the distribution of barium
in the body, 714.
Neuridine, 515.
Neurino, 41.
Neuwiedcr green, 644.
Nevin's (Dr.) experimente on animals
with terter emetic, 606, 609, 610.
Newcastle white, 619.
Nicander of Colophon, 3.
Nickel. See Cobalt.
Nicloux and Gautier, Detection of CO, 76.
Nicotoine, 263.
Nicotelline, 263.
Nicotianum tebacum, N. rustica, and
N. porsica, 272.
Nicotine, 250, 263, 264, 265, 266, 272-
283.
„ Antidote to, 283.
,, distinguished from coniine,
276.
„ Effecte on animals, 277.
,, ,, man, 278.
„ Estimation of, in tobacco, 273.
„ Excretion of, 281.
,, Fatel dose of, 282.
„ Physiological action of, 281.
„ Post-mortem appearances after
poisoning bv, 282.
,, Pro}>erties ana constitution of,
275.
,, Separation of, from organic
matters, 282.
,, Teste for, 276.
,, Treatment in poisoning by,
(App.)728.
^^^^^^^^■^^^^^^^^^^ INDEX. ^^^^ ^^^H
H Nicotinine, 203.
Kux vomictt, StAtii^tic^ of poisoning by, ^^^^^|
H Ntkitiu on the iLetiDii of ^fgut, 464*
^^^H
^m i, ou tbe fat&I dost^ of bcl^rotia
tincture ( B. P, ), 330, ^^^H
■ acid, iei.
^^^^^1
H Kttmto of potAah, S&e Pelaxtic niirai^.
Oboldnbiu on the separation of eolcbi- ^^^^H
■ Nitre. Siie iV^^OMi^ ntlra/^.
^^^^1
■ Nitri0 acid/lOB-ne.
CEnniithe crocato. See Water Jtemhsk, ^^^^^M
^^^^ „ Action ofj on TegetatioUr
Ogier^s method for dcstr^iying organic ^^^^H
^H
matter, 53. ^^^^1
^^^L tf Detection snd estimation
Ogier, J,, and Herscheri Biological te»t ^^^^^|
^^H
for blood, ee, ^^^^1
^^^^1 Direct flsparatioD from
OgstoD, F., Test for cbloral hydrate, ^^^H
^^^^1 org^itilo Tuatter, 115.
^^^H
^^^H EJteots of liquid, 11 U
Oidtmann on the loealtitation of lead, ^^^^H
^^H Fatal doee of, 109,
^^^H
^^^1 Local action of, 112.
0 11 o f bitter almonds, Cistimation of HCK ^^^H
^^^^1 fioiaoniog, Museum apeci*
^^^H
^^H mens ofp lia, 114.
Puiaoning by, 220. ^^^H
^^^^H Post- mortem appearances
^^^^H after pgi^oning Dj, 119,
Oils, Essential, 139. ^^^M
Oldham cases of food poisoning, &30, ^^^^^|
Oleander digital in. See Neriin. ^^^^^M
^^^H Properties of, lOS.
^^^H^ „ St^tiatks of poisoning by^
Qleandnn, 448. ^^^^1
^^M
Oliver, T., on hydric aalphide polKm- ^^^^^|
^^^^m 8jniptum& of poiMtning by^
^^H
^^H
Onage, 447, ^^^^^|
^^^1 Vne of, in the arts, 109.
Onanm on the elTects of barium salts on ^^^^^|
^^^^1 ,j vapour, Poisonous action of,
animals, 712. ^^^^^|
^^V
on the phjuiological action of ^^^^^|
V Nitro-benxene, 193-193,
oxalic iM^id, 539, ^^^^^
^L ,, Detection of, 197*
Opolina rattanun, 43, ^^^^H
^^^ , Fat^l dose of, 1 96.
O phio toscin ,499. ^^^^H
^^^^^ Oil of bitter altnoDds dm-
Opianic aciaj 316. ^^^^^|
^^^^^^H tingui^iihed froaii 19S.
Opiatiinc, 286. ^^^^H
^^^^^^B E^utlRilogical appeamnceii
Opiaiiy), 324, ^^^H
^^^^^^H in jioisoniDg liy, 1D7.
Opium group of alkiloidti, 285- S2&, ^^^^H
^^^^^^H Phy Biological action of,
Action on animals, 303. ^^^^^|
^^^^H
nmn, 306-309. ^^^M
^^^^^^1 Propeittesof, 193.
Action of Bot vents on, 287. ^^^^^|
^^^^^^^B Separation from orgjania
Ammouiatfid tincture of, 290« ^^^^H
^^^^^1 matters, 1&7>
and lead pills, 290. ^^^M
^^^^^^^H Symptoms of poisoning by ,
,, Aromatic powder of chalk and, ^^^^^|
^^^^H
^^^1
^^^^^^^M Treatment poisoning
Assay of, 237. ^^H
^^^^P by, (App0 729.
Qompoaltion of, 285. ^^^H
Nitrous oxidfl g?*a^ Treatment in poison*
CompottDd powder of, 290* ^^^^H
Confection of, 291. ^^^H
in^hy, (App.J729.
Nutting liau J oia&s of food pobotiing, 53 0*
Detection of, 295. ^^^^1
wbite, ei9.
Dose of, 294. ^^^H
Novy, F, 0, , Toxines of liog cholera, 52S»
eating, 310. ^^^^H
NoyeB, W. A.t on the df?tcction of
Exiructof, 291. ^^^H
strycbuine, M5.
KaUl doee of, 295. ^^^H
Nunueley on the detection of strychnine.
Llntmentof, 29L ^^^H
345,
lozenges, 291. ^^^^^|
Nuimeley's ex penmen ta with HCK un
Medicinal and other preparaUona ^^^^^M
dogi, 212.
^^^M
Hntflfis' drojts, 292.
The ointment of gsMt^ and, ^^^^H
Nnssbnum on tnurtality from chloroform
^^^H
vapour ( 150.
Falfot and non^ officinal prejiatm' ^^^^^|
Nui vomica, 326.
ikn\R of, 292. ^^^^|
^^ 1, Analysis of, 330,
Fotsou i rig of ehild nsu by , 294 . ^^^^H
^^^^ Aqueous ettmct of, 329,
^^^^H Pharmaceutical prepaimtiona
poisoning, Posi-mmlffm apjiear- ^^^^H
^^H
ancee after* 312. ^^^^H
^^^^^ Spiritous extmct ofj 329,
„ Slutistios of, 293, ^^^^H
76o
INDEX.
Opium iwisoning, Treatment in, 312, 727.
„ Tincture of, 290.
,, wine, 291.
Opistoglypha, 498.
Orange red, 619.
Ordeal bean, 409.
Ore's (M.) injection of chloral hydrate,
164.
Orfila on a case of arsenic poisoning with-
out symptoms, 563.
J, ,, poisoning by acid oxa-
late of potash, 588.
,, ,, poisoning by tartar
emetic, 607.
,, jwisoning by verdigris,
648.
,, on arsenic in bones, 588.
,, on perforation of stomach due to
potassic nitrate, 130.
,, on poisoning by water hemlock,
474.
