\ ■Cv~dN Columbia Winihtx^itf \^^5 in tiie Cit? of iSeto Horfe College of ^i)?£(ician£; antj ^urseonsi ^titxtntt %ihvavp MICRO-CHEMTSTRY OF POISONS, INCLUDING THEIR PHYSIOLOGICAL, PATHOLOGICAL, AND LEGAL RELATIONS; WITH AN APPENDIX ON THE DETECTION AND MICROSCOPIC DISCRIMINATION OF BLOOD: ADAPTED TO THE USE OF THE MEDICAL JURIST, PHYSICIAN, AND GENERAL CHEMIST. BY THEODORE G. WORMLEY, M.D., Ph.D., LL.D., PROFESSOR OF CHEMISTRY AND TOXICOLOGT IN THE MEDICAL DEPARTMENT OF THE rNIVERSITT OF PENNSTLTANIA. WITH NINETY-SIX ILLUSTRATIONS UPON STEEL. "Atto neiprjQ w&vra avdpiinoiOL fcMec -yivecdai. — Herodotus. SECOND EDITION. PHILADELPHIA: J. B. LIPPINCOTT COMPANY. 188 5. Copyright, 1886, by Theodore G, Woemi-ey. (SIEREQT YPERS andPRI NTE^RSl TO ifi^t WHO, BY HER SKILFUL HAND, ASSISTED SO LARGELY IN ITS PREPARATION, %\ih l^ohm ^ AFFECTIONATELY INSCRIBED. c:K Digitized by the Internet Archive in 2010 with funding from Open Knowledge Commons http://www.archive.org/details/microchemistryoOOworm PREFACE TO THE SEOOIS'D EDITION. On issuing this edition of the Micro-Chemistry of Poisons, nothing need be added in regard to its scope and design to what was said in the Preface to the former edition. The work has been thoroughly revised, and much enlarged in matter, especially by the addition of illustrative cases, largely American, and by new tests and methods of recovery of poisons from organic mixtures; and, also, by the addition of an entirely new chapter on Gelsemium poisoning, and an Appendix on the Nature, Detection, and Microscopic Discrimination of Blood. Among other subjects added might be mentioned Poisoning by Potassium Chlorate ; Post-Mortem Diffusion of Arsenic ; Arsenic in Medicines, in Fabrics, and in Glass;* Dragendorff's method for the recovery of Vegetable principles; Nature of Ptomaines; and the preparation, properties, and recovery of Jervine. The chemical nomenclature of the former edition has been en- tirely revised and made to conform with the more recent views of chemists on that subject. After due consideration, it was concluded to retain the English * The glass of some American beakers examined since the text on this sub- ject was in print contained 0.34 per cent, of metallic arsenic. 6 PEEFACE TO THE SECOND EDITION. system of weights for indicating the behavior of given quantities of the different poisons with reagents, since this system is much more familiar to lawyers likely to consult the work, and even to most American physicians at present, than the metric system. To the pro- fessional chemist it matters little which of these systems of weights is employed for this purpose. If the reader is more familiar with metric than with English weights, he need only, after reading the fractions employed throughout the work to indicate the amount of the poison or substance present, substitute the word solution for the word " grain," and bear in mind that, unless otherwise stated, the reaction refers to the behavior of about 0.0648 gramme (one grain) of the solution. Thus, for yto grain, read y^ solution. The various solutions mentioned throughout the text are equally readily obtained by either of these systems of weights, by dissolving, by the aid of an acid or alkali if necessary, one part (grain 'or gramme) of the substance in one hundred parts by weight of water, when what is known as a 1-1 00th solution will be obtained. Ten parts of this solution mixed with ninety parts of water will consti- tute a 1-lOOOth solution. And ten parts of the last-named solution with ninety of water will form a l-10,000th solution ; that is, one part by weight of this solution will contain 1-1 0,000th of its weight of the substance dissolved. In like manner solutions in any other relative proportion may be prepared. In determining the behavior of solutions of a substance with reagents, it is necessary to observe not only the degree of dilution of the solution, but also the quantity operated upon. Thus, for ex- ample, if in one instance only a single drop of a 1-lOOth solution is employed, whilst in another one hundred times that quantity of the solution is used, the precipitate, if any is produced, will be one hundred times greater in quantity in the latter than in the former instance, although the degree of dilution is the same in both in- stances. Similar results would be obtained from different quantities of like solutions of all strengths until the degree of dilution exceeded PREFACE TO TFIK SErOXD EniTIfjX. 7 the insolubility of the substance or compound produced or set free by the reaijent, when no quantity of the solution, no matter how great, would yield any precipitate wiiatever. Hence, before apply- ing reagents the solution to be tested should he concentrated as far as practicable with the application of the tests to be employed. Two new steel Plates, including twelve illustrations of micro- scopic crystals, have been added to the work. These illustrations, like those of the former edition, were drawn from nature and executed upon steel by her to whom the work is inscribed. A steel Plate showing the apparent size of the red corpuscles of the blood of six different mammals, under a power of 1150 diameters, has also been added. These latter illustrations were drawn on steel by my daughter, Mrs. J. Marshall, and are accurate, on the steel, within at most about 1-lOOOth of an incii. A chromo-lithograph of Blood-Spectra and some wood-cut illustrations have also been added to the work. The author would here ackuowledge his indebtedness to Dr, Leo Mees, formerly his assistant, for much valuable assistance in collecting, mounting, and in the measurement of the corpuscles of the various bloods herein considered. Uhivkksitt of Pbnsstlvania, Philadelphia, March, 1885. TABLE OF CONTENTS. INTRODUCTION. Micro-Chemistry of Poisons, Definition Application of the Microscope Import of the term Poison Causes modifying the action of Poisons 1. Idiosyncrasy 2. Habit 3. Disease Classification of Poisons Sources of Evidence of Poisoning I. Evidence from the Symptoms 1. The Symptoms occur suddenly . 2. They rapidly run their course . Diseases resembling Poisoning . Duties of Medical Attendant II. Evidence from Post-mortem Appearances . Appearances rarely characteristic . Irritant Poisons, usual effects of . Narcotic Poisons Narcotico-Irritants .... Appearances common to Poisoning and Disease Redness of the Stomach Softening of the Stomach Ulceration and Perforation Points to be observed in Post-mortem Examination III. Evidences from Chemical Analysis Importance of Chemical Evidence Substances requiring Analysis Precautions in regard to Analyses Failure to detect Fatal Quantity . Value of individual Chemical Tests Failure to detect Poison Of Chemical Reagents Of Chemical Apparatus ..... Qualifications of the Analyst .... PAQE 33 34 34 35 35 35 36 37 38 38 38 41 42 42 43 43 43 44 44 , 44 44 45 45 46 47 47 47 48 50 50 54 56 58 58 10 TABLE OF CONTENTS. I]SrORGAE"IO POISOI^S. CHAPTER I. THE ALKALIES: POTASH, SODA, AMMONIA. General Chemical Nature Physiological Effects Symptoms .... 1. Of the Fixed Alkalies 2. Of Ammonia Period when Fatal Fatal Quantity Treatment .... Post-mortem Appearances Nitrate of Potassium Chlorate of Potassium Tartrate, Sulphate, and Oxalate of Potassium Chemical Properties of the Alkalies Distinguished from each other Section I. — Potassium Oxide. General Chemical Nature .... Density of Solutions of Potassium Oxide Special Chemical Properties .... 1. Chloride of Platinum Test . 2. Tartaric Acid, and Sodium Tartrate 3. Picric Acid Other Eeagents .... Spectrum Analysis Separation from Organic Mixtures Quantitative Analysis ..... PAOE 61 61 62 62 63 64 65 66 67 69 70 72 73 73 73 74 75 76 78 80 81 82 83 84 Section II. — Sodium Oxide. General Chemical Nature Density of Solutions of Soda . Special Chemical Properties . . Coloration of Flame 1. Metantimoniate of Potassium Test 2. Polarized Light . Behavior with Picric Acid . " " Tartaric " . " " Platinic Chloride Separation from Organic Mixtures 84 85 85 85 85 87 89 TABLE OF CONTENT8. 11 Section III. — Ammonia. Genenil Cliemical Nutiiro Density of Solutions of Aminoniu . Special Cheniical Propcrtios . 1. Pliitinic Chloriflo Tost . 2. Turtiiric Acid and Tartrate o 3. Picric Acid 4. Nesslor's Test Mercuric Chloride Sonnenschein's Test Separation from Organic Mixtures Quantitative Analysis f Sodium PA 'IK 89 80 'M) !)0 01 02 93 05 95 96 96 CHAPTER II. THE MINEKAL ACIDS: SULPHUEIC, NITRIC, HYDEOCHLORIC. General Nature and Bffects 97 Section I. — Sulphuric Acid. History Symptoms Period when Fat;il . Fatal Quantity Treatment Post-mortem Appearances General Chemical Nature Density of Solutions of Sulphuric Acid Special Chemical Properties . 1. Chloride of Barium Test 2. Nitrate of Strontium . 3. Acetate of Lead . 4. Veratrine . Other Reactions . Separation from Suspected Solutions Contents of the Stomach From Organic Fabrics Quantitative Analysis . Section II. — Nitric Acid Symptoms Period when Fatal Fatal Quantity Treatment Post-mortem Appearances General Chemical Nature Density of Solutions of Nitric Acid 98 98 100 101 101 102 105 106 106 107 110 111 112 112 118 116 118 118 119 121 121 121 121 123 124 12 TABLE OF CONTEXTS. Special Chemical Properties 1. Copper Test 2. Gold Test . 3. Iron Test . 4. Indigo Test ■5. Brucine Test 6. ISTarcotine Test 7. Aniline Test Iodine and other Tests Separation from Organic ilixtures Contents of the Stomach From Organic Fabrics Quantitative Analysis . PAGE 124 125 126 127 128 129 131 182 133 134 136 136 137 Section III. — Hydrochloric Acid. Symptoms 138 Period when Fatal 139 Fatal Quantity 140 Treatment 141 Post-mortem Appearances . . . . . . . . . . 141 General Chemical Nature .......... 141 Density of Solutions of Hydrochloric Acid . . . . . . .142 Special Chemical Properties .......... 143 1. Silver Nitrate Test 144 2. Xercurous Nitrate ......... 14-5 3. Lead Acetate 14-5 Separation from Organic Mixtures ........ 146 Contents of the Stomach 147 From Organic Fabrics ......... 148 Quantitative Analysis . . . . . . . . . . .148 CHAPTER III. OXALIC AND HYDROCYANIC ACIDS AND PHOSPHOPvUS. Sectiox I. — Oxalic Acid. History .............. 1-50 Symptoms ............. 1-50 Period when Fatal '. . . .1-52 Fatal Quantity . . . . . . . . . .1-53 Treatment • .... 1-54 Post-mortem Appearances . . . . . . . . . .1.54 General Chemical Nature . . . . . . . . . . 155 Special Chemical Properties . . . . . . . . . .1-56 1. Silver Nitrate Test 157 2. Calcium Sulphate . . . . . . . . .1.58 3. Barium Chloride . . . 159 TABLE OF CONTENTS. 13 4. Strontium Nitrate 6. Lead Acetate 6. Copper Sulphate . Separation from Organic Mixtures Contents of the Stomach . The Urine Quantitative Anal3-sis . Section II. — Hydrocyanic Acid. History .... Symptoms Period when Fatal Fatal Quantity Treatment Post-mortem Appearances Chemical Properties General Chemical Nature Special Chemical Properties 1. Silver Nitrate 2. Iron Test . 3. Sulphur Test Relative Delicacy of these Tests Other Reactions . Separation from Organic Mixtures Examination for the Vapor Method by Simple Distillation Distillation with an Acid From the Blood and Tissues Failure to detect the Poison Quantitative Analysis . Section III. — PnosPHORrs. History ......... Symptoms Period when Fatal Fatal Quantity Treatment ........ Post-mortem Appearances ..... Chemical Properties ...... General Chemical Nature Solubility Special Chemical Properties 1. Mitscherlich's Method for Detection . 2. Hydrogen Method .... 3. Lipowitz's " . . . . Phosphoric Acid General Chemical Nature PAOB 160 IGl 162 102 164 166 166 167 168 172 173 174 175 177 177 178 178 181 184 186 187 187 188 188 189 191 192 192 193 193 195 196 197 198 199 199 200 201 202 205 207 207 207 14 TABLE OF CONTENTS. Special Chemical Properties .... 1. Silver Nitrate Test 2. Magnesium Sulphate . 3. Molybdate of Ammonium . Other Eeactions .... Separation of Phosphorus from Organic Mixture Mitscherlich's Method Lipowitz's Method . . Dusart's " Kecovery as Oxide of Phosphorus . Failure to detect the Poison . Quantitative Analysis PAGE 208 208 209 210 212 212 213 214 214 215 215 216 CHAPTER IV. ANTIMONY. History 217 Tartar Emetic 217 Symptoms 218 Period when Fatal 219 Fatal Quantity 220 Treatment 221 Post-mortem Appearances . . 221 General Chemical Nature 222 Solubility 222 Special Chemical Properties 223 1. Sulphuretted Hydrogen Test 223 2. Acetate of Lead 225 3. Zinc Test . . .225 4. Copper Test 226 5. Antimonuretted Hydrogen 227 Action of the Mineral Acids 231 " " Caustic Alkalies 232 Other Pveactions ' . . ' . . 233 Separation from Organic Mixtures " . . 233 From the Tissues 236 " " Urine . .237 Quantitative Analysis 238 CHAPTER V. APvSENIC. I. Metallic Arsenic. History and Chemical Nature 239 Physiological Effects 240 Special Chemical Properties 240 Compounds of Arsenic 241 TABLE OF CXJNTEXTh. 15 II. Arsenious Oxide. — Arsenious Acid History nnd Varictiis . Symptoms Period wlieii Fatal Fatal Quantity Treatment Post-mortem Appearances Antiseptic Properties General Chemical Nature Solubility Special Chemical Properties Of Solid Arsenious Oxide Vaporization . Sublimation Reduction Of Solutions of Arsenious Acid 1. Ammonio-Nitrate of Silver Test 2. Ammonio-Sulphate of Copper 3. Sulphuretted Hydrogen 4. Reinsch's Test 5. Marsh's Test Bloxam's Method 6. Bettendorffs Test Other Reactions . 1. Lime-water 2. Potassium Iodide 3. Copper Sulphate and Potassium Hydrate Separation from Suspected Solutions Vomited Matters Contents of the Stomach From the Tissues Fresenius and Babo's Method Method of Gautier " " Danger and Flandin " " Duflos and Hirsch By Distillation Boeke's Method . From the Urine Distribution of Absorbed Arsenic Failure to Detect the Poison Detection after Long Periods Post-mortem Diflusion of Arsenic Arsenic in Chemicals, Medicines, and Fabri " " Glass . Quantitative Analysis . fAOE •-'41 242 246 246 247 250 251 252 253 256 256 256 257 257 260 261 263 264 271 279 293 295 296 296 296 297 297 298 299 300 301 306 307 308 308 309 309 310 312 312 313 316 319 321 16 TABLE OF CONTENTS. III. Arsenic Oxide.— Arsenic Acid. General Chemical Nature Physiological Effects Special Chemical Properties . 