,, on the destruction of organic
matter, 585.
ctTects of barium salts on
animals, 712.
elimination of antimony,
610.
imbibition of arsenic
after death, 590.
inflammatory effects of
arsenic, 575.
post-mortem appearances
in arsenic poisoning,
573.
separation of iron from
organic matter, 700.
time after death nicotine
may be detected, 282.
Orfila's experiments on animals with
lead, 622.
,, experiments on animals with
oxalic acid, 536.
,, experiments on ether, 150.
Organic matter, destruction of, 52, 585.
„ drying of, 51.
Orpiment, 551.
Osenbrliggen's case of nitric acid poison-
ing, 111.
Otori, J., on the amines, 510.
Otto on a coniine-like alkaloid, 272.
Oubain, 418.
Overend and Hofman on the action of
curare, 420.
Overton, Researches on narcotics, 36.
Oxalate of lime, 534.
Oxalic acid, 533-544.
,, Effects of, on animals, 535.
,, ,, leeches, 537.
,, ,, man, 537.
,, Estimation of, 544.
,, Fatal dose of, 535.
,, in the form of vapour, 587.
„ Pathological changes pro-
ducedby, 540.
Oxalic acid, Physiological action of, 539.
„ Properties of, 533, 534.
,, Separation of, 541.
,, Statistics of poisoning by,
535.
,, Treatment of poisoning by,
(App.)729.
,, Uses in the arts of, 535.
Oxalmethyline, 545.
Oxalpropyline, 545.
Oxyhsemoglobin, 60, 61.
Oxymandelic acid, 241.
Oxynarcotine, 286.
Page, Dr. D., on poisoning by anti-
monial lozenges, 606.
Pagel's process for destroying organic
matter, 54.
Palm, R. , Separation of picrotoxin, 468.
Palmer, William, the ])oisoner, 333.
Papaveramine, 286.
Pai>averine, 264, 266, 286.
„ Effects of, 321,
,, Melting and subliming tem-
peratures, 261.
,, Properties and constitution
of, 321.
, , Spectrum of colour reactions
58.
Papaver somniferum, 285.
Paradigitaletin, 434.
Paraldehyde, 170.
Paramenispermine, 465.
Paraphenylenediamine, 519.
Parcfioric, 290.
Parillin, 450.
Paraffin oil, 134.
Partition coefficients of narcotics, 87.
,, ,, Chemical deter-
mination of, 38.
,, „ Physiological deter-
mination of, 38.
Pattison's white, 619.
Paul, M., on the hereditary effects of
lead poisoning, 629.
Paul or ^gina on the effects of lead on
the nervous system, 626.
Paulet on the effects of thallium salts,
707.
Pauly, E])inephrin, 505.
Payne and (jhevallier on the action of
organic fluids on zinc, 688.
Pedler on the poison of the cobra, 499.
Pehkschen's formula for jervine and
pseudo-jervine, 404.
Pelikan on the effects of saponin, 451.
,, on the poisonous action of mer-
curic cyanide, 222.
Pelletier and Cahours on the solubility
of strychnine, 327.
„ and Caventou on the solubility
of brucine, 349.
„ and Thiboumeiy discover
pseudomorphine, 323.
INDEX.
761
Peunavaria on a case of poisoninc by oel
blood, 489.
Pentamethylencdiamine. See Cadaverine,
Pental, 170.
Pentane, 170.
Peptotoxiiie, 524.
Pereirine, 363.
Perls on the lungs in phosphorus poison-
ing, 240.
Pemn, Alcohol in the brain, 146.
Personne's method of estimating mercury,
685.
Pesci and Stroppa on the urine in phos-
phorus poisoning, 246.
Petrol, 135.
Petroleum, 135.
„ etlier, 135, 136.
,, Poisonous effects of, 136.
,, Sei>aration of, 137.
,, spirit, 135, 136.
Petromyzon Huviatilis, 489.
Pottenkofer on cantliaridcs in blood, 496.
„ on the solubility of mor-
phine, 296, 297.
,, ,, solubility of strych-
nine, 327.
PfaflTs prussic acid, 203.
Pfeitfer*s (E.) experiments on animals
with oxalic acid, 537.
Phallin, 429.
Phasco-lunatin, 204.
Phenic acid. See Carbolic add.
Phenol. See Carbolic acid,
Phenylaniinoaceto nitrile, 223.
Phenylenediamine, 40.
Phenylhydrazine, 40.
Phenylic alcohol. See Carbolic acid.
Phenyl sulphate of iK)tash, Sei)aration of,
from urine, 191.
„ „ Tests for, 191.
Phenyl sul])huric acid, 184.
Phi})son, Active principles of Agaricus
niber, 430.
Phisalix and G. Hertrand on bufonin^
485.
,, and r;. Bert rand on the poison
of the common viper, 504.
Phloroghicin, 34.
Phosphinc, 225, 235.
Phosphomolybdic acid reagent, Pro|»ara-
tion of, 249.
,, ,, Colour reaction
with alkaloids,
260.
Phosphoratcil oil, 226.
Phosphorus, 5, 224-274.
,, Antidote for |K)i8oning by,
235, 729.
,, Chronic poisoning by, 234.
,, Detection of, 241.
,, Estimation of, 246.
„ Fatal dose of, 229.
„ matches and vermin-paste,
226.
Phosphorus, Medical preparations of, 226.
,, poisoning. The blood in,
235.
,, ,, DifTerenoe be-
tween yellow
atrophy and
fatty liver, 241.
„ „ Effects of, 229,
232.
,, „ Se(juele to, 232.
,, ,, Unnein, 246.
,, ,, When symptoms
commence, 232.
,, Post-mortem appearances
after poisoning oy, 237-
241.
Properties of, 224.
,, Statistics of |x>isoning by,
228.
,, Time after which it may be
recognised in dead bodies,
247.
,, Time of death after taking,
232;
,, Treatment in poisoning by,
(App.)729.
,, Urine in poisoning by, 234,
246.
,, vajwur. Poisoning by, 232.
Phospho-tungstic acid reagent, 261.
Phosphurett^ hydrogen, 226.
Photogen, 136.
Physostigma faba, 409.
Physostigmine, 409-413.
,, Effects on animals, 411
,, „ man, 412.
,, Fatal dose of, 413.
,, Pharmaceutical prepara-
tions of, 411.
,, Physiological action of,
412.
, Poisoning by, 412.
,, Post-mortem appearanceb
after, 412.
,, Properties of, 409.
,, Sejiaration of, from
organic matter, 412.
, S])ectrum of colour re-
actions, 68.
„ Tests for, 410.
,, Treatment in i>oisoning
^. . .. .« by,(App.)722.
Picnc acid and Picrates, 470.
„ Effects of, 470.
Tests for, 471.
Picrotin, 466, 467.
Picrotoxin, 465-469.
,, Effects on animals, 467.
,, ,, man, 468.
,, Fatal dose of, 467.
,, Melting and subliming
temDeraturw, 262.
„ Physiological actioD, 468.
,, Propertiee of, 466.
762
INDEX.
Picrotoxin, Separation of, from organic
matter, 468.
,, Treatment in poisoning by,
(App.)730.
Picrotoxinin, 466, 467.
Pica* tongues. Poisoning by, 630.
Pilocarpine, Melting and subliming
temperatures, 262.
, , Treatment in poisoning by,
(App.)730.
Pilula asiatica, 553.
,, hydrargyri subchloridi composita,
603.
,, plumbi cum opio, 618.
PinewoKxi test for carbolic acid, 187.
Piotrowski, G., on carbon monoxide in
blood, 63.
Piperidoaceto nitrile, 223.
Piperine, 260, 266.
Pirondi on the fatal dose of barium salts,
713.
Piturie, 283.
Platinic chloride reagent, 249.
Plenk on poisoning by sabadiUa powder,
407.
Plowright on a death from eating Agari-
cus phalloides, 430.
,, Oxalic acid and oxalates in
fungi, 533.
Plugge on the action of aconitine on
reptiles, 367.
Plumstead murder case, 631.
Pohl on the iioison of Synanceia brachio,
487.
Poison, Definition of, 20, 22, 23.
, , French law relating to, 22.
,, General method of search for,
48-56.
,, German statute relating to, 21.
„ lore, 1-13.
Poisons, Classification of, 23-29.
,, Statistics relating to, 29-32.
Polygallic acid, 450.
Pomeroy, A case of poisoning by chloro-
form, 165, 166.
Pommerais, Conty de la, 444, 446.
Popoirci's (H.) method of estimating
nicotine in tobacco, 273.
Poppies, Syrup of, 292.
Pork, Poisoning by, 629, 630.
Porta, J. Baptista, 10.
Porte, Effects of ferric chloride on
animals, 697.
Portsmouth cases of food poisoning,
630.
Posner, Effects of chromium compounds
on animals, 702.
Potash (potassa caustica), 122.
,, Carbonate of, 123.
,, Pharmaceutical preparations,
122.
,, Properties, 122.
Potassic bi(mromate, 701.
„ „ Use of, in arts, 702.
Potassic chlorate, 130.
,, ,, Detection and estiiiia-
tion of, 132.
,, ,, Effects on man, 131.
,, ,, Elimination of, 132.
„ ,, Experiments on ani-
mals with, 120.
„ „ Poisonous properties of,
130.
„ „ Uses of, 130.
,, chromate, 701.
,, cyanide. See Hydrocyanic eund,
„ ferro-cyanide, 221.
„ nitrate, 128, 129.
„ „ Post-mortem appear-
ances after poisoning
by, 130.
,, ,, Statistics of poisoning
by, 129.
,, ,, Treatment in poisoning
by, 728.
, , phenyl-sulphate, Separation from
urine, 191.
„ „ Tests for, 191.
,, sulphate, 128.
,, sulphocyanide, 222.
,, tartrate. Elimination of, 128.
„ „ Hydro-, 128.
,, ,, Poisonous action of, 128.
,, xanthogenate, 174.
,, -zinc ic^ide reagent, 251.
Potassium salts. Neutral, 128-134.
Pot-curare, 418.
Pouchet, Elimination of antimony, 610.
Poudre epiUtoire, 711.
'* Poudres de succession,** 12.
Poullson, Poisoning by male fern, 481.
Powell's balsam of aniseed, 292.
Power and Cambier, Active principle of
locust tree, 481.
Power, F. B. , and Lees, F. H. .. on a prussic
acid yielding glucoside, 204.
Praag, L. v., Action of aconitine on fish,
367.
,, Action of aconitine on
birds, 369.
Preyer on the action of hydrocyanic acid
on a rabbit, 210, 211.
,, separates curare alkaloids, 419.
Prichard, Mrs., poisoned by antimony,
607.
Priestley, Preparation of hydrochloric
acid, 97.
,, and Boussingault, Experiments
on the influence of mercurial
vapour on plants, 670.
Prochorow, Poisoning by Petromyzon
fluviatilis, 489.
Propylamine, 613.
Protocuridine, 418.
Proteroglypha, 498.
Protocuriue, 418.
Protocurarine, 418.
Protopine, 286.
INDKX.
763
Protoveratridine, 402, 404.
Prout, Hydrochloric acid in gastric
juice, 99.
Pnissic acid, 202. See Hydrocyanic
add,
,f Treatment in poisoning
by, (App.) 730.
Pseudaconitiue, 362, 363.
Pseadaconitines, 362, 363.
Pseudaconhydrine, 269.
Pseudo-hyoBcyamine, 377, 896.
Pseudo-jervine, 402, 404.
Pseudomorphine, 286, 298, 323.
Ptomaines. See Animal toxines.
Putrescine, 518.
Puff adder (Vipera arietans), 504.
Pyrethmm rosea as an insecticide, 45.
Pyro-catechin, Separation of, from urine,
184.
Pyrogallol, 34.
Pyrrol, 40.
QUEBRACUINE, 353.
,, spectrum of colour re-
actions, 58.
Quebracho bianco, 353.
Quillaja sapotoxin, 450.
Quillaiic acid, 450.
Quinidine, 265.
Quinine, 250, 265, 266.
,, Si>ectrum of colour reactions,
58.
Rabuteau on the poisonous proj)erties
of amyl alcohol, 148.
Radecki on the effects of cantharides,
493.
Rajpoots as takers of opium, 311.
Rattlesnakes, 503.
Raubenheimer, J. A., Case of phenol
poisoning, 180.
Rayner, Henry, Effects of lead on the
nervous system, 626.
Realgar, 551.
Red lead, 619.
Reece, Dr., on tlie imbibition of arsenic
after death, 590.
Reg. V. Masscy and FeiTaud, 477.
Reg. V. Moore, 677.
Reichard*s (C.) test for morphine, 301.
Reiche, Effects of sulphuric acid on
kidney, 91.
Reid, Dr., Cases of carbon monoxide
j^isoning, 69, 73.
Reinsch's test for arsenic, 584.
Rendle, Detection of arsenic, 581.
Resorcin, 36.
,, dimethyl, 36.
Retford cases of food poisoning, 530.
Rettgers, J. W. , on arsenic mirrors, 583.
Rejpold*8 gout specific, 423.
Rhigolene, 135.
Ribau on coriamyrtin, 409.
Richardson on blood, 65.
Richardson, Sir B. W., on bichromate
disease, 702.
,, ,, on methene
dichloride,
170.
,, ,, on mortality
from chloro-
form vapour,
156.
,, ,, on action of
amyl nitrite,
149.
,, ,, on dose of
chloral, 165.
,, ,, on effects of
turpentine,
140.
„ ,, on the poison-
ous proper-
ties of amyl
alcohol, 148.
Richardson's (Sir B. W.) experiment
with strychnine, 341.
Richet, M., on the toxic action of
strychnine, 337.
Richet's experiments with strychnine,
341.
Richter on the detection of strychnine,
345.
Riegler's reagent for blood, 60, 61.
Riemeron the post-mortem appearances
in silver nitrate poisoning, 660.
Riess, 0. L., Distinction between phos-
phorus poisoning effects and atrophy
of liver, 241.
Riner*s pnissic acid, 203.
Ringer, S., on the action of aconitine,
375.
,, and H. Saintsbury on neutral
alkali salts, 128.