1. Sulphuretted Hydrogen Test 2. Ammonium-Copper Sulphate 3. Silver Nitrate 4. Keinsch's Test 5. Ammonio-Magnesium Sulphate Other Eeactions . Quantitative Analysis .... PAGE 322 322 328 323 325 326 326 327 328 328 CHAPTER VI. MEKCURY. General Properties • ■ 330 Physiological Effects 330 Combinations • . . . . 330 Corrosive Sublimate • 331 Composition ........••• 331 Symptoms 331 Period when Patal .......-•■ 335 Fatal Quantity 335 Treatment • • ■ • • .336 Post-mortem Appearances 337 General Chemical Nature 339 Solubility ' • ■ • -339 Special Chemical Properties 340 In the Solid State 340 Of Solutions of Corrosive Sublimate 343 1. Ammonia Test ... '. 343 2. Potassium and Sodium Hydrates 344 3. Potassium Iodide 345 4. Sulphuretted Hydrogen 345 5. Stannous Chloride • .347 6. Copper Test . . ." • • 348 7. Silver Nitrate . 353 Other Eeagents • • ■ • • 354 Separation from Organic Mixtures ■ .354 Suspected Solutions . ■ 355 Vomited Matters . 356 Contents of the Stomach 356 From the Tissues . . .358 " " Urine 360 Failure to Detect the Poison .361 Quantitative Analysis '^"'^ TARLK OF CONTENTS. 17 CHAPTP]ll VII. LEAD, COPPEll, ZINC. Section I. — Lkad. History nnd Chomical Nnturp riiysiological Effects Acetate of Lead Symptoms Chronic Poisoning Period when Fatal Fatal Quantity Treatment Post-mortem Appearances General Chemical Nature Solubility Special Chemical Properties In the Solid State . Of Solutions of Acetate of Lead 1. Sulphuretted Hydrogen Test 2. Sulphuric Acid . 3. Hydrochloric Acid 4. Potassium Iodide 5. Potassium Chromate 6. Potassium Hydrate and A 7. The Alkaline Carbonates 8. Ammonium Oxalate . 9. Zinc Test . Other Pveagents . Separation from Organic Mixtures Contents of the Stomach From the Tissues The Urine Quantitative Analysis . . PA OP. ZP,?, 3G4 3G4 364 365 366 367 367 368 368 369 369 369 370 371 372 373 374 375 376 377 377 377 378 378 379 380 381 381 Section II. — Copper. History and Chemical Nature 382 Combinations ........... 383 Sulphate of Copper and Verdigris 383 Physiological Effects ........... 383 Symptoms ............. 384 Period when Fatal 385 Fatal Quantity . . 386 Treatment ............. 386 Post-Mortem Appearances .......... 386 2 18 TABLE OF CONTENTS. PAGE Chemical Properties ^°' In the Solid State • ^^'^ Of Solutions of Salts of Copper . . . ^87 1. Sulphuretted Hydrogen Test 2. Ammonia 390 3. Potassium and Sodium Hydrates 391 4. Potassium Ferrocyanide ^^^ 5. Iron Test ^93 6. Platinum and Zinc Test 393 7. Potassium Arsenite • • • • 394 8. Potassium Chromate .' ■ • • • 394 9. Potassium Ferricyanide 395 10. Potassium Iodide s . . • 395 Guaiacum Test , . . . 396 Detection of the Acid - • • 396 Separation from Organic Mixtures 396 Contents of the Stomach . . 397 Prom the Tissues 398 The Urine . . • • • 399 Quantitative Analysis . . 400 Section III. — Zinc. History and Chemical Nature 400 Sulphate of Zinc . . . . - 402 Chloride of Zinc . 402 409 Symptoms Treatment 405 Post-mortem Appearances . . . , • 405 Chemical Properties of Salts of Zinc . . .... • • .406 In the Solid State 406 When in Solution 407 1 . Sulphuretted Hydrogen Test 407 2. Potassium Hydrate and Ammonia 408 8. Potassium Perrocyanide 409 4. Potassium Ferricyanide ......•• 409 5. Oxalic Acid 410 6. Potassium Chromate ■ • 410 7. Sodium Phosphate 411 Detection of the Acid . . • • • ■ • ■ • 411 Sopiiration from Organic Mixtures ..... . • • ■ 412 Contents of the Stomach 412 From the Tissues . • ■ ••,-.■ ■ ■ • 413 .Quantitative Analysis • • , • . • • 413 TABLE OF CONTENTS. 1!) PA.RT SKCOND. VEGETABLE POISOIsrS. INTRODUCTION. PAOP. General Nature of Vegetable Poisons 417 Separation from Complex Organic Mixtures . . ... 418 1. Method of- Stas 418 2. Kodgers and Girdwood's Method 423 3. Method of Uslar and Erdmann 424 4. Process of Graham and Hoffmann ...... 426 5. Method by Dialysis 427 6. Dragendorff's Method 429 Ptomaines 431 CHAPTER I. VOLATILE ALKALOIDS: NICOTINE, CONINE. Section I. — Nicotine. (Tobacco.) History .... Preparation . Symptoms Period when Fatal Fatal Quantity Treatment Post-mortem Appearances General Chemical Nature Solubility Special Chemical Properties 1. Platinic Chloride Test 2. Corrosive Sublimate 3. Picric Acid 4. Iodine in Potassium Iodide 5. Auric Chloride . 6. Bromine in Bromohydric Acid 7. Tannic Acid Other Reagents . Separation from Organic Mixtures Suspected Solutions and Contents of the Stomach From the Tissues From the Blood General Method of Distillation 434 434 435 437 438 438 438 439 439 440 441 442 444 444 445 446 446 447 447 448 450 450 452 20 TABLE OF CONTENTS. Section II. — Conine. (Conium Maculatum.). History .... Preparation . Symptoms Treatment Post-mortem Appearances General Chemical Nature Solubility Special Chemical Properties 1. Auric Chloride Test 2. Picric Acid 8. Mercuric Chloride 4. Iodine in Potassium Iodide 5. Bromine in Bromohydric Acid 6. Silver Nitrate 7. Tannic Acid Other Keagents Fallacies Separation from Organic Mixtures PAGE 453 453 454 455 456 456 457 457 459 460 460 460 461 462 462 462 463 464 CHAPTER II. OPIUM AND SOME OP ITS CONSTITUENTS. I. Opium. History and Chemical Nature . 466 Symptoms 467 Period when Fatal . . .469 Fatal Quantity .470 Treatment .472 Post-mortem Appearances .......... 474 Physical and Chemical Properties . . 475 II. Morphine. History and Preparation 476 Symptoms 476 Period of Death, and Fatal Quantity 477 Treatment and Post-mortem Appearances . 480 General Chemical Nature 480 Solubility 480 Special Chemical Properties . . . 483 In the Solid State 483 Of Solutions of Salts of Morphine 483 1. Potassium and Sodium Hydrates . . . . . 483 2. Ammonia 484 3. Nitric Acid 485 TABLE OF CONTENTS. •21 4. Iodic Acid . 5. Ferric Chloride . 0. Sulpho-Molybdic Acid 7. Potnssium Iodide 8. Potnssium Chromiite . 9. Auric Chloride . 10. Platinic Chloride 11. Iodine in Potnssium Iodide 12. Bromine in Bromohydric Acid 13. Picric Acid 14. Chlorine and Ammonia Other Keugents . Kelative Value of the Preceding Tests l-AOK 48G 487 488 490 490 491 492 492 493 493 493 494 495 III. Meconic Acid. History ...... Preparation Physiological Effects General Chemical Nature Solubility Special Chemical Properties . 1. Ferric Chloride Test . 2. Lead Acetate 3. Barium Chloride 4. Hj'drochloric Acid 5. Silver Nitrate 6. Potassium Ferricyanide 7. Calcium Chloride Other Keagents . SEPARATION OF MECONIC ACID AND MOKPHINK FROM ORGAN Suspected Solutions and Contents of the Stomach Meconic Acid .... Morphine .... Porphyroxine .... Examination for Morphine alone From the Tissues ..... From the Blood The Urine Failure to Detect the Poison Quantitative Analysis of Morphine 495 495 496 496 496 497 497 499 500 501 502 502 502 503 IC MIXTURES. 503 504 506 509 .510 510 511 513 513 514 IV. Narcotine. History 515 Preparation 515 Physiological Effects 516 22 TABLE OF CONTENTS. PAGE Chemical Properties .......•••■ 516 1. The Alkalies and their Carbonates 517 2. Sulphuric Acid and Potassium Nitrate . . . • .518 3. Potassium Acetate 519 4. Potassium Chromate ......••• 520 5. Potassium Sulphocyanide 520 6. Auric Chloride • • • 521 7. Iodine in Potassium Iodide ....... 521 8. Bromine in Bromohydric Acid ,...-•• 521 9. Potassium Perrocyanide ......■• 522 10. Picric Acid 522 Other Eeagents . . . . . • • • . . 522 V. Codeine. History 523 Preparation .......•••••• 523 Physiological Effects 523 Chemical Properties 524 1. The Caustic Alkalies 525 2. Iodine in Potassium Iodide 526 8. Bromine in Bromohydric Acid • • 526 4. Potassium Sulphocyanide 527 5. Potassium Dichromate 527 6. Auric Chloride 527 7. Platinic Chloride • • • .528 8. Picric Acid • • 528 9. Nitric Acid and Potassium Hydrate 528 Other Eeagents 528 VI. Narceine. History and Preparation .....■■■■ k 529 Physiological Effects 529 Chemical Properties 529 1. Iodine in Potassium Iodide Test 531 2. Bromine in Bromohydric Acid 531 3. Auric Chloride 532 4. Platinic Chloride • .532 5. Picric Acid 532 6. Potassium Dichromate . . . •■ • • • • 532 Other Eeagents • • 532 VII. Opiantl. History . . . . . • 533 Preparation 533 Physiological Effects 533 Chemical Properties ... . , 533 1. Iodine in Potassium Iodide Test 534 TARLE OF CON I KM S. 23 PAor. 2. Bromino in Bromohydric Acid ...... 536 3. Sulphuric Acid and Ilciit ^SS Other Reagents •'jSO CHAPTER II T. NUX VOMICA, STRYCHNINE, BKUCINK. I. Nux Vomica. History and Composition .......... 537 Symptoms ............. 537 Period when Fatal 539 Fatal Quantity 539 Treatment 540 Post-mortem Appearances 540 Chemical Properties 541 II. Strychnine. History and Preparation 542 Symptoms ............ 543 Period when Fatal 549 Fatal Quantity .550 Treatment 552 Post-mortem Appearances 555 General Chemical Nature 557 Solubility 558 Special Chemical Properties ; . . 559 In the Solid State 559 Of Solutions of Strychnine . . 559 1. The Caustic Alkalies 561 2. Color Test 562 3. Potassium Sulphocyanide . . - . . . . . 575 4. Potassium Iodide 575 5. Potassium Bichromate . . . . . . . . 576 6. Auric Chloride 578 7. Platinic Chloride 579 8. Picric Acid 580 9. Corrosive Sublimate 581 10. Potassium lodohydrargyrate 581 11. Potassium Ferricyanide ........ 582 12. Iodine in Potassium Iodide 588 13. Bromine in Bromohydric Acid 584 14. Physiological Test 584 Other Reagents 586 Separation from Nux Vomica ......... 586 Suspected Solutions and Contents of the Stomach .... 587 Method by Dialysis 590 24 TABLE OF CONTENTS. From the Tissues The Blood rrom the Urine Failure to Detect the Poison Quantitative Analysis . III. Brucine. History and Preparation Physiological Effects General Chemical Nature Solubility Special Chemical Properties . 1. The Caustic Alkalies 2. Nitric Acid and Stannous Chloride . 3. Sulphuric Acid and Potassium Nitrate 4. Potassium Sulphocyanide 5. Potassium Dichromate 6. Platinic Chloride 7. Auric Chloride . 8. Picric Acid . 9. Potassium Ferricyanide 10. Iodine in Potassium Iodide 11. Bromine in Bromohydric Acid Other Keactions . Separation from Organic jVIixtures PAGE 590 593 596 597 600 600 601 601 601 602 603 603 605 605 606 607 607 608 608 609 609 609 611 CHAPTER IV. ACONITINE, ATEOPINE, DATUEINE. Section I. — Aconitine. (Aconite.) History and Preparation 613 Symptoms ............. 615 Period when Fatal 617 Fatal Quantity 618 Treatment 621 Post-mortem Appearances 623 Chemical Properties . 624 Solubility 625 Of Solutions of Aconitine 625 1. The Caustic Alkalies .626 2. Auric Chloride 626 3. Picric Acid . . .627 4. Iodine in Potassium Iodide 627 5. Bromine in Bromohydric Acid 627 Other Reagents 628 Fallacies of Preceding Tests • . .628 Physiological Test 628 TABI.E OF CONTENTS. 25 Separation from Organic Mixtures .... Siispcclod Solutions imd Contents uf the Stomaoli From tlio niodd PAOB '•.29 •;29 t;30 Skction [I. — Atropine. (Belladonna.) History ........ Preparation ..... Symptoms ....... Treatment ....... Post-mortem Ap]tt';n-aiR'o.< .... Chemical Properties ..... Solubility Of Solutions of Atropine .... 1. The Caustic Alkalies . 2. Bromine in Bromohydric Acid Test 3. Picric Acid 4. Auric Chloride .... 5. Iodine in Potassium Iodide Other Reagents .... Physiological Test Separation from Organic Mixtures From the Blood .... 631 631 633 638 639 640 640 641 641 641 642 643 643 644 645 645 647 Section III. — Daturine. (Stramonium.) History and Preparation ...... . 647 Symptoms . 648 Treatment : . .650 Post-mortem Appearances . 651 Chemical Properties . 651 Separation from Organic Mixtures .... . 652 CHAPTER V. VERATRINE, JERVINE, SOLANINE. Section I. — Veratrine. Jervine. (White and American Helle- bores.) History and Preparation 653 Symptoms. — Veratrum Album 656 Veratrum Viride 657 Veratrine 659 Treatment 660 Post-mortem Appearances 660 Chemical Properties 660 Solubility 662 26 TABLE OF CONTENTS. Of Solutions of Veratrine 1. The Caustic Alkalies . 2. Sulphuric Acid Test . 3. Auric Chloride . 4. Bromine in Bromohydric Acid 5. Iodine in Potassium Iodide 6. Picric Acid . 7. Potassium Dichromate Other Eeagents . Jervine, Chemical Properties In Solid State . Of Solutions of Jervine . Separation of Veratrine and Jervine from Organic Mixtures From the Blood PAGE 662 663 663 665 665 666 666 667 667 667 668 668 670 671 Section II. — Solanine. (Nightshade.) History .672 Preparation 672 Symptoms 673 Treatment 675 Post-mortem Appearances .......... 675 Chemical Properties " 675 Solubility 676 Of Solutions of Solanine 677 1. The Caustic Alkalies 677 2. Sulphuric Acid Test 678 3. Iodine in Potassium Iodide 679 4. Potassium Chromate ' • • • 679 5. Bromine in Bromohydric Acid . ... . . . 680 Other Eeactions 680 Separation from Organic Mixtures 681 CHAPTER VL GELSEMINE, GELSEMIC ACID. (YELLOW JESSAMINE.) History and Preparation . . ....... . 683 Gelsemine ........... 683 Gelsemic Acid 684 Physiological Effects 684 Symptoms 685 Period when Fatal 687 Fatal Quantity . 688 Treatment . . . . 689 Post-Mortem Appearances .......... 690 TAHLK OF CONIKNIS. ' 2ili ' IrXQK. Chemical Properties 'il^l I. Gelsemic Acid ...... . 09 1 Solubility . (;92 Chemical Reactions .... . 092 With Acids . 692 In Solution ..... . 693 II. Gelsemine . 694 Solubility . 695 Reactions in Solid State . . 695 In Solution . 696 1. Ammonia .... . 696 2. Picric Acid .... . 696 3. Iodine in Potassium Iodide . . 697 4. Bromine in Bromobydric Acid . 697 5. Auric Chloride . 697 6. Platinic Chloride . . 697 7. Mercuric Chloride . G97 Other Reagents . 697 Separation from Organic Mixtures . 698 a. Gelsemic Acid ..... . 698 b. Gelsemine . 699 From the Tissues . 699 From the Blood . 700 APPEI^DIX. BLOOD. PROPERTIES— DETECTION— DISCRIMINATION. . General Nature of Blood 701 Physical Characters Composition Coagulation Corpuscles Non-Nucleated 701 701 702 702 703 Nucleated 704 Action of Water and Reagents on Corpuscles Circular Corpuscles Oval " 705 705 706 White Corpuscles 706 Blood-Stains 707 28 TABLE OF CONTENTS. II. Chemical Tests for Blood 1. Heat 2. Ammonia ..... 3. Guaiacum Test .... 