,, and Murrell on physiological
action of gelsemine, 854.
Rinman's gi^n, 688, 693.
Ritter on the blood in phosphorus
poisoning, 235.
Roberts' test for morphine, 300.
Robertson, A., and Wynne, A. J., on
cases of poisoning by eating Phaseolus
lunatus, 213.
Robertson, Dr., on the effects of lead on
the sight, 627.
Robinia pseudo-acacia, 481.
Robiquet's pnissic acid, 203.
Roburite factories. Poisoning in, 199.
Roger on the effect of copi»er leguminate,
645.
Rogers (Leonard) on the poison of sea-
snake, 498.
Rohrig on the effects of oil of savin, 475.
„ on the excretion of milk dimin-
ished by chloiAl, 168, 194.
,, on the p^ysiol^^gioil ^
piorotozm, 468.
Boman knowledge of ]
764
INDEX.
Romellaere on the blood in phosphorus
poisoning, 235.
Roos, Separation of cadaverine, 516.
Rose on the effects of santonin, 454.
„ on the estimation of arsenic, 597.
Rosenstein's experiments on animals with
lead, 622.
Rosenthal and Krocker on action of
nicotine on the brain, 281.
Ross, Dr., on the poisonous effects of
dinitro-benzol, 199.
Rossbach, N. J., on Opalina ranarum, 44.
,, on the action of ergot,
464.
,, on the effects of colchi-
cine, 423.
Rouget, on the ellects of silver nitrate on
animals, 659.
Roussin, Effects of sulphate of zinc as a
poison, 690.
Roussin's crystals, 276.
,, test for purity of chloroform,
152.
Ruberine, 430.
Rubi-jervine, 402, 405.
Rusma, 551.
Russeirs viper (Duboia russellii), 504.
Rutter, Dr. J. T., on arsenic eating, 561.
Sabadilline, 401.
,, Sj)ectrum of colour rwic-
tions, 58.
Sabadine, 401.
,, SjKJctrum of colour reactions,
58.
Sabina communis, 475.
Saint Ignatius' bean. Extract of, 329.
Saintsbury, Toxic effects of the neutral
salts of the alkalies, 128.
Salamander, The {wison of the, 483.
,, The water, Poison of, 484.
Salerne, C, on the action of ergot, 464.
Salet, M., detection of phosphorus by
8j»ectroscoi)e, 243.
Salicin, Melting and subliming tempera-
tures, 262.
Salicylic acid, 36.
,, methyl, 36.
Salkowsky on the lessening of the alka-
loids of the blood, 88.
,, „ liver in phosphorus
poisoning, 240.
,, ,, i)Ost-mortem appear-
ances in antimony
poisoning, 610.
,, ,, separation of poison of
mussels, 526.
Salmon, Tinned, Poisoning by, 530.
Salzberger isolates protoveratridine, 404.
,, on rubi-jervine, 405.
,, on the melting-point of rubi-
jervine, 406.
Izberger's (6.) protoveratrine, 402.
Sal volatile, 118.
Samandaridin sulphate, 484.
Samandrin, 483.
„ sulphate, 488.
Samuel, S., Ol«ervations on local action
of ammonia, 124.
Sanarelli, G., on the poison of the
scorpion, 486.
Sand, H. J., and Hackford, J. EL, The
estimation of arsenic, 594.
Sanderson, Dr. Burden, on the action of
gelsemine on respiration, 855.
Sanguinarin, Spectrum of colour re-
actions, 58.
Sansom on deaths under chloroform
vapour, 169.
Santonin, 463-456.
,, Effects on animals, 454.
man, 454.
,, Fatal dose of, 454.
,, Poisoning by, 453.
,, Post-mortem appearances after
poisoning by, 455.
, , Proj)erties of, 463.
,, Separation of, from organic
matter, 455.
Sapindus-sapotoxin, 460.
Saponin, 450-453.
Effects of, 451, 452.
,, Identification of, 453.
, , Melting and subliming tempera
tures, 262.
,, Properties of, 460.
,, Separation of, 462.
Sa])onaria officinalis, 450.
Saprine, 522.
Saporubin, 450, 451.
Sarsaparilla-sai>onin, 450.
Sarsa-sai>onin, 450.
Sausages, Poisoning by, 530.
Sautesson, The poison of the Heloderma,
486.
Savin, Oil of, 475.
,, ,, Post-mortem appearances
after {toisoning by, 476.
,, ,, Separation and identifica-
tion of, 476.
, , Treatment on poisoning by, ( Ap^K )
781.
Scattergood on the toxic effects of silver
nitrate on man, 660.
Schaafs cases of camphor poisoning, 142.
Schacht's method of assaying opium, 288.
Schaueustein on a case of atropine poison-
ing, 385.
,, on a case of strychnine-
laudAnum duplex poison-
ing, 336.
,, on a case of suicide by
chloroform, 167.
,, on poisoning by hellebore,
447.
,, on strychnine in the urine,
334.
INDEX.
765
Schanenstein on the statistics of strych-
nine poisoning, 332.
ff on undissolved strychnine
in the stomach, 342.
Schautfele on the action of organic fluids
on zinc, 688.
Scheele killed by prussic acid, 207.
Scheele's green, 555.
,, prussic a<:id, 203.
Schcibler*s process for separating alka*
loids, 256.
,, reagent for alkaloids, 251.
Scherer*8 test for phosphorus, 245.
Schindelmeiser, J., on the solubility of
mort)hine, 297.
Schindlcr on codeine in opium, 317.
SchlimjKirt on the solubility of morphine,
297.
,, on the solubility of strych-
nine, 327.
Schmidt, Hydrochloric acid in gastric
iuice, 99.
„ on hyoscine, 895.
Schmidtmann on |)oisoning by mussels,
526.
Sohmiedeberg on aniline poisoning, 284.
,, on digitalin, 435.
,, on the poisonous action of
chloroform, 154.
, , on the poisonous glucosides,
445.
,, on the active principles of
oleander leaves, 448.
,, on the physiological action
of atropine, 389.
,, and Harnack on nmscarino,
428.
,, and K()])i)o isolate muscar-
ine, 428.
Schmiedel)erg*s digitonin, 432.
,, method of estimating
chloroform, 161.
S<»honl)ein on the action of pnissic acitl
on the blood, 209.
,, on the oxidation of arsenical
stains, 583.
Schr.nbein's test for HON, 216, 217.
Schraeder's j»russio acid, 203.
Schraube, 0.. Statistics of phosphorus
|K)isoning, 228.
Schn)fr on the (Mst- mortem appearances
after i»oisoning by colchicine,
425.
„ on }K>isouing by colchicine, 424.
SchrofTs antidote for physostigminc,
412.
Schuchardt, Effects of jihosphorus on the
blood, 235.
Schulcr on the action of strychnine,
338.
Schultzen, Secretion of sulphuric acid,
95.
Schultzen, O., and 0. L. Riess, on fatty
liver in phosphorus poisoning, 241.
Schultzen, 0., and 0. L. Rieas, on the
urine in phosphorus poisoning, 234.
Schiilz, Penetrability of carbon mon-
oxide, 75.
,, and Praag, Action of aconitine
on fish, 367.
Schulz(H.)and Mayer's experiments on
the oxalic group of poisons, 545.
Schulz, W. von, on saporubin, 451.
Schulze's reagent for alkaloids, 251.
Schumacher and W. Juny*s method of
detecting mercury, 684.
Schumm, 0. , on the detection of mercury,
683.
Schiitte, W., on the alkaloids in the
belladonna plant, 378.
Schweinfurt green, 555.
Scillain or sculitin, 448.
Scillotoxin, 440.
Sclererythrin, 459.
Sclerocrystallin, 459.
Scleroidin, 459.
Scleromucin, 457.
Sclerotic acid, 458.
Sclerotium clavus, 456.
Scolosuboif on the localisation of arsenic
in the body, 586.
Scopola carmolica, 391.
Scopolamine, 378, 395.
Scorpio euro})8BUS, 486.
Scorpion, The })oison of the, 486.
Sea-snakcH (Hydr«>phinie), 498.
Sea-hare, 3.
Secalin -toxin, 458.
Sedgwick on the sym])toms of poisoning
by cytisine, 400.
,, on the effects of cantharides,
495.
Seeliger, Toxicity of copier oleates,
639.
Seibert and Kraft's spectroscope, 57.
Seidel on the action of hydrocyanic acid
on a man, 211.
,, on the etfects of mercurial vajwur,
671.
,, on ])ost-morteni api>earancea after
alcoholic poisoning, 145.
Selmi on the urine in phosphorus {Kuson-
ing. 246.
Selmi's process for S4>]Kirating alkaloids,
253.
Senegin, 450.
Siebold, Destruction of organic matter,
52.
Siebold's test for morphine, 302.
Siem, Paul, on the motion of alum salts
on annuals, 708.
Sicveking (m the effects of santonin,
455.
Silico-tungstic acid as a reagent for
alkaloids, 250.
Silver, 657-662.
,, Chronic )>oisoning by salts of, 060.
,, chloride, 657.
766
INDEX,
Silver ^anide, 222, 661.
„ Detectioii of, 661.
„ Doses of salts of, 659.
,, Use of, in the arts, 658.
,, nitrate, 658, 661.
„ „ Deaths from, 660.
„ „ Effects of, on man and
animals, 659, 660.
,, Tests for, 661.
„ oxide, 658.
,, Post-mortem appearances in cases
of poisoning by salts of, 660.
,, Separation of, 661.
„ salphide, 657.
Sippell, Toxicity of cryptopine, 323.
Sjokviflt's method of estimating HCl in
stomach, 107.
Smith, Angus, on chlorides in plants,
108.
Smith, F. J., on a case of aniline poison-
ing, 285.
Smith, R., on a case of poisoning by
petroleum, 137.
Smith, T. and H. , discover cryptopine,
323.
„ „ on the change of ferric
hydrate to oxy-
hydrate, 577.
Smith, Dr. Watson, on a case of poison-
ing by chromate of lead, 704.
Smoier, 0., on the urine in sulphuric
acid poisoning, 95.
Snakes, Bite of. Treatment in poisoning
by, (App.)731.
„ Poisonous, 498-504.
Snell, Simeon, on the poisonous effects of
dinitro-benzol, 199.
Snow, Dr. , on a case of poisoning by lead
carbonate, 622.
Soap-pill, The compound, 291.
Soda, Caustic, 123.
SodaB carl)onas, 1 23.
,, ,, exsiccata, 123.
Sodic cyanide, 221.
„ nitrate, 129.
Sodium bicarbonate, 123.
„ hydrate, 123.
,, nitro-prusside, 223.
„ salts, Neutral, 127-134.
Sokoloff, N. , on separation of HON from
organic matter, 218, 219.
Solanacew, Alkaloids of, 377.
Solanine, 250, 396, 398.
,, Melting and subliming tempera-
tures, 261.
,, Poisoning by, 398.
„ Properties of, 397.
,, Separation of, from organic
matter, 398.
, , Spectrum of colour reactions, 58.
„ Tests for, 397.
,, Treatment in poisoning by,
(App.)731.
Soianidine, 397.
Solannm dulcamara, 396.
,, niffrum, 896.
„ taberosum, 396.
Somoform, 170.
Sonnenschein on a case of nicotine
poisoning, 279.
,, on a case of poisoning by
hyoacyamine, 395.
„ on poisoning by ferro-
cyanide, 221.
,, on the detection of
phosphorus, 242.
,, on detection of phos-
phorus long after death,
247.
,, on the estimation of phos-
phorus, 246.
,, on the imbibition of
arsenic after death, 587.
Sophora tomentosa and speciosa, 398.
Sonbeiran on the bitter taste of brucine,
349.
Sparteine, 263, 264, 284.
Spartium scoparium, 284.
Spectroscope as an aid to the identifica-
tion of poisons, 56.
Spectroscopic appearances of blood, 60.
Spectrum of phosphorus, 244.
Speichert, Case of arsenic poisoning, 573.
Spermoodia ciavus, 456.
Sphacelic acid, 465.
Sphacelo toxin, 458.
Spiders and insects, Poisonous, 489-497.
Spiritus ammonias aromaticus and fccti-
dus, 117.
Stadeler*s fuchsine test for alcohol in
chloroform, 152.
Stadelmann on ingestion of oxybutyrio
acid, 88.
Stadelmann's experiments on animals
with arsine, 549.
Stadthagen and Brieger on the isolation
of animal toxines, 510.
Stannius on the influence of digitalis on
the heart, 440.
Starling, E. H., and Hopkins, F. Q., on
the urine in phosphorus poisoning, 234.
Stas separates nicotine in the Fougnies
case, 278.
Stas-Otto process for separating alka-
loids, 252.
Statira, Poisoning of, 6.
Steinfeld, Toxic effects of bismuth, 653.
Stevenson, T., on the antimony found in
the Chapman case, 609.
,, on carbon monoxide in
blood, 63.
,, on dangerous doee of
nitro-b«nzene, 196.
,, on poisoning by water
gas, 72.
,, on the post-mortem ap-
pearances after poison-
ing by lead, 632.
INDEX.
767
Stevenson, T., and Dupr^, Separation of
aoonitine, 876.
Stevenson, Dr. T., and Dr. Fagge, Action
of digitalin on frog's heart, 442.
Stibine, 614.
Stillmark on the toxalbumin of castor-
oil seeds, 478.
Stockmann and Dott on the physiological
action of morphine, 805.
Stolnikow, 86.
Stramonium extract, 880.
,, Treatment in poisoning by,
(App.)731.
Stranssmann and Schulz, Experiments
on CO, 76.
Strophantin, 440, 447.
,, Treatment in |>oisoning by,
(Api).) 781.
hispidus, 447.
Strophanthus hispic
Stroppa on phosphine in the urine,
246.
Strychnine, 250, 264, 265, 266.
„ acetate, 328.
,, Action of, on animals, 387.
,, ,, man, 338.
,, chromate, 328.
,, Diagnosis of poisoning by,
340.
,, double salts, 329.
,, Elimination of, 344.
,, Fatal dose of, 384.
„ in atropine. Test for, 383.
, , in brucine, Detection of, 33 1 .