4. Hsemin Crystals .... Other Eeactions .... III. Optical Properties of Blood . Micro-Spectroscope Blood-Spectra .... Examination of Suspected Stains Fallacies ..... IV. Microscopic Detection and Discrimination Oviparous Blood .... Mammalian Blood Limit of Determining Differences By Unaided Eye . By Microscope Measurement hy the Microscope Average Size of Mammalian Corpusc Distribution for Measurement Uniformity in Size Table of Average Size Limit of Discrimination V. Examination of Dried Blood Liquids Employed Kesults Obtained Cases . Fallacies Location of Stains Blood-Suckincj Insects PA8E 708 708 709 709 711 713 714 714 715 718 720 721 721 723 723 723 724 725 728 728 729 733 735 737 737 738 739 739 740 741 ILLUSTRATIONS. Chromo-Lithooraph of Blood-Spectra. {Frontispiece.) UPON STEEL. PLATE I. Fig. L j^ grain Potassium Oxide, as nitrate or ctiloride, -|- Platinic Chloride. 2. -j^ grain Potassium Oxide, as nitrate, + Tartaric Acid. 3. ^-Q grain Potassium Oxide, as chloride, + Sodium Tartrate. 4. j^^ grain Potassium Oxide, as nitrate, + Picric Acid. 5. Y^TS grain Ammonia, as ammonium chloride, + Picric Acid. 6. tJ*j grain Sodium Oxide. + Picric Acid. PLATE IL Fig. 1. ^-yoiF grain Sodium Oxide, -\- Potassium Metantimoniate. " "^- Tff grain Sodium Oxide, -}- Tartaric Acid. " ^- ttjW grain Sodium Oxide, as chloride, -|- Platinic Chloride. " ^- 1^0 grain Sulphuric Acid, -|- Barium Chloride. " 5. Htdrofluosilicic Acid, -f -Sariwm CA^orirfe. " ^- TF(T g^^^^ Sulphuric Acid, +'S^^owi(iMW lYt^ra^e. PLATE III. ■Y^ grain Hydrochloric Acid, + Lead Acetate. TO'ws grain Oxalic Acid, on spontaneous evaporation. T^Vo" grain Oxalic Acid, -j- Calcium Chloride. yi^ grain Oxalic Acid, -{-Barium Chloride. " ^- TW grain Oxalic Acid, -\- Strontium, Nitrate. " ^- Tffrr grain Oxalic Acid, + Lead Acetate. PLATE IV. Fig. 1. xrj 00 grain Hydrocyanic Acid vapor, + Silver Nitrate. " ^- 1 6 6 ^0 6 grain Hydrocyanic Acid vapor, -f- Silver Nitrate. " ^- 1 0^0 grain Phosphoric Acid, + Ammonium, Magnesium Sulphate. " 4. Tartar Emetic, from hot supersaturated solution. " 5. Arsenious Oxide, sublimed. " 6. -j^ grain Arsenious Oxide, -{-Ammonium Silver Nitrate. 29 IG 1. 11 2. (1 3. Cl 4. 30 ILLUSTEATIONS UPON STEEL. PLATE V. Fig. 1. Y-Qo grain Arsenic Oxide, -\- A^jiTnonium Magnesium Sulphate. 2. Corrosive Sublimate, sublimed. 3. y^ grain Lead, -f- diluted Sulphu7nc Acid. 4. yig- grain Lead, -f- diluted Hydrochloric Acid. 5. ■ij^Vs' grain Lead, + Potassium Iodide. 6. Yo^o o' grain Zinc, + Oxalic Acid. PLATE VL Fig. 1. j^ grain Nicotine, -j- Platinic Chloride. 2. Yo^ grain Nicotine, -|- Corrosive Sublimate. 3. x^Vo grain Nicotine, -|- Picric Acid. 4. Conine, pure, -f- vapor of Hydrochloric Acid. 5. Yo^ grain Conine, -j- Picric Acid. 6. Y^ grain Morphine, -\- Potassium Hydrate. PLATE VIL Fig. 1. ^ho grain Morphine, -f- Potassium, Iodide. 2. j-Iq- grain Morphine, + Potassiw>n Chrom,ate. 3. Y^ grain Morphine, + Platinic Chloride. 4. ^^ grain Meconic Acid, -j- Barium Chloride. 5. Yho gi'^in Meconic Acid, + Hydrochloric Acid. 6. YTo grain Meconic Acid, -|- Potassium Ferricyanide. Fig. 1. 2. 3. 4. 5. 6. PLATE VII L yig grain Meconic Acid, -|- Calcium Chloride. ToVo grain Narcotine, -\- Potassium Hydrate. yip grain Narcotine, -f- Potassium Acetate. yig grain Codeine, -j- Iodine in Potassium Iodide. yi^ grain Codeine Iodide, from alcoholic solution, -i-g. grain Codeine, + Potassium Sulphocyanide. PLATE IX. Fig. 1. -j-^Q^ grain Codeine, + Potassium Dichromate. 2. yig- grain Codeine, -f- Potassium Iodide. 3. y-J^ grain Narceine, + Iodine in Potassium Iodide. 4. ^^ grain Narceine, -f- Potassium, Dichromate. 5. ^1^ grain Opianyl, ~\- Iodine in Potassium Iodide. 6. .^ig. grain Opianyl, + Bromine in Bromohydric Acid. PLATE X. J^IG. 1. .j^ grain Strychnine, -|- Potassium Hydrate or Annmonia. 2. j-ig grain Strychnine, + Potassium Sulphocyanide. 3. .^^ grain Strychnine, + Potassium Dichromate. 4. -^L^ grain Strychnine, + Potassium Dichromate. 5. ^^^ grain. Strychnine, + -^wric Chloride. 6. yJg-^ grain Strychnine, + Platinic Chloride. ILLUSTRATIONS UPON STKKF,. 31 TLATK XI. Fio. \. ^-^f^f^ giiiin Strychnine, + Picric Add. 2. .j-Jj grain Strychnine, -(- Corrosive Sublimate. 3. yjj grain Stkychnink, + Potassium Ferricyanide. 4. y^5j grain Stkychnink, -|- todine in Potassium Iodide. 5. 1^ grain Brucink, -}- Potassiuin Hydrate or Ammonia. 6. ^^ grain Brucine, -f- Potassium Sulphocyanide. PLATE XII. Fig. L yjj grain Brucine, + Potassium. Dichromate. 2. xA^Tf grain Brxtcine, + Platinic Chloride. 3. y-Ju grain Brucine, + Potassium Ferricyanide. 4. ^ijj grain Atropine, + Potassium Hydrate or Ammonia. 5. ^1^ grain Atropine, + Bromi^ie in Bromohydric Acid. 6. xryJwc gr^iii Atropine, -f- Bromine in Bromohydric Acid. PLATE XIIL Fiii. ]. yjjj grain Atropine, -j- Picric Acid. 2. yIt) grain Atropine, + Auric Chloride. 3. ^hf) grain Veratrine, + Auric Chloride. 4. ^^ grain Veratrine, + Bromine in Brom.ohydric Acid. 5. SoLANiNE, from alcoholic solution. 6. yi_ grain Solanine, as sulphate, on spontaneous evaporation. PLATE XIV. Fig. 1. j-^ grain Morphine, + Iodine in Potassium Iodide. 2. Y^jj grain Morphine, + Potassium lodohydrar gyrate. 3. Jertine, from ethereal solution. 4. .j^ grain Jervine, + Sulphuric Acid. 5. y-J-j grain Jervine, -}- Nitric Acid. 6. Jervine, from blood of cat. PLATE XV. Fig. 1. Gelsemine Hydrochloride. " 2. Gelsemic Acid, from ethereal solution. " 3. Gelsemic Acid, sublimed. " 4. -j-j^ grain Gelsemic Acid, -(- Sulphuric Acid, then Ammonia " 5. H^MATix Hydrochloride. " 6. H^MATiN Hy'drochloride, from -i^ grain of blood. PLATE XV L Fig. 1. Blood-Corpuscles of Man, x 1150 diameters. " 2. " " Dog, X " 3. " Mouse, X " 4. Ox, X ' • 5. " " Sheep, X '' (j. " " Goat, X MICRO-CHEMISTRY OF POISONS. INTEODUOTION. definition; application of the microscope IMPORT OF THE TERM POISON ; modifying circumstances — classification OF poisons — sources of evidence of poisoning: evidence from symptoms — from post-mortem appearances — FROM chemical ANALYSIS. By the terra Micro-Chemistry of Poisons, we under.stand the study of the cheraical properties of poisons as revealed by the aid of the raicroscope. Although the scope of the present work is not limited to this department of the subject, yet, as that branch of the science forms a main element of the treatise, we have designated it by that title. The instrument requisite for investigations of this kind may be comparatively simple ; and but little accessory apparatus will be re- quired. The stage of the instrument should be sufficiently large to receive a watch-glass having a diameter of not less than two inches. Object-glasses of only low power are usually required. Very often an amplification of from thirty to forty diameters will answer the purpose best, but more frequently, perhaps, a power of about seventy- five .will be the most satisfactory, while in some few instances an amplification of about two hundred and fifty will be required. The objectives best suited for these powers are the inch and a half, two- thirds inch, and one-fifth inch, respectively. In these investigations, as in all others with the microscope, the lowest amplification that will reveal the true character of the object examined will be the most satis- factory. A. polarizing apparatus will sometimes be necessary to deter- mine the true nature of an object ; and in some instances a micromete)' will be found useful to ascertain the absolute size of the object. 3 33 34 INTRODUCTION. In applying the microscope to the examination of the result of a chemical reagent upon a suspected solution, a single drop of the liquid, placed in a watch-glass or upon a glass slide, is treated with a very small quantity of the reagent, added by means of a pipette, and the mixture, with as little agitation as possible, transferred to the stage of the instrument. If, as is sometimes the case, the crystalline deposit produced by the reagent be readily broken up by agitation, the watch- glass containing the drop of fluid to be examined is placed on the stage of the instrument before the addition of the reagent. In many instances, as will be noticed hereafter, the formation of a precipitate is much facilitated by stirring the mixture with a glass rod. Should the mixture evolve fumes injurious to the object-glass, a flat watch- glass having a ground edge is selected, and this is covered by a piece of very thin glass. Any special directions in regard to the use of this instrument will be pointed out hereafter, as occasion may require. A Poison is any substance which, when taken into the body and either being absorbed or by its direct chemical action upon the parts with which in contact, or when applied externally and entering the circulation, is capable of j)roducing deleterious eifects. There is no doubt that all poisons are to a greater or less extent absorbed into the circulation. In fact, with most of them this is certainly a condition essential to the production of their effects ; yet it would appear that in the action of some substances, which produce local chemical changes, death, in some instances at least, can be referred only to the effects of the changes thus produced. The mineral acids and caustic alkalies are the principal poisons which have a direct chemical action upon the parts with which they are brought in contact. This action is due to a mutual affinity existing between the agent and the tissue. In this respect, the action of these substances differs from that of certain heated liquids, such as boiling water, which are inert at ordinary temperatures, but which, simply on account of their con- dition, induce a chemical change in the part to which they are ap- plied, without themselves being chemically concerned in the change. When applied externally, some poisons are absorbed by simply being brought in contact with the unbroken skin ; whilst others do not enter the circulation unless applied to an abraded or wounded surface. Poisons differ greatly in regard to the quantity necessary to prove injurious. Thus, the fiftieth part of a grain of aconitine has seriously endangered the life of an adult, while, on the other hand, an ounce of CAUSES MODIFYIN(t THE ACTION OF POISONS. 35 magnesium sulphate may generally be administered with impunity ; yet in large quantities the latter suhstanee has in several instances caused death, and is strictly a poison, although not commonly reputed as such. As yet we know of no substance that is poisonous in every proportion. Any of the most powerful poisons may be administered in certain quantities without producing any ai)preciable effect, and most of them may be so employed as to constitute valuable remedial agents. In medico-legal inquiries, the leading idea connected with the term poison is whether the given results are directly traceable to the substance and the intention with which it was employed. Poisons not only diifer from each other in regard to the quantity necessary to destroy, life, but the effects of the same substance may be much modified by circumstances, and even substances which to most persons are harmless may, on account of certain peculiarities of constitution, produce deleterious effects. Cau.ses which modify the effects of Po/son.s.— Among the causes which may modify the effects of poisons, may, in this connection, be mentioned Idiosyncrasy, Habit, and a Diseased State of the System. 1. Idiosyncrasy, or a peculiarity of constitution, may variously modify the effects of substances. Thus, in some persons ordinary medicinal doses of certain drugs, such as opium or' mercury, produce violent symptoms, and even death. In other instances, substances which to most persons are harmless, and even ordinary articles of food, produce symptoms of irritant poisoning. This has been ob- served in the eating of certain kinds of fish, honey, pork, veal, and mutton. In still another form of idiosyncrasy, there is a diminished susceptibility to the action of certain substances which to most per- sons are active poisons. This peculiarity of constitution is very rare, and is most generally observed in regard to the action of mer- cury and opium. Dr. Christison relates an instance in which a gentleman, unaccustomed to the use of opium, took without injury nearly an ounce of good laudanum. 2. Habit may render certain poisons harmless in doses which to most persons would prove rapidly fatal. The influence of habit is daily seen in the use of opium, tobacco, and alcohol ; and it is well known that certain other agents when administered medicinally, in frequently-repeated doses, after a time lose their ordinary effects. 36 rNTRODUCTio]sr. Persons accustomed to the use of opium have taken daily, for long periods together, quantities of laudanum that Avould prove fatal to several persons unaccustomed to its use. Although this influence has principally been observed, as remarked by Dr. Christison, in regard to the action of certain organic poisons, especially such as act on the brain and. nervous system, yet it seems now to be fully established that certain persons in Styria accustom themselves even to the eating of arsenic in doses of several grains daily, and continue the practice for many years without experiencing any of the usual eifects of the poison. The statements formerly made by Dr. Tschudi and others in regard to the existence of this practice have been dis- credited by most writers on toxicology ; but the accounts more re- centlv published by Dr. Roscoe, as quoted by Dr. Taylor [Jled. Jur., Amer. ed., 1861, 693), and the direct observations of Dr. Maclagan, of Edinburgh (Chemieal Xews, London, July, 1865, 36j, while on a visit to Styria, seem to leave no doubt whatever of its existence. In one of the cases observed by Dr. Maclagan, the individual, a muscu- lar young man, aged twenty-six years, swallowed, in connection with a very small piece of bread, five grains of genuine powdered arseni- ous oxide, or white arsenic, which he stated was about the quantity he was in the habit of taking twice a week. In the urine passed by this individual two hours afterward, as also in that passed after twenty-six hours. Dr. Maclagan detected a very notable quantity of arsenic. It is but proper to observe that the experience of most medical practitioners in the use of this substance does not accord with the results of this Styrian practice. 