„ iodide, 329.
,, Melting and subliming tem-
peratures, 261.
nitrate, 328.
,, ,, Fatal dose for
rabbits, 361.
,, not destroyed by putre-
faction, 345.
,, Pharmaceutical preparations
containing, 329.
,, Physiologic^ action of, 340.
,, ,, test for, 347.
„ Post - mortem appearances
after poisoning by, 341.
,, Properties of, 326.
,, Quantitative estimation of,
348.
,, Separation of, from organic
matter, 342.
, , Spectrum of colour reactions,
58.
,, Statistics of poisoning by,
332.
,, sulphate, 828.
,, sulpho-cyanide, 329.
,, Symptoms of poisoning by,
338.
„ Tests for, 346.
„ trichloride, 329.
,, Treatment in poisoning by,
342, (App.)731.
Strychnos castelnaca, 418.
,, colubrina, 826.
„ ignatius, 326.
„ nnx vomica, 326.
„ tieut^, 326.
,, toxifera, 418.
Strove on the detection of HON long
after death, 220.
Stuart's (Anderson) experiments on
nickel and cobalt salts, 693.
Substituting poisons, Loew's, 41.
Succus conii, 270.
Su^r of lead, 617, 633.
Suicide by poison, 2.
Sulphsemoglobin, 61, 62.
Sulphates in sulphuric acid poisoning,
96.
Sulphides of metals, Identification of,
612.
Sulpho group, 41.
Sulphonal, 37, 171.
Sulphones, 171.
,, Separation and identification,
172.
Sulphuretted hydrogen. See Hydric
sulphide.
Sulphuric acid, 81-97.
„ ,, Aromatic, 82.
„ ,, Blood in poisoning by,
96.
„ ,, Chronic poisoning by, 92.
„ ,, Detection and estimation
of, 93-97.
„ „ Excretion of, 94,
,, ,, Fatal dose of, 86.
,, ,, Local action of, 85.
,, ,, Museum specimens of
pharynx, gullet, etc.
after poisoning by, 92.
,, ,, Nordhausen, 82.
,, „ Poisoning by, 83.
,, ,, Post-mortem appearances
after poisoning by, 90.
,, ,, Properties, 81.
,, ,, Punfication from arsenic,
682.
,, „ Spots of, on organic
matter, 86, 87.
,, ,, Statistics of ]K)isoniug by,
82.
,, ,, Symptoms of poisoning
by, 87-89.
,, ,, Treatment of poisoning
by, 89.
„ anhydride, 82.
Sulphur trioxide, 82.
Superbin, 440.
Suppositoria plumbi composita, 618.
Surucucu (Lachesis muta), 503.
Susotoxine, 528.
Swieten on the non-fatal dose of sugar
of lead. 633.
Synanceia brachio, 487.
Syringin, 450.
768
INDKX.
Tauaea, 6., on tetrodon poison, 487.
TakmhAshi, D., and G. Inoko, on tetrodon
poison, 487.
Tamus communis, 481.
Tanghinia venenifera, 440.
Tanqueril on the etTects of lead poison-
ing, 625, 626.
Tanret, C, on the active principles of
ergot, 457.
Tar acids, 174-193, 449.
Tarantula, 490.
Tanlieu on phosphorus }K>isonin^, 237.
,, on the action of digitalis on
man, 436.
,, ,, eflfects of cantharides,
495.
,, ,, eiTtiCts of phosphorus,
229.
,, ,, nervous form of arsenic
poisoning, 568.
,, and Boussin on a case of poison-
ing by zinc, 690.
Tardieu's case of prussic acid poisoning,
207.
Tartar emetic, 601.
„ ,, Antidotes for, 610, 720.
,, „ Effects of, on animals, 605.
,, ,, ,, on man, 606.
,, ,, Estimation of, 601.
,, ,, Treatment in poisoning
by,(App.)720.
„ Salt of, 123.
Tartarated antimony. See Tartar
emetic,
Tartarate of potash and antimony. See
Tartar emetic.
Tartaric acid, Treatment in |K>isoning by,
(App.)732.
Tartra on gas formation in nitric acid
|K>Lsoning, 112, 113.
Tartra*s treatise on nitric acid ])oisoning,
111.
Taube on ergot epidemics, 461.
Taxine, 416, 417.
,, Effects on animals, 416.
man, 417.
,, Poisoning by, 416.
,, Post-mortem ap]>earances after
poisoning by, 417.
,, Properties of, 416.
Taylor, A. S., A case of alcohol poison-
ing, 144.
, , A case of ammonia }>oison-
ing, 120.
,, A case of antimony
chloride poisoning, 61 1 .
,, A case of arsenic poison-
ing, 563.
,, A case of carbonate of
])ota8h ()oisoning, 125.
„ A case of chloroform
poisoning, 155.
,, A case of coniine j)oison-
ing, i.'71.
TkyloT„ A. S., A CAM of hydiic salphida
poisoniiiff, 79.
A case of hydrochloric
acid poiBonin^, 103.
A case of merconc chloride
poisoning, 675, 676.
A case of morphine
poisoning, 309.
A case of naphtha poison-
ing, 188.
A case of nicotine poison-
ing, 279.
A case of nitro-benzene
poisoning, 194.
A case of oxalic acid
poisoning, 539.
A case of fietroleum
poisoning, 137.
A case of phosphorus
poisoning, 237.
A case of prussic acid
poisoning, 213.
A case of tartar emetic
poisoning, 606.
A case of taxine poison-
ing, 417.
Cases of turpentine poison-
ing, 140.
Cases of white precipitate
|)oisoniug, 677.
on chronic poisoning by
copper, 648.
on chronic lead poisonine.
629. *
on the action of chloro>
form, 154.
on the effects of digitalis
on man, 437.
on the effects of oil of
savin, 475.
on the fatal dose of
cantharides, 498.
on the fatal dose of
colchicine, 423.
on the fatal dose of oxalic
acid, 535.
on the fatal dose of prussic
acid, 208.
on the fatal dose of
strychnine, 836.
on the minimum lethal
dose of sulphuric acid,
85.
on the post-mortem ap-
pearances after aconi-
tine poisoning, 376.
on the post-mortem ap-
pearances after alcoholic
poisoning, 145.
on the solubility of
arsenious acid, 547.
Poisoning by nitric acid
vapour. 111.
Teichmann's crystals, 63.
^^^^p 769 ^^^1
Teilleus^Tbe active principles of Lath jrm
Thudiehuni on examination of urine in ^^^^^|
ntiTtu, 480,
carbolic a<^id poisoning, ^^^^|
TirebeBthetie, 1S$,
^^^H
Terpenes, 13$.
ou the excretion of alcohol, ^^^^^|
Tnachemftcher arnJ Smith** method of
^^^H
i«Baying opium ^ 2S7.
,i. on the excretion of eulphunc ^^^^^|
Tetanic noid test for morphine^ 30 1«
acid, ^^^^1
Tetaaine, 5t25.
on the uriue after taking ^^^^H
Ttstanotoiiue, 525,
carbolic acid, 135, ^^^^H
TetttTJU^ Polsonci connected with, 525«
Thnillier on the cauae of ergot epidemical ^^^^H
Tetra - methyl- diami no -phenyl - methane
^^H
Tidy, G. M., on a ease of poisoning by ^^^^H
test for lead, 63ft,
b&hum niimte, 714. ^^^^H
Tetrodoa, 487.
on the comiHssittoo of ^^^^^H
arsenical violet [Hiwderf ^^^^H
Tetrodonic acid, 487,
Tetrode nin, 487.
^^^1
Tetrooal, 17 L
Eaaction with old blood- ^^^^H
n 37.
fltain^ ^^^^H
That^terg K,, Separation of helleborlu,
Tilluer, E., on the detection of HON long ^^^^|
440.
after death, 220, ^^^^1
Thallium, 707.
Tine turn veratri viriditt, 406. ^^^^|
,f Separation of^ 707,
Tu^ot on ergot epidemics, 461, ^^^^H
ThalUuui suits, Eflwts of, 707.
TfNid, The piaona of, 484. ^^^H
Tobaooo. See Nkoiine. ^^^M
Thebftine, 2*54, 266, 2BB,
K ,, m&dbi of, d'22.
Tobacco leav'es, Compoeiticn of, 273, 274. ^^^^H
^^^H MeUitig aod subliming tom-
emoke, Composition of^ 230. ^^^^|
^^^H pemtures, 261.
puisonijjg, 279, ^^^^^1
^^H Pro[>erti^^ of, Z22.
Totlaua, ^^^H
^^H Te#Ufor, 322.
To II ens, Karl, ou fatal doae of tar adds, ^^^^H
^^^H 1 1 nitrate^ Fatal doae for rabbits,
^^^H
^^V
Tolmatacheff on Che ix>iaotious action of ^^^^H
Thcine, 250, 26fi.
mercuric cyanide^ 222. ^^^^H
tj Melting and Biiblimiug tempera*
Toluyleuediamine, 40. ^^^^M
Tolylaminoa^eto uitrilea, 223. ^^^H
turea, 262,
Theobromine, 40, 41, 250^ 266.
Ttmlmrjucbe, M., Poisoning by wat^r ^^^^^|
ft Subliming temperature,
hemlock, 473. ^^^H
202.
Toxie action and chemical oomposition, ^^^^^|
TheraphosA airiculariai 489.
^^^H
,, hlondii, 490.
Tr^ube ou Ihe iutlaence of digitalis on ^^^^^|
1, javauen^is, 460.
the heart, 440, ^^^H
Tlievatia ueriifoJia, 440, 447.
Treatment in casea of poisoning. (A Dp, ) ^^^^^|
,, iccotli, 440.
^^H
Thevetin, 447-
Trenpel, Relation between toxicity and ^^^^^|
Thiboiimery, Proptirtiea of psetldo-
condition of moleeiOe, 35, ^^^^^|
morpbiu«, ^I'S,
TrtaeetiUi 37. ^^^H
ThompBon, W., on coptter in a water, 64 1.
,, on itn? solubility of
Trichlormorphiue, 305, ^^^^^|
Trie thy lamine, 513. ^^^^^|
ooi»per in oil, $^8.
Thompson^a experiniflDU ou auimalB with
TrigouoeephAltiA eontortus, 503. ^^^^H
oxalic acid, 536,
Trimeresurua, 503, ^^^^^|
, , hair destroyer, 7 1 L
Trimrtbylamliit', 513. ^^^^^|
Thoni apple, 379.
TrimetUyloxyammonium hydrticblonde, ^^^^^|
Thome, L. T., mid JeHer^, E. H on the
purification of hydrochloric acid, SS2.
^^^H
Trioual, 37, 171, ^^^H
Thome^a(L T,} method of purifying zinc,
Tritou erisUtUB, 434. ^^^H
6S0.
Tritopine, 235, 324. ^^^H
Thorpe, T. £., on carbon monoxide from
Trix!hL^i aodoe bicarbonati^i. 121. ^^^^H
buugen burner, 69,
Tr'^j^'Cocaiot], 356, ^^^^^H
^_ ,, Eetim*tionofCO, 76,
Tri>p:rolin test for mineral acid, 105, ^^^^|
^^H , , Lead in lead glaze, e22.
a.^Tmxi11inv, 356. ^^^H
^^^F ftlethod of estimating
iS-Truxilline, 356. ^^^H
^P ara«inic^ 592,
Tschif^h on chronic poiiioning bv copper, ^^^^H
^L Thudichmii on the elimioatton of leadj
^^^M
^^^ ess.
otk copper oleatoj 639. ^^^^^|
^^^^^
^^M
770
INDEX.
Tschirch on phyllocyanate of copper, 642.
,, on the toxic dose of copper, 646.
Tube-curare, 418.
Tubo-curariiie, 418.
Tungstic acid test for morphine, 301.
Tunstall on a case of chronic alkali pois-
oning, 126.
Turbith, 666.
Turner's yellow, 619.
Turpentine, Elimination of, 140.
Oil of, 189.
,, Poisonous effects of, 140.
,, Treatment in poisoning by,
(App.)732.
Tutin, 469.
Typhotoxine, 529.
Tyrosin in phosphorus poisoning, 246.
Tyrotoxicon, 527.
Udransky, L. v., and Baumann, K., on
the isolation of animal toxines, 510.
Uffelmann method of distinguishing be-
tween the acidity due to free and to
combined acids, 106.
Ulex europeus, 398.
Ullmann on the elimination of mercury,
679.
Unguentum antimonii tartarati, 602.
,, phimbi acetatis, 618.
,, ,, carbonatis, 618.
,, iodidi, 618.
,, veratrinae, 406.
Upas tree (Antiaris toxicaria), 445.
Uppmain's (J.) experiments on animals
with oxalic acid, 536.
Uranium, 710.
,, Detection and estimation of,
710.
Urechitoxin, 440, 449.
Urecthin, 440, 449.
Urine, Examination of, for sulphuric
acid, 94.
,, in phosphorus poisoning, 245.
Urobutylcnloral acid, 168.
Urochloral acid, 168.
Vacuum apparatus, 50.
Valentin, The poison of the scorpion, 486.
Valette's (Dr.) cases of arsenic poisoning,
551.
Vallance on the symptoms of poisoning
by cytisine, 400.
Van Kobell's test for bismuth, 655.
Vanadic acid test for morphine, 801.
Vapor conii, 270.
Vaughan on tyrotoxicon, 527.
Vauqueliu's prussic acid, 203.
Vas, F., on the composition of tobacco
smoke, 277.
Veal pie, Poisoning by, 530.
Vee on the extraction of physostigmine,
409.
,, on the fatal dose of physostigmine,
413.
Venetian poisoners, 9.
Venturoli on separation of HON from
organic matters, 219.
Veratralbine, 402, 406.
Veratridine, 401, 402, 403.
Veratrine, 250, 264, 266, 266, 401, 402.
,, Commercial effects on animmls,
407
,, Effects on man, 407.
,, Fatal dose of, 407.
,, Pharmaceutical preparatiaiis
of, 406.
,, Properties of, 406.
,, Separation from oi^gaDic
matters, 408.
,, Spectrum of colour reactions.
58.
,, Symptoms of poisoning by.
Tests for, 406.
,, Treatment in poisonine by
(App.)783.
Veratroidine, 402, 405.
,, Spectrum of colour re-
actions, 58.
Veratrum — Used by Romans, 4.
,, alba, 401.
,, sabadilla, 401.
,, viride, 401.
„ Old knowledge of, 4.
Veratrums, ThealkaloicUof the, 401-409.
Verdigris, 644.
Vermin killers, 332.
Vermin paste, 226.
Veronal, 172.
Veryken on destruction of organic
matter, 52.
Vidali's test for chloroform, 161.
,, ,, morphine, 301.
Vienna paste, 123.
Victor, li.. Action of sulphuric acid on
living animal tissues, 86.
Vigla on the mental effects of chloroform,
159.
Villiers, H., and Fa voile, M., Test for
hydrochloric acid, 105.
Villiers' method for destroying organic
matter, 53.
Vinum antimoniale, 602.
Vinvlamine, 41.
Violet powders. Composition of, 562.
Viper, The poison of the conmion, 604.
Viperid», 498, 503.
Viperinae (vipers), 498.
Viperin, 504.
Virchow on the post-mortem appearances
after phosphorus poisoning, 238.
Vitali, D., on arsenic in the urine, 677.
,, on the separation of digitozin
434.
Vitali*8 test for atropine, 382.
,, method of detecting cyanide of
mercury, 681.
Vivisection Act, 45.
INDBX.
;/'
Vagel on the excretion of lulphunc ftaid^
95.
Voiain and Liouville's ex|ienmcnta with
curare, 419.
V<iit on the ^ILmiriftdfin of merouty, 079.
J, ,, excr@tioD of morphine, 313.
Volatile matter^ Separation of, 49.
Von FnrLh, Epmepnrin, 5u6.
Vosaler, Fatal doae of iiicrotoxin, 467*
Vrewen, Distinction DetwoeD Lyofloya-
mine iLud atropine^ 383.
VuIpiEto, Thtf fioieon ot the water a&la^
mander, 484.
Wachhol^ itnd Lembergi^r, Eij^eri-
meuts on C0| 75.
Wall, Dr. A. T. r on the elfecta of oobn
poiBOQ ot] man, 501.
Waller, E. , on the eatimation of carbolic
acid, 191,
Wah's di^taletin, 43 S.
Wanklyn on the estimation of carbon
monoxide^ 7tj.
Ward's red pill, 604.
Warner on the fatal dose of atfychnine,
335, 336.
Wartmanti, Physiological effects of
aconitinep 375.
Water ^, 98, 72.
Water hemlock, i73.
t , Poet- mortem appvftnuacet
after poiaonuig hj,
474.
Watt^ J., on the effect of barium salti on
aninialfl, 71 L
Weehuizen*s (F.) test ftir HON, 217.
Weil and Meilmizen, Action of digitaHn
on rrog*g heart, 443,
Webke'a eiperimeati with aulphtirio
acid, 92.
Wei beck epidemic ot food pctB«)Eiiag,
630,
Weldou proceas for preparing bleaching
powder. 77,
Wenzef s ergotinine, 457*
,, ecboline, 457,
Werniek on the action of orgi>t, 464,
Weylj Isolation of tetanine^ 525,
WbaUey, J, C, cu edeeta of sul phonal,
171.
Wbitdiureh case^ of fx)d poLsoning, 530*
White lead, 619,
White oil, a liniment for homes, 117*
Wliitt% Prof. , on the poisonous effeetaof
dioitro-bento!, 199.
Wldte precipitate, S65, (J77,
White vitriol, 687,
Whilfllock, Dr.^ on jwiMining bj carbolio
acid lotion, 18Q.
Wigner, G. W. , and Harlaud, E, H., on
tiie composition of commcTcial cat'
bonate of le^d, 613.
Williams' appantoS) 45,
Wilson, Margaret, The uaae of Reg, u,,
424.
Wilifon, W. H,, on the poiaon of the
scorpion, 486,
Wiike, Lead (>oiBomng from, 622.
WiHBcl on the compoiition of nux vomica,
330.
Witkowftky, Physiological efVecta of
physosUgmiiie, 411.
Wittuiann, FurifiGatJon of Bolanitie, 3fi7,
WJttBtein on the solubility of atrychnine,
327.
Wittstock on the separation of colchicine,
426,
Woehler and Siebold, on the destruction
of organic matter, 52.
Wohler on aniygilalin, 204.
,, on the elimination of potassic
chlorate, 132.
Wolckenhaar on an alkaloid Eke luoo*
tine, 283,
W'ylflenBtein on the scopolamines, 396.
W oil as ton, Dr, C, Obaervatious on ergot
poisoning, 462,
Wolyerhampton cases of food poiaoning, '
Wo4.»d on the eatiiuation of arsenic, 597.
Woodland on the amount of opium in
laudanum, 290.
Wormley on the aolubility of stijchiiiiiet
327'
WoudretoUj Ckjnleseion of, 8,
Wright, A. , and A. F, LutT, on tbeeitrac
tton of veratnim alkaloids,
4Q1,
,, and A. F. LulT, onjervitieand
t»eeudo' lor vine, 404
,, and A, P, Luff, on rubi-
jernno, 405.
Wright, W. H,, on the poisonous effect*
of kati{to bite, 491.
Wumtienauer, Karl, on the electrolytic
estimation of bismuth, 857.
Wunderlich, C. A., on the appeatance of
the intestine after nitric acid poisoning,
Wynne, A. J,, Cases of poisoning by
hydrocyanic acid, 213,
Wyas, Oscar, A case of sulphuric acid
poisoning, 90,
,» on the liver in phospbofus
poisoning, 240.
It oti th e u rt lie t n p hoepb onis
poisonings 234.
«« on the urine in sulphuric
acid pon»oning, 95,
Xj^TttALtNE, 286.
Xanthine, 39, 40, 80,
XjAuthogeuio acid, 174.
Ysw (T^tii baecata), 416.
Yuiagi M. E, , on cephalopoda, 44«
772
INDBX.
Zalaokab' (0. ) antidote to nicotine, 288.
Zangrilli on tarantula poison, 490.
Zeisel on the constitution of colchicine,
422.
Zeisel, 8., and Wittman, J., on solanine,
897.
Zeisel's method for methoxyl groups,
268.
Ziegenbein, H., Experiments with digi-
toxin, 433.
Zinc, 686-693.
„ carbonate, 687.
„ chloride, 687, 690.
,, chromate, 688.
, , Detection of, in organic matter, 692.
,, Effects of, on animals, 689.
,, „ man, 689.
„ Fatal dose of, 689.
Zinc fever, 689.
„ green, 688.
„ in the arts, 688.
„ lactate, 688.
,, Museum specimens, illustrating
effects of, 691, 692.
,, oxide, 687.
„ sulphate, 687, 690.
„ sulphide, 687.
,, Pharmaceutical preparations of,
687.
„ Post-mortem appearances in pois-
oning by, 691.
,, purification from arsenic, 580.
,, Treatment in poisoning by, (App.)
733.
Zweifler on sulphates in newly -bom
infants, 96.
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