3. Disease. — In certain diseased conditions of the system, there is a diminished susceptibility to the action of certain poisons ; whilst in others, there is an increased susceptibility, even to the action of the same substance. Thus, in tetanus, hydrophobia, mania, and de- lirium tremens, quantities of opium which in ordinary states of the system would be fatal may often be administered with beneficial eifects. In a case of tetanus related by Dr. A\^atson {Praotioe of Physic), something over four ounces of laudanum was taken on an average daily, for twenty days ; after which the patient recovered. The same writer quotes another instance of the same affection, in which an ounce of solid opium was taken, in divided doses, daily, for twenty-two days. So also, in inflammation of the lungs, enormous doses of tartar emetic have been given with advantage. On the CLASSIFICATION OF I'OISONS. 37 other hand, in cases in which there is a predisposition to apoplexy, an ordinary dose of opium may cause death. In like manner, in certain diseases, there is an increased suscej)til)ility to the action of" mercury and dthcr minei-al suhstancps. Classification of Poisons. — Poisons may bo arranged, accord- ing to the symptoms they produce, under three classes, — namely, Ir- ritants, Narcotics, and Narcotico-Irritants. Since, however, there are many poisons the effects of which are subject to great variation, and others which according to their ordinary effects might with equal propriety be placed in one or another of these classes, this classification is open to much objection. Irritant Poisons, as a class, produce irritation and inflamma- tion of the stomach and bowels, attended or followed by intense pain in these parts, tenderness of the abdomen, and violent vomiting and purging, the matters evacuated being often tinged with blood. Some of the members of this class, such as the mineral acids and caustic alkalies, also possess corrosive properties, and accordingly occasion, in addition to the effects just mentioned, more or less disorganization of the mouth, throat, oesophagus, and stomach. The action of these substances, if not too dilute, is immediate, and is attended with a sense of burning heat in the parts with which they come in contact. When highly diluted, any of the corrosive poisons may act by simply inducing irritation and inflammation. The irritant poisons may be divided into three sections, according to the kingdom of nature to which they belong, — namely, mineral, vegetable, and animal. The first section is much the largest, and embraces, with the exception of some gaseous substances, all strictly inorganic poisons. Gamboge and cantharides are, respectively, ex- amples of the second and third sections. Narcotic or Cerebral Poisons are such as act principally on the brain and spinal marrow, more especially on the former. They induce headache, vertigo, stupor, impaired vision, delirium, insensibility, paralysis, convulsions, and coma. This class contains comparatively few substances, the principal of which are opium and hydrocyanic acid. Several of the poisonous gases belong to this class. Narcotico-Irritants partake, as indicated by their name, of the action of both the preceding classes. Thus, they may produce, as a result of their irritant action, nausea, pain in the stomach, 38 INTRODUCTION. vomiting, and purging; and as a result of their action on the nervous system, stupor, delirium, paralysis, coma, and convulsions. Some of them, however, do not usually produce well-marked symptoms of irritation ; and all of them produce their most marked effects on the nervous system. A few, such as strychnine and brucine, act chiefly on the spinal cord, and produce violent tetanic convulsions, without any other prominent symptom. Hence these have been termed the Con- vukives or Spinal poisons. All the members of this general class, which is quite numerous, are derived from the vegetable kingdom. In referring the symptoms in a given case to the action of either of the above classes, it must not be forgotten, as already intimated, that the members of each do not always produce the same effects. Thus, arsenic has occasioned symptoms similar to those of narcotic poisoning ; whilst opium has produced effects resembling poisoning by an irritant. Sources of Evidence of Poisoning. The medical evidence in cases of poisoning is derived chiefly from — 1. The symptoms; 2. The post-moiiem appearances ; and, 3. Chemical analysis. 1 . Evidence from the Symptoms. In forming an opinion in a case of suspected poisoning, the medi- cal examiner should acquaint himself with not only the special character of the symptoms present, but also, as far as practicable, the previous health and habits of the patient, when food or drink was last taken, whether in taking it any peculiar taste or odor was observed, and whether others partook of the same food. Among the characters of the symptoms of poisoning usually mentioned by writers on this subject, the most constant are — 1. The symptoms arise suddenly, and soon after the taking of food, drink, or medicine ; and, 2. They rapidly prove fatal. 1. The symptoms occur suddenly, and soon after the taking of some solid or liquid. — The greater number of poisons, when taken in fatal quantity, manifest their action either immediately or within a short period, the symptoms of but few being delayed, under ordinary circumstances, much beyond an hour. Many instances might be cited in which a knowledge of the time that elapsed between the taking of food or drink and the appearance of the suspected symp- SVMI'TOM.S A.S KVIUKNCE OF I'OISONING. 39 toins wiis ill itself .sutticicnt to deterniiiie that tliey wore really toms within five minutes afterward, and they usually appear within thirty minutes; yet they have been delayed, in one instance at least, for three hours. It is well known that antimony, arsenic, lead, and various other poisons, when taken into the system in repeated small doses, may give rise to effects wholly different from those usually produced by a single poisonous dose of the substance. As a general rule, poisons act more speedily when taken in the state of solution than in the solid form. On the other hand, a full stomach, and, according to Dr. Christison, sleep, may delay the ac- tion of certain substances. That the action of one poison may be modified by the presence of another, is well illustrated by the follow- ing case. A man, aged twenty-nine years, swallowed three grains of strychnine, one drachm of opium, and an indefinite quantity of quinine. When seen by a physician ticelve hours afterward, he only complained of feeling " queer." But there was extreme cerebral excitement; the pulse quick, full and strong; pupils contracted; the whole face of a deep-red color ; tongue tremulous and covered with a brownish-white fur ; surface of the body hot, with profuse perspira- tion ; body and limbs in violent tremor, and at intervals spasmodic action of all the muscles, alternating with comparative quiet and drowsiness, from which he was easily roused. Upon the administra- tion of full emetic doses of zinc sulphate, opium was freely ejected. One hour later, the patient became quite drowsy, but when roused would start violently and remain delirious for some minutes. In two hours more, complete stupor suddeuly supervened, and continued, with but little change, till death, which occurred forty hours after the mixture had been taken. [Chicago Jledieal Journal, November, 1860.) How far the first appearance and character of the symptoms of a particular poison may depart from their ordinary course, can be 40 INTRODUCTION. learned only from a comparison of well-authenticated cases. In this respect, our knowledge at present in regard to the effects of very many substances is extremely limited, and there is no reason to be- lieve that in regard to any we have as yet met with the greatest deviation possible. In this connection, it must also be borne in mind that there are certain natural diseases, the symptoms of which resemble more or less those of poisoning, and which may appear suddenly at any time. In fact, some of these diseases, such as apoplexy and perforation of the stomach, are more likely to occur soon after the taking of food than at any other period. Instances of this kind, however, are of rare occurrence, and the subsequent history of the case will usually enable the practitioner to determine without difficulty its true nature. Nevertheless, cases have occurred, the nature of which could be estab- lished only by the post-mortem appearances and chemical analysis. When two or more persons who have eaten of the same food are suddenly seized with violent symptoms, there is, of course, increased reason for suspecting the presence of a poison. This cir- cumstance has in some instances at once revealed the source of the poison. Results of this kind, however, may be due to an unwhole- some or diseased condition of the food ; or to its having accidentally become contaminated with a poisonous metal, such as copper, lead, or zinc, during its preparation. On the other hand, several persons may partake of the same meal, or even of the same food, and poison have been designedly introduced only into the portion intended for a particular individual. Thus, in a case in which we were consulted, and which will be referred to hereafter, a family of several persons having mush and milk for supper, the mush was placed on the table in one dish, while the milk was distributed at the usual places of sitting, in bowls. Into one of the bowls strychnine had been intro- duced, and its intensely bitter taste was, perhaps, the only circum- stance that saved the life of the person for whom it was intended; only, however, to become the victim a few days afterward of a fatal quantity, under a form in which its taste was entirely concealed. In another instance, the plum-pie served for dinner was furnished to the several members of the family, on separate plates ; under the crust of one of the pieces, arsenic had been placed, and proved fatal to the person who ate it. From what has already been stated, it is obvious that several persons may even partake of the same poisoned SYMrTOMS AS EVIDEXCE OF POISONING. U food, and the results be very dilVereiit. \h\ llcrk quotes several striking examples of this kind. Lastly, in inquiries of this kind it must be remembered that poisons may be introduced into the system in other ways tlian with food, drink, or medicine. Thus, jioisoninj; by the external applica- tion of the substance is not of unfrecjuent occurrence; the same is also true of the inhalation of certain vapors and gases. Instances of this kind, however, are usually the result of accident. Several instances are recorded, in which jwisons were criminally introduced into the rectum and vagina; and Dr. Christison cites a case in which a fiital quantity of suli>huric acid was poured into the mouth of an individual while asleep. 2. The symptoms rapidly rim their course. — The duration of the symptoms of poisoning, like their appearance, is subject to great variation, even with regard to the same substance. Some few poisons, as hydrocyanic acid, nicotine, and conine, usually prove fatal within a few minutes, and most of them within comparatively short periods. Yet, as just intimated, great differences have been observed even in regard to the action of the same substance. Thus, the fatal period of hydrocyanic acid poisoning has been protracted for several hours ; whilst, on the other hand, arsenic, which on an average perhaps does not prove fatal in less than twenty-four hours, has caused death in less than two hours. As a general result, a large -dose of a given substance will prove more rapidly fatal than a small one, yet this is by no means always the case. Half a grain of strychnine has caused the death of an adult in less than twenty minutes, while in a case in which between five and six grains were taken, death was delayed for six hours ; and even larger quantities than the last mentioned have been followed by recovery. The vegetable poisons as a class, usually, either prove fatal within at most a very few days, or the patient entirely recovers ; but many of the mineral substances frequently do not cause death until after the lapse of several days. In fact, many of the members of the latter class may give rise to secondary effects which may extend through an interval of many weeks, or even months. The usual period within which each of the more common poisons proves fatal, and how far it has departed from its ordinary course, will be pointed out hereafter in the special consideration of the individual substances. In considering the duration of the symptoms in a case of suspected 42 INTEODUCTION. poisoning, it must be remembered that the symptoms of some natural diseases not onlj closely resemble those of certain kinds of poison- ing, but also run their course with equal rapidity. In most instances, however, a careful examination of the symptoms, with a full history of the case, when this can be obtained, will enable the medical prac- titioner to form a correct diagnosis ; but cases not unfrequently occur the true nature of which can be established only by the post-mortem a*ppearances and chemical analysis. The diseases most likely to give rise to symptoms resembling irri- tant poisoning are, cholera, inflammation of the stomach and bowels, and perforation of the stomach ; and those that may simulate narcotie poisoning — apoplexy, inflammation of the brain, and organic diseases of the heart. Cholera has been mistaken for poisoning by arsenic, and, on the other hand, arsenical poisoning has been mistaken for that disease. The same has also been true in regard to apoplexy and opium poisoning. The symptoms of disease of the heart, in the rapidity of their action, may closely resemble the effects of hydro- cyanic acid and of nicotine. The true nature of some of the fore- going diseases is readily revealed upon dissection ; but others, like the poisons with whose symptoms they may be confounded, leave no well-marked morbid appearances. In the examination of a case of suspected poisoning, the medical attendant should obtain as far as possible a full history of the progress of the symptoms and their relation to the taking of food, drink, or medicine. All suspicious articles of this kind should be collected ; and if vomiting has occurred, the matters ejected should also be col- lected and their character noted. All articles thus obtained should be carefully sealed, if solid, in clean white paper, and if liquid, in clean glass jars, distinctly labelled, and preserved for future examina- tion, the collector being careful not to permit any such article to pass out of his possession until delivered to the proper person. A chemical examination of some of these articles may at once re- veal the true nature of the symptoms. It need hardly be remarked that a failure to discover poison under these circumstances will by no means be conclusive evidence that a poison had not been taken. On the other hand, the detection of poison in a remnant of food or medicine taken by the person will not of itself be conclusive proof that a poison had been taken. Symptoms of poisoning have been feigned and poison put into articles of this kind for the purpose of MORBID APPEAKANCES OF POISONING. 43 charging another with an attempt to murder. Tlie existence of this tact can, oi' course, be determined only by the attending circumstances. Some years since we were engaged in a case in which it clearly ap- pearetl that a man maliciously put a large quantity of white arsenic into an alcoholic medicine he was using, and actually swallowed suffi- cient of the mixture to produce serious symj)toms ; lie tiien charged his wife with the poisoning. 2. Evidence from Post-mortem Appearances. There are very few instances in which the post-mortem ap- pearances are peculiar to ])oisoning. Nevertheless, this part of the evidence should always be very carefully considered, for when taken in connection with the symptoms and other circumstances, it may fully establish the true character of a case which would otherwise be doubtful. In death from natural disease, a post-mortem examina- tion may at once discover the fact. However, appearances of ordi- nary disease may be present, and death have resulted from the effects of poison. Several instances, in which coincidences of this kind ex- isted, might be cited. The presence of some few poisons, as opium and hydrocyanic acid, may sometimes be recognized by their odor ; and others, when in the stomach, by their color or botanical char- acters. It is a popular belief that great lividity of the body and rapid decomposition always attend and are characteristic of death from poisoning ; but these results are rarely produced, and are by no means peculiar. Some poisons leave no appreciable morbid changes in the dead body ; and of those that usually do, the appearances are subject to great variety, and in many instances similar to the effects of ordinary disease, or even the results of cadaveric changes. The mineral acids and caustic alkalies usually leave the most marked evidence of their action, and in some instances this is quite characteristic. The irritant poisons as a class usually produce irritation and inflammation of one or more portions of the alimentary canal, the effects being sometimes confined to the stomach, while at other times they extend to a greater or less degree throughout the entire canal. In some instances the coats of the stomach become ulcerated and softened, and even perforated. Poisons of this class, however, may cause death without leaving any discoverable change in the body. This has been the case even in respect to some of the more acrid and 44 INTEODUCTIOJSr. corrosive substances. In several instances of poisoning by arsenic, which generally produces strongly marked appearances in the stomach and bowels, nothing abnormal was found upon dissection. In the minute examination of the tissues of the alimentary canal, M. Bailloa advises the inspection to be made under transmitted light. Narcotic poisons in some instances produce more or less distention of the veins of the brain, but in others they leave no marked morbid appearances, and in none are the appearances peculiar. According to Orfila, the lungs almost always present livid and black spots, and their texture is more dense and less crepitant. These appearances, however, may result from ordinary causes. In some few instances there has been more or less irritation of the alimentary canal ; but this condition was most probably induced by the vehicle in which the poison was taken, or by the remedies subsequently administered. Narcotico-irritants partake in the nature of their effects of both the preceding classes. Thus, they may produce irritation and even ulceration of portions of the alimentary canal, and congestion of the lungs and of the veins of the brain and its membranes. But in most instances the morbid changes are not well marked. The usual morbid changes produced by the individual poisons will be pointed out hereafter ; but in this connection may be briefly mentioned some of the appearances which may be equally produced by ordinary disease or cadaveric changes and by poisoning. Appearances common to Poisoning and Disease. — Redness of the stomach and intestines as the effect of poisoning, cannot in itself be distinguished from that arising from natural disease. This condition is not only frequently the result of active disease, but it has often been observed immediately after death in cases in which during life there were no indications of derangement of the stomach or bowels. Moreover, various pathologists have observed that pseudo-morbid redness of the mucous membrane of the stomach sometimes makes its appearance several hours after death. Dr. Christison is of the opinion that an effusion under the villous coat of the stomach, and incorporation with its substance, of dark brownish-black blood, is characteristic of violent irritation, if not of the effects of poison alone. It is well known that colored substances within the stomach, and the contact of this organ after death with the adjacent parts, may cause it to become more or less colored. But these appearances are readily distinguished from the effects of poison. MORBID APPEARANCES OF POISONING. 45 Softening of the stomach is another appearance which may give rise to embarrassment. When dne to the action of poison, it is usnally acconii)anii'(l hy other a|)pearanccH winch readily distingnislj it from the effects of ordinary disease or post-mortem changes. Dr. Carswell has sliown that this condition is not unfreqnently ])roduced by the chemical action of the gastric jnice after death. lie also observes tliat in softening of the mucous membrane of the stomach as the result of inflannnatory action, the tissue is always more or less opaque, and the action attended by one or more of the products of this pathological state; whereas in post-mortem softening, the tissue is always transparent, and the action never attended with serous effusion or other concomitants of inflammation. Ufceixition and perforation of the stomach arc not unfreqnently produced by corrosive poisons, but they, especially tlic latter, are rarely met with as the result of the action of the simple irritants. As the effect of natural disease or post-mortem action, they are not uncommon. In many instances these appearances, as the result of poisoning, can be distinguished from those arising from other causes only by a history of the symptoms during life, or by the detection of poison in the tissues or other parts of the body. This distinction is usually well marked in the action of the mineral acids and caustic alkalies. Perforation of the stomach has not uufrequently occurred from gelatinization of its tissues, and in cases in which during life there was no evidence of a diseased state of that organ. These appear- ances have been chiefly observed in cases of violent or sudden death. It was formerly believed that this condition was always a morbid process, and characteristic of a special disease. But, since the re- searches of modern pathologists have shown that the gastric juice has the property of dissolving the dead stomach, and that many of these lesions have undoubtedly been due to the action of that fluid after death, there is little doubt that they may all be referred to post-mortem changes. When the gastric juice escapes through the aperture thus produced, it may, as has often been the case, exert its solvent action upon the adjacent organs. As these appearances are unattended by signs of irritation, they are usually readily dis- tinguished from the effects of poisoning. Should, however, a per- foration of this kind occur in a case in which prior to death the stomach was affected with signs of irritation, it might be impossible 46 INTEODUCTION. from the appearances alone to determine the true character of the perforation. Perforation of the oesophagus and of the intestines, as the result of poisoning, is not at all likely to occur. In fact, there seems to be only one instance of the former, and none of the latter, on record. But these conditions, as the result of disease, have often been ob- served ; and they have even resulted from the action of the gastric juice after death. Points to he observed in post-mortem examinations. — All investiga- tions of this kind should be made in the presence of the proper law officer; and it is well for the examiner to have the assistance and corroboration of another physician. All appearances observed, whether abnormal or otherwise, should be fully written down at the time of their observance. The length of time the person has been dead ; how long he survived the first symptoms ; and the condition of the body in respect to external appearances, should as far as prac- ticable be learned and carefully noted. In the dissections, the con- dition of the entire alimentary canal, and of all the organs essential to life, should be minutely examined ; in the female, the vagina and uterus should also be inspected. The stomach with its contents, and a portion of the small intestines, properly ligatured, should be removed from the body. The condition of these organs, and the nature of their contents, may then be examined. In some instances, however, it is best not to open these organs until they are delivered to the chemist. A portion of the liver and of the blood should also be removed for chemical analysis. And in some instances it is im- portant to remove other parts of the body, as the kidneys, spleen, heart, and brain, and even portions of the muscles, for chemical examination. All the organs and the blood thus removed should be collected in separate, clean glass vessels, great care being taken that none of the reserved substances at any time be brought in contact with any sub- stance that might afterward give rise to suspicion. Before passing out of the sight of the examiner, the bottles should be securely sealed and fully labelled. They should then be retained in his sole possession until delivered to the proper person. VALUK OF <'IIF:MI('AL axalvsis. , 47 .'). J'Audencc J'roni Chcmicdl Analjixix. Importance of chemical evidence. — In most charges of" poisoning, the final issue depends ii[)on the results of the chemical analysis. In fact, in many instances in which the evidence from symptoms, post-mortem appearances, and moral circumstances is very equivocal or in part wanting', a chemical examination may at once determine the true cause of death. It must be remembered, however, that a person may die from the effects of poison and not a trace of its ])res- ence be discoverable in any part of the body ; while, on the other hand, the mere discovery of a poison in the food or drink taken or in the body after death, is not in itself positive proof that it occasioned death. It has been claimed that a failure to detect poison in the dead body, by proper chemical skill, was evidence that death was the result of some other cause; but this claim is entirely groundless. The symptoms and pathological appearances, at least in connection with moral circumstances, are often sufficient in themselves fully to establish death from poisoning ; and a number of convictions have very properly been based on these grounds in instances in which chemical evidence was ^vanting, and even when it had entirely failed. There are a number of organic poisons which at present cannot be recognized by chemical tests; and instances are recorded in which death resulted from large quantities of some of the poisons most easy of detection, and not a trace could be discovered in any part of the body. It is obvious that the discovery of minute traces of such poisons as are used medicinally could not, independently of symptoms and other circumstances, be regarded as evidence of poi- soning. Substances requiring analysis. — The substances that may directlv become the subject of a chemical analysis, in a case of suspected poisoning, are : the pure poison in its solid or liquid state ; suspected articles of food or medicine; matters ejected from the body by vomiting or purging; the urine; suspected solids found in the stomach or intestines after death ; the contents of the stomach or bowels; any of the soft organs of the body, as the liver, spleen, etc. ; and the blood. Sometimes it is only necessary to examine one of the above- mentioned substances ; but in many instances two or more of them 48 INTRODUCTION. require examination. If a poison be thus detected, it will sometimes become necessary to examine substances other than those specified, in order to determine its real source. The evidence of poisoning is, of course, most complete when the poison is recovered from some of the soft organs of the body, after it had been absorbed. So, also, the proof will be more direct when the poison is detected in the contents of the stomach or intestines, than in articles of food or medicine. Precautions in regard to analyses. — When called to make a chemi- cal examination of any suspected material, the analyst should obtain, as far as practicable, a knowledge of the symptoms, and, if death has taken place, of the post-mortem appearances, observed in the suspected case : since these, when known, will generally enable him to decide at least to which class of poisons the substance belongs, and in some instances will even indicate with considerable certainty the individual substance. He may thus, by following these indications in the analysis, save much labor, and — which in many instances is of much more importance — be enabled fully to establish the presence of poison when present in quantity too minute to be recognized under other circumstances. It must not be forgotten, however, that irritant poisons have produced symptoms resembling those induced by some of the narcotics, and that the latter may produce symptoms of irritant poisoning. So, also, before applying any chemical test to a suspected solid or liquid, its quantity — of the former by weight, and of the latter by measure — should be accurately determined. In the application of the reagents, the very least quantity of the material that will answer the purpose should, at least at first, be employed for each test. In like manner, in the preparation of complex mixtures, the residual solution should be reduced to the very smallest volume compatible with the application of the tests that it may become necessary to apply. There is little doubt that in many of the reported instances of non-detection of poisons the failures have resulted from a neglect of this point. It should always be borne in mind that a given quantity of a poison, when in solution in a small quantity of fluid, may yield, with a given reagent, perfectly characteristic results, whereas if the solution be but slightly more dilute, the reaction may entirely fail. Thus, the hundredth part of a grain of nicotine in one grain of water yields with platinic chloride a copious and rather VALUE OF CHKMICAL ANALYSIS. 49 characteristic crystalline precipitiite, wliilo the .siinic (jiiaiititv in fen grains of that liquid yields no j)reci])itate whatever. In the preparation of the contents of the stoniaeli and (if the solid organs of the body, it is often advisable to employ oidy ;ibunt, one-half or two-thirds of the matter for the first examination. This proportion will perhaps in all cases, at least in regard to mineral poisons, suffice to show the poison if present, while in case of acci- dent the analysis could be repeated. When, however, the analyst has perfect confidence in his ability to go safely through with the examination, it is perhaps best not to make this division of matter, at least in the investigation for certain organic poisons. The minute quantity of poison usually taken up by the blood, especially in the case of the alkaloids, renders it necessary to operate upon compara- tively large quantities of this fluid, and to conduct the examination with extreme care. When the symptoms or attending circumstances do not point to a particular poison, or at least to the class to which it belongs, it is obvious that a division of the matter submitted for examination becomes absolutely necessary. Under these circumstances, great care should be exercised not to subject the matter to any process that would preclude the possibility of examining for any poison for which it might afterward become necessary to look. It need hardly be observed that during investigations of this kind the examiner should never lose sight of the suspected material, except when it is in some secure place ; and the greatest possible care should be taken that it is not brought in contact with any substance the nature of which is not fully understood. A neglect of these direc- tions may prove fatal to the results of a chemical examination. The careful analyst need not be cautioned against hasty conclusions in regard to the results of reagents. After the presence of a poison is fully established, it is in most instances only necessary to be able to state the probable amount present; but sometimes it is necessary to determine its exact quantity. In all cases in which it is practicable, it is best to determine the actual amount recovered ; but it not unfrequently occurs, especially in the detection of absorbed poison, that the quantity present is so small as not to admit of a direct quantitative analysis. Under these circumstances, we may often, by accurately noting the volume of solution obtained and observing the comparative reaction of several 4 50 INTEODU€TION. tests, estimate very closely the strength of the solution, and from this deduce within narrow limits the amount of the poison present. It was formerly claimed that unless a quantity of poison suffi- cient to destroy life was found in the dead body, the chemical evidence of poisoning was defective. But it is now a well-known fact that a person may die from the effects of a large dose, and very little or even not a trace of the noxious agent remain in the body at the time of death. As any of the poison remaining in its free state in the stomach at the time of death had no part in producing the fatal result, it is obvious that to recover a fatal quantity from that which had been absorbed, and which was really the cause of death, even granting that none had been eliminated from the body with the excretions, would require an analysis of the entire body and the recovery of every portion of the poison from the complex mass, — the first of which is impracticable and the second impossible. It is only, therefore, in cases in which more than a fatal dose remains in the body at death that we are able to recover sufficient to destroy life. Moreover, as already stated, the amount of poison in the body at the time of death is in itself no index whatever of the actual quantity taken. Value of individual chemical Tests. — The result of a chemical examination will depend, at least in great measure, upon how far we are acquainted with reactions peculiar to the substance under consid- eration ; the delicacy of these reactions ; and, in many instances, our ability to separate the substance from foreign matter. There is usually no difficulty in recognizing the presence of any of the mineral poisons, even when present only in minute quantity; but the case is very different in regard to the detection of many of the organic poisons. For the recognition of many poisons we are at present familiar with several tests, the reaction of each of which is charac- teristic of the substance; while for the detection of others we are acquainted with only one such reaction ; there are others still for which we have no specific reagent, but whose presence can be fully established by the concurrent result of several tests; lastly, there are some organic poisons for the detection of which, at present, there is not known even any combination of chemical reactions by which their presence can be determined. Some of the poisons of the last- mentioned class may, in the form of leaves, seeds, or roots, be rec- ognized by their botanical characters ; and others, by their peculiar VALUK OF CHEMICAL ANALYSIS. 51 physioloj^ieal effects, especiiiUy when llicse are (akcii in connection with some of their ooncral chcMuical in-opcrties. Anionj^ the poisons that can he readily dek-ctcd when in (heii- pure state, tliei-e are some which when present, even in (pntc notalih; (|iianlit\', in complex organic mixtures, adhere so (cnaciously to the foreij^n orIIVSl(iI,()(;i('AI- Kl'FKCrS. 65 On the otliur hiaul, two .sisters, aj^ud respectively twelve unci six- teen years, took by mistake about half an ounce of subcarbonate of potassium each. Violent symptoms immediately ensued, and in the case of the elder continued with little interruption for about two months, when death took place. In the case of the other, the symp- toms abated after a few days; but they again returned, and finally proved fatal after the lapse of nearly three months. {Beck's Med. Jur., ii. 524.) In a case reported by Dr. Deutscli, a solution esti- mated to contain about half an ounce of caustic potash did not prove fatal until after a period of twenty-eig-ht weeks. And in another, a quantity of impure carbonate of sodium produced stricture of the gullet, of which the patient died two years and three months after having taken the poison. Sir C. Bell relates a case of this kind, in which death did not take place until after the lapse of twenty years. Solutions of ammonia have proved rapidly fatal. In a case related by Pleuck, a quantity of liquor amraoniffi poured into the mouth of a man who had been bitten by a mad dog caused death in four minutes. {Christison on Poisons, 194.) Dr. Kern relates the case of a man of intemperate habits, aged seventy years, who took two swallows of spirits of ammonia; he was immediately afterward seized with a seuse of suffocation, cough, and vomiting, and, notwith- standing prompt treatment, he died within fou7- hours; death being preceded by delirium, stupor, and spasms. {Amer. Jour. Med. Sci., Jan. 1870, 275.) A case in which a solution of ammonia proved fatal in six hours has already been cited. In a case reported by Dr. Fran9ais {A^m. d'Hi/g., 1877, i. 556), ninety grammes (about three ounces) of aqua ammonise, taken by a young woman, did not prove fatal until the eighth day. The vapor of ammonia applied to the nostrils of a lad laboring under a fit of epilepsy induced bronchitis which proved fatal in forty-eight hours. In a somewhat similar case, death ensued on the third day. Fatal quantity. — It is impossible at present to state with any degree of certainty the smallest quantity of either of the substances under consideration that might prove fatal. In most instances the effects will depend rather upon the degree of concentration under which the substance is taken, than upon the absolute quantity. In an instance recorded by Dr. Taylor [op. cit., 328), one ounce and a half of the common solution of potash of the shops proved fatal to an adult in 66 THE ALKALIES. seven weeks. The quantity of the caustic alkali taken in this case did not perhaps exceed forty grains, which is the smallest fatal dose we find recorded. There are not less than four cases reported, two of which have already been cited, in which half an ounce of the car- bonate of potassium proved fatal : in all of these, as in the preceding case, death was due to the secondary effects of the poison. Solutions of ammonia have proved fatal when taken in small quantity. In the case related by Dr. Stevenson, a teaspoonful of strong liquor aramonise proved rapidly fatal to an adult. And at least two fatal instances are reported in each of which not over two drachms of the solution had been taken. Instances of recovery from solutions of this alkali have been of more frequent occurrence than from the fixed alkalies. A man swal- lowed by mistake three drachms of a strong solution of ammonia, and as much of the sesquicarbonate, dissolved in two ounces of oil ; but under appropriate treatment he recovered in about eight days. (Jlliarton and Stille's Med. Jur., 502.) Dr. Blake reports a case in which a girl, aged fourteen years, swallowed a mixture of half an ounce of aqua ammonise and one ounce of olive oil, and, although she lingered in great agony for many weeks from the effects of the mix- ture, she eventually recovered. (St. George's Hosp. Rep., 1870, 75.) In another case, a boy, aged two years, took half an ounce of very pungent spirits of hartshorn, and recovered. Instances are related in which recovery took place even after more than an ounce of the solution had been taken. In a case reported by Dr. Pellerin, a young woman with suicidal intent swallowed at a draught upwards of ten drachms of a solution of ammonia. Dr. Pellerin found the patient in the sitting position, having on her knees a basin containing a large quantity of stringy salivary fluid with a few streaks of blood. The face was pale, the eyes were haggard and injected. The lips pre- sented much swelling, and also redness, which extended to the mouth and fauces. There was complete aphonia ; pain in the pharynx and epigastrium ; the pulse was slow, the limbs cold. The loss of voice lasted three days, and deglutition was almost impossible. Under active treatment the woman was convalescent in a week. {Ifedico- Chir. Rev., April, 1857, 500.) Teeatment. — The antidote for poisoning by any of the fi'ee alkalies or their carbonates, is the speedy administration of a solution of some of the mild vegetable acids, — such as acetic acid in the form POST-MORTEM APPEAKANCES. 67 of diluted viiioo:ar, or the juiee of any of the acid fruits, — by which the j)oison will to a certain extent be neutrali/x'd. Large quantities of olive oil iiave in some instances been administered with advantage. This substance may convert the alkali into a soap, and thus prevent its caustic action. Lar2:e draughts of milk may also be used with benefit. In poisoning by the vaj)or of ammonia, Dr. Pereira recom- mends the inhalation of the vapor of acetic or of dilute hvdrochioric acid. Post-mortem Appearances. — These will depend in a great measure upon the length of time the patient survived the taking of the poison. In acute cases, the mucous membrane of the parts with which the substance comes in contact is more or less disorganized, being inflamed and broken up in patches; sometimes there is ex- travasation of disorganized blood upon the walls of the organs thus affected, which causes them to present a bluish or black appearance. This appearance is sometimes well marked in the mouth. In some instances, large portions of the mucous membrane of the mouth, oesophagus, and stomach are entirely removed. In Mr. Dewar's case, in which death was produced in twelve hours by a solution of carbonate of potassium, the appearances were much the same as those just described. Thus, the mucous membrane of the pharynx and oesophagus was almost entirely destroyed, and dark blood extravasated beneath the pulpy mass; in the stomach, the mucous membrane was destroyed in two places, and these patches covered with clotted blood. Similar appearances were found in the case that proved fatal in twenty-four hours. In the case related by Dr. Ogle, in which a quantity of caustic potash proved fatal after about two months, the organs of the thorax, the tongue, fauces, and pharynx were found natural ; but at the upper part of the oesophagus three distinct cicatrized bands were observed, contracting the mucous membrane ; the lower part of the tube was much contracted, its lining membrane quite destroyed, and the muscu- lar coat exposed. The external tissues of the oasophagus were much thickened, and the tube was strongly adherent to all the neighboring parts. The cardiac orifice of the stomach was so contracted as barely to admit the passage of a director ; the mucous membrane at the pyloric end of the organ presented a large and dense cicatrix, which so involved the adjacent parts as to obstruct all communication with the duodenum, except by a small orifice which only admitted 68 THE ALKALIES. an ordinary-sized probe. The other portions of the stomach, and the remainder of the intestinal tube, as also all the other abdominal organs, were healthy. In a case in which death was caused by the taking of a solution of caustic potash four months previously, there was found a stricture of the oesophagus four or five inches in extent, rendering swallowing impossible. (Chem. News, Oct. 1867, 197.) In Dr. Deutsch's case, already cited, the mucous membrane of the lower portion of the oesophagus was found so greatly thickened that the ojDening into the stomach was nearly obliterated. In Dr. Kern's case, in which a solution of ammonia proved fatal in four hours, the mouth and throat were found denuded of epithelium, and inflamed ; the stomach contained a bloody fluid having the odor of ammonia; at its lower portion the epithelium of the stomach was destroyed, and the muscular coat changed into a black pulpy sub- stance. The duodenum and the serous coat of the stomach nearest the bowel were inflamed. The blood remained of a thin fluid con- sistence. In the case in which a teaspoonful of liquor ammonise proved rapidly fatal, related by Dr. Stevenson, the mucous membrane of the mouth and pharynx was found red and glazed. The oesopha- gus was intensely red throughout, more especially at its lower part, which was of a dark-purple color ; this color ceased abruptly at the stomach. The upper portion of the oesophageal mucous membrane was shreddy in a longitudinal direction. The epiglottis was slightly oedematous ; the loose tissue about the larynx much so. The mucous membrane of the trachea and bronchi was thickened and injected. Both lungs were gorged with blood and oedematous. A circular patch of the gastric mucous membrane, about four inches in diameter, was injected, and the membrane here was thin ; elsewhere it was thick, pale, and coated with slimy mucus. Both sides of the heart contained dark fluid blood. In the case in which eight ounces of liquor ammonise had been taken, there were signs of inflammation all along the digestive tract. The mucous membrane of the stomach was charred and destroyed, and there was great congestion as far as the lower end of the jejunum. The stomach contained about ten ounces of dark altered blood. In another case, fatal in three days, the lining membrane of the trachea and bronchi was softened and covered with layers of false membrane ; while the larger bronchial tubes were completely obstructed by casts of this membrane. The mucous membrane of the gullet was soft- NITRATE OP POTASSIUM. 69 ened, aud the lower ei)(l oi" the tube completely destroyed. The an- terior wall of the stomach contained an aperture about an inch and a half in diameter, through which the contents of the organ had escaped. In chronic cases, the lower portion of the o'sophagus and the stomach are frequently much contracted. The walls of the stomach are often thickened, and the lining membrane wholly destroyed. An ulcerated and o;angrenous state of the mucous membrane of the stomach and intestines has also been observed. And in sonie in- stances other of the abdominal organs have been much disorganized. XiTRATE OF Potassium. — This salt, commonly known by the name of saltpetre or nitre, has in several instances been taken by accident, with fatal results. To produce serious effects, however, it requires to be taken in large quantity, such as half an ounce or more. The symptoms usually observed are severe burning pain in the stomach and abdomen, nausea, vomiting and purging, fol- lowed by coldness of the extremities, tremors, and collapse. The effects of large doses have, however, been subject to considerable variation. In a case recorded by Dr. Beck, a dose of this salt taken in mistake for Glauber's salt, proved fatal to an aged man m half an hour; and in an instance cited by Orfila, one ounce caused death in three hours. A man who took three ounces and a half of the salt at a dose, apparently suffered but little for five hours, when he suddenly fell out of his chair and expired. In a more recent case, about an ounce of the salt caused the death of a strong young man in six hours. When first seen by a physician, a few hours after taking the dose, the patient was lying on his back, completely insensible, the skin cold, clammy, and blue; pulse irregular, almost imperceptible; from time to time there were sudden contractions of the pectoral muscles, which continued for some seconds; the eyes were fixed, pupils greatly contracted and immovable. {Jour, de Chim. Med., Dec. 1873, 542.) Recovery has in several instances taken place even after so much as two ounces of the salt had been taken. The treatment consists in the speedy removal of the poison from the stomach, aud the subsequent exhibition of demulcents. No chemical antidote is known. After death, the stomach has been found highly inflamed, mottled 70 THE ALKALIES. with dark-colored patches, and the mucous membrane partially de- tached. Similar appearances have also been observed in the small intestines. In at least one instance, the coats of the stomach were perforated by a small opening. In the case fatal in six hours, mentioned above, all the signs of asphyxia were found : thick black blood filled the right heart, and there was great congestion of the lungs. The bronchial ramifica- tions were filled with froth ; their mucous membrane was normal, as also that of the alimentary canal. The liver, spleen, and kidneys presented nothing abnormal ; the brain was healthy, but the sinuses were gorged with thick black blood. Analyses of the blood and urine showed the presence of a potassium salt. Chlorate of Potassium. — Although usually regarded as non- poisonous, this salt has of late years caused death in a number of in- stances. In one of these, an elderly man took in mistake for Epsom salt something over an ounce fthirty-five grammes) of potassium chlorate. Death, which followed in seven hours after the ingestion of the salt, was preceded by the following symptoms : vomiting, colic, and diarrhoea, general weakness and rigidity of the limbs. After death the skin of the dorsal and lumbar regions presented a slate-colored appearance. [Med. Times, Jan. 1881, 287.) In a case related by Dr. Kennedy {Amer. Jour. Pharm., 1878, 112), about half an ounce of the salt proved fatal in seven hours, under vomiting, purging, and stupor, to a child aged two and a half years. M. Marchand reports a series of cases in which four children, from three to seven years of age, took ten, twelve, and twenty-five grammes of this salt in less than a day, or at most thirty -six hours. They sud- denly vomited ; the urine was scanty and bloody, the skin yellow ; there was rapid emaciation and loss of strength ; finally cerebral symptoms, delirium, and coma, ending in death in three instances. In the post-mortem examinations of the fatal cases, and of animals used for experiment, the most characteristic lesions found were those of the blood and of the kidneys. The blood presented a peculiar brown or chocolate color, which was unchanged on exposure to the air. The kidneys were enlarged, of a brown color on the surface, and, under the microscope, the urinary canaliculi of the medullary substance were distended with brownish, granular cylinders, proceed- ing evidently from the disintegration of the red corpuscles ; the renal CHLORATE OF POTASSIUM. 71 iiiHainmatory action was of secondary importance. Under the spec- troscope, the blood presented the spectrum of metha)moglol)in. The poisonous action of ])otassium chlorate, accordinj^ to M. Marchand, is due to its oxidizing action upon the haemoglobin of the blood, by which the corpuscles acquire a great tendency to aggluti- nate. Thus modified, the corpuscles accumulate in the different organs, but more especially in the kidneys, where they form brownish conglomerate masses. Death results either directly from tlie change in the blood, or from disturbance of the renal functions, whereby uraemic phenomena are produced. {Annales d'Hygi^e, Nov. 1880, 485.) Dr. Satlow, of Leipsic, reports tlie case of a boy, aged fifteen years, who swallowed a solution of potassium chlorate containing from twenty-five to thirty grammes of the salt. Soon after drinking the solution, the patient was seized with frequent vomiting of dark green masses very similar to thin faecal discharges. Death ensued on the fourth day, resulting gradually from increased weakness of the heart, accompanied by dyspnoea and feelings of coldness and paraly- sis of the feet progressively extending upwards. On inspection, the blood was found of a peculiar brown color, the density of syrup, and the red corpuscles especially affected, being pale and glutinous, and gathered together in irregular clumps. A large quantity of reddish- brown fragments, supposed to be haemoglobin, had been passed with the urine two days before death. (Boston 3Ied. and Surg. Jour., Jan. 1882, 81.) In a case reported by Dr. Ferris, in which a large spoonful of the salt proved fatal to a strong man, on post-mortem examination the auricles of the heart were found distended to their utmost capacity by dark coagula, homogeneous, and of sufficient tenacity to support their own weight and sustain the coat of the cavities from which they were drawn. The large vessels communicating with the cavities were also full of similar coagula. On removal of the heart, but little blood flowed from any of the severed vessels. {Medical Record, 1873, 482.) In a fatal case of poisoning by potassium chlorate, M. Ludwig examined the blood, the contents of the stomach, and the urine. The urine was turbid, acid in reaction, and contained an abundant sedi- ment, composed of blood-globules in small number, and large granu- lar casts. He failed to find the salt either in the blood, in the urine, 72 THE ALKALIES. or in the contents of the stomach. (Boston Med. and Surg. Jour., Feb. 1882, 127.) Dr. T. Croft relates a case {Gaillard's Med. Jour., Julv, 1883, 15) in which a young woman, directed to gargle with a solution of potas- sium chlorate, and occasionally swallow a little of the solution, used in this manner nearly half a pound of the salt within a few days. Violent symptoms then appeared, followed by death seven days later. At first there was violent vomiting and diarrhoea. This was soon followed by complete constipation and stoppage of the urinary secre- tion, persistent nausea, and general cyanosis, the blueness extending even to the finger-nails and toe-nails. After death, the skin became clear, and marble -like. In a case reported by Dr. Bohn {Med. Times, May, 1884, 666), a man took in teaspoouful doses during thirty-six hours about two ounces of the salt. Symptoms of general collapse followed, and there was complete suppression of urine. A little urine drawn from the bladder contained blood-corpuscles and brownish tube-casts, and exhibited the spectrum of methsemoglobin. Death occurred on the third day, being preceded by jaundice. On inspection, the spleen, liver, and kidneys were found of a brown color, and the nriniferous tubules were filled with brownish masses. The Tartrate, Sulphate, and Oxalate of Potassiujj: have in several instances destroyed life. The noxious effects of the last-mentioned salt, however, chiefly depend upon the oxalic acid which it contains. In a case of fatal poisoning by common alum, or sulphate of potas- sium and aluminiurn, in which a man, aged fifty-seven years, swal- lowed with some cold water, in mistake for Epsom salt, about an ounce of the calcined salt, the following symptoms were observed : at first a sense of violent constriction in the mouth, throat, and stomach; incessant nausea, followed by a single bloody vomiting, without any purging; extreme depression, great agony ; small, quick pulse; rapid respiration, repeated syncope, and death in eight hours. The post-mortem examination revealed a yellow, abraded condition of the mouth, pharynx, and oesophagus, with swelling of the tongue and uvula; general inflammation of the peritoneum; kidneys much injected ; bladder empty ; heart dilated, with soft clots of a currant- jelly color. [Annales d'Hygi^ne, Jan. 1873, 192.) potassium oxidk. — potash. 73 Chemical Properties of the Ai.kai.irs. Distinguisking propei'ties. — Solutions of the caudic alkalies are distinguished from those of their carbonates hy tiie latter efferves- cing, from the escajie of carbonic acid gas, when acted upon by hydro- chloric or any of the strong acids. Sulphate of Magneshjm, at ordinary temperatures, throws down from solutions of the normal carbonates {protocarhonates) of i\\Q fixed alkalien a white precipitate; whereas with the acid carbonates [bicarbonates) it })roduces no pre- cipitate. This reagent fails to precipitate solutions of either of the carbonates of ammonium. Nitrate of Silver produces in solutions of the ^xecZ caustic al- kalies a brown precipitate, which is insoluble in excess of the alkali ; while in a solution of ammonia it produces a somewhat similar precipitate, readily soluble in excess of the alkali : when, therefore, the reagent is not added in sufficient quantity, the ammoniacal so- lution fails to yield a precipitate. Solutions of the carbonates of either of the alkalies yield with this reagent a yellowish- white precipitate, which in the case of the fixed alkalies is insoluble in excess of the alkaline salt, while that from either of the carbonates of ammonium is soluble in excess of the alkaline compound. The precipitation of the acid carbonates by this reagent is attended with effervescence, due to the escape of carbonic acid gas, but this result is not observed in the case of the normal carbonates. Corrosive Sublimate throws down from solutions of the fixed alkalies a bright yellow precipitate, which is insoluble in excess of the alkali; from the normal carbonates a reddish-brown ; but in solutions of the acid carbonates it produces no precipitate. With ammonia and its carbonates this reagent produces a tchite precipitate, which is somewhat soluble in excess of the alkaline solution, especially in the presence of ammoniacal salts. The different alkalies will now be separately considered, in regard to their chemical nature and reactions, and the methods by which they may be recovered from organic mixtures. Section I. — Potassium Oxide. — Potash. General Chemical Nature. — Potassium oxide, known also as anhydrous jJotash, is a compound of the elements potassium and oxy- gen, KjO ; in combination with the elements of water, with which it 74 POTASSIUM OXIDE. — POTASH. unites with great energy, it forms potassium hydrate, KHO ; thus, K2O + H20 = 2KHO. Potassium hydrate, known also as hydrate of potash, potassa fusa, and caustic potash, when pure, is a white, brittle solid ; as usually met with in the shops in the form of little sticks, it has sometimes a grayish or brownish color, due to the pres- ence of foreign matter. When exposed to the air, it deliquesces and slowly absorbs carbonic acid, becoming changed into the carbonate of potassium. Potassium hydrate dissolves, with the evolution of heat, in about half its weight of water ; it is about equally soluble in alcohol. Its solubility in alcohol enables us to separate it from many of its salts, such as the different carbonates, nitrate and sulphate, which are insoluble in this liquid. An aqueous solution of caustic potash changes an infusion of violets or of red cabbage to green, an infusion of turmeric to reddish-brown, and immediately restores the blue color of reddened litmus, even, according to Harting, when the alkali is dissolved in 75,000 parts by weight of water. A saturated aqueous solution of the pure caustic alkali has a density of about 2, and contains about 70 per cent, of the anhydrous alkali. The following table, by Dalton, indicates approximately the per- centage of anhydrous potassium oxide (K2O) in solutions of the alkali of the diflPerent given specific gravities : STRENGTH OF AQUEOUS SOLUTIONS OF POTASSIUM OXIDE. >p. Gr. 1 78 Percentage K2O. 56.8 51.2 ... 46 7 Sp. Gr. 1.36 Percentage K2O. 29.4 1 68 1 33 26.3 1 60 1.28 23.4 1 52 42 9 1.23 19.5 1 47 39 6 1.19 16.2 1 44 36 8 1.15 13.0 1 42 ... . 34 4 1.11 9.5 1.39 32.4 1.06 4.7 Caustic potash, in its action upon animal tissues, is the most de- structive of the alkalies. When rubbed between the fingers, by its chemical action on the skin, it imparts a soapy feel. It forms soluble compounds with many of the constituents of the animal tissues ; and it may dissolve and perforate the coats of the stomach even more readily than the mineral acids. The salts of potassium are colorless, except those in which the SPECIAL CHK\fICAT. rROI'KRTIES. 75 cotistitucnt acid is colored; and tliey generally oryslallize without water of crystallization, in wliich tliey diller in most instances from the correspond in<^ salts of sodium. With very few exceptions, they are freely soluble in water. Special Chemical Properties. — Potassiimi compounds when heated upon a clean platinum wire, in the reducing l>low-pipe flame, impart a violet color to the outer flame. This reaction may be entirely masked by the presence of even a small quantity of sodium, which gives a strong yellow color to the outer flame. In like manner, an alcoholic solution of the alkali or of any of its salts burns with a violet flame ; but this reaction is also obscured by the presence of sodium compounds. On account of the solubility of most of the compounds of potas- sium, there are but few reagents that precipitate it from solution, and these only when tlie solution is comparatively strong. Before apply- ing any liquid test for the detection of potassium oxide or either of the alkalies, the absence of metallic oxides other than those of the alkalies should be established. This may be done by treating a small portion of the solution, acidulated with hydrochloric acid, with sulphuretted hydrogen ; another, and neutral portion, with sulphide of ammonium; and a third portion, with carbonate of sodium: when, if these reagents fail to produce a precipitate, it follows that the metallic oxides mentioned are absent. In applying a liquid reagent, a drop of the suspected solu- tion may be placed in a watch-glass, and a small portion of the reagent added by means of a pipette. The mixture may then be examined by the microscope. If there be no immediate precipi- tate, it must not be concluded that the base in question is entirely absent; but the mixture should be allowed to stand, even in some instances for some hours, before deciding the entire absence of the substance. In the following examinations of the behavior and limit of the different tests for the alkali under consideration, solutions of potas- sium chloride and of potassium nitrate were chiefly employed. The vulgar fractions used indicate the fractional part of a grain of anhy- drous potassium oxide under the form of the salt employed, in solu- tion in one grain measure of pure water ; and the results, unless otherwise stated, refer to the behavior of one grain of the solution, treated in the manner above described. 76 POTASSIUM OXIDE. — POTASH. 1. Chloride of Platinum. Platinic chloride throws down from solutions of salts of potas- sium, when not too dilute, a yellow precipitate of the double chloride of platinum and potassium, 2KC1 ; PtCl^, which, either immedi- ately or after a very little time, becomes converted into beautiful octahedral crystals. Solutions of the free alkali should be treated with slight excess of hydrochloric acid, before the addition of the reagent. From dilute solutions, the presence of a little free hydro- chloric acid, or of strong alcohol, facilitates the formation of the precipitate. The precipitate is soluble in about one hundred and eight parts by weight of pure water at the ordinary temperature, but it is much more freely soluble in hot water; it is somewhat less soluble in water containing a trace of hydrochloric acid, and almost wholly in- soluble in absolute alcohol. One part by weight of anhydrous potas- sium oxide or its equivalent in the form of a salt, yields 5.2 parts of the double salt. 1. Jq- grain of potassium oxide in the form of potassium chloride, in solution in one grain of water, yields with the reagent an im- mediate yellow crystalline precipitate, which very soon increases to a copious deposit. On stirring the mixture with a glass rod, it leaves lines of crystals where the rod has passed over the watch-glass. The same amount of potassium oxide in the form of nitrate, yields about the same results. 2. Y^ grain as chloride : crystals are immediately perceptible, and soon there is a fine crystalline deposit, which under the micro- scope presents the appearance represented in Plate I., fig. 1. When the potassium is in the form of nitrate, the precipitate is a little more slow in forming, and does not become quite so abundant. grain : in about two minutes there is a perceptible precipitate, and after a little time a quite good crystalline deposit. If the mixture be stirred, it yields streaks of granules. From the nitrate of potassium, the precipitate is more slow to form and does not become so abundant, the crystals being confined to the border of tlie mixture. A l-200th solution of the nitrate yields only about the same results as a l-250th solution of the chloride. 1 25 SPECIAL rilEMICAI. PIKJPERTItiS. 77 4. ijJ^Q grain : in about ten minutes crystals appear around tlie mar- gin of the mixture; these increase, and in about three-quarters of an liour there is a quite satisfactory deposit scattered through tlie body of the drop. Stirring the mixture does not seem to lacilitate the formation of the deposit. The forms of the crys- tals are much the same as illustrated above. A l-400th solution of the nitrate yields only about the same reaction as a l-500th solution of the chloride. A l-500th ho- lution of the nitrate, however, will yield a perceptible deposit after standing about an hour. In these experiments, concen- tration of the mixture from evaporation was guarded against, perhaps, however, not perfectly. Harting placed the limit of this test, when applied to a solution of the nitrate, at one part of potassium oxide in 205 parts of water. {Gmelins Handbook, iii. 15.) Lassaigne fixed the limit for sul- phate of potassium at one part of the alkali in 200 parts of water. {Jour. Chim. Med., 8, 527.) And for the acetate, Pettenkofer placed the limit at one part of potassium oxide in 500 parts of water, after standing from twelve to eighteen hours; but he states, when common salt is present, the reaction is limited to one part of the alkali in 100 parts of water, or even less. {Gmelin, x. 276.) Neither of these observers, however, states the quantity of solution employed in the experiment. Fallacy. — Chloride of platinum also produces a similar yellow crystalline precipitate in solutions of salts of ammonium. The ab- sence of these salts should, therefore, be established before concluding that the precipitate consists of the potassium compound. This may be done by adding some hydrate of lime or caustic potash to a small portion of the suspected solution and heating the mixture, when if it contain an ammoniacal salt the odor of this alkali will be evolved. Or, the precipitate produced by the platinum reagent may be heated to redness, when the potassium compound will leave a residue of chloride of potassium and metallic platinum, which, when treated with a small quantity of hot water and the filtered liquid acted upon by a solution of nitrate of silver, will yield a white precipitate of chloride of silver, due to the presence of the alkaline chloride; whereas the ammonium compound will leave upon ignition a residue of only metallic platinum, which, of course, will yield no precipi- tate with nitrate of silver. 78 POTASSIUM OXIDE. — POTASH. 2. Tartaric Acid, and Sodium Tartrate. Tartaric acid, when added in excess to somewhat strong solutions of potassium compounds, produces a white crystalline precipitate of acid tartrate of potassium, KH.CJiJJQ. From somewhat dilute solutions the precipitate is slow in appearing ; in such cases, its for- mation is much facilitated by agitation, as also by the addition of alcohol. The precipitate is soluble in the mineral acids, and free alkalies and their carbonates; if, therefore, either of these substances be present in excess, the formation of the precipitate will be en- tirely prevented. The precipitate is insoluble in free tartaric and acetic acids. When a solution of a potassium salt is treated with free tartaric acid, it is obvious that the acid of the salt is set free : thus, KNOgH- HaC^HPe^ KHC4HPg + HNO3. The acid thus set free may in a measure redissolve the potassium tartrate produced by the reagent, especially if it be one of the stronger acids. This elimination of the acid may be prevented by using the reagent in the form of a solution of the acid tartrate of sodium (NaHC4H406), as first recommended by Mr. Plunkett. {Chem. Gaz., xvi. 217.) Under these conditions, there would simply be an interchange of the metals, the sodium eliminated from the tartaric acid combining with the acid radicle set free from the potassium salt. This reagent is readily prepared by dividing a strong solution of tartaric acid into two equal parts, exactly neutralizing one of them with pure carbonate of sodium, and then adding the other. In the following investigations a very strong solution of free tar- taric acid, and a saturated solution of the acid tartrate of sodium, were employed as the reagents. 1. _i_ grain of potassium oxide in the form of chloride or nitrate, yields with free tartaric acid an immediate crystalline precipi- tate, which soon increases to a very good deposit. The tartrate of sodium produces much the same results, except, perhaps, the precipitate is somewhat more copious ; the general forms of the crystals, however, are quite different. The neutral tartrate of sodium produces no precipitate. 1 100 grain : crystals immediately begin to separate, and after a little time there is a good crystalline deposit. Plate I., fig. 2, represents the usual forms of the crystals produced by free tar- SPECIAL CHEMICAL PROPERTIES. 79 taric acid. Acid tartrate of sodiiuii produces a somewhat more abundant precipitate. 3. Y^ grain : in a lew moments crystals appear, and very soon there is a qnitc satisfactory deposit. Witli the tartrate of sodium and chloride of pottussium, the precij)itate is somewhat more prompt in appearing. Plate I., fig. 3, represents the forms of crystals usually produced by the sodium reagent. 4. y^ grain as chloride: within a few minutes granules appear; these soon become crystalline, and after a little time there is a quite satisfactory crystalline and granular deposit. From the nitrate of potassium the precipitate separates much more slowly, and is chiefly confined to the border of the mixture ; under the microscope, however, the reaction is quite satisfactory. After standing about half an hour, either of these solutions yields a quite good deposit of crystals having the forms illustrated above. When acid tartrate of sodium is employed as the reagent, the precipitate is much more prompt in appearing, particularly from a solution of potassium chloride. 5. -y-g-jj- grain as chloride: after about ten minutes, small granules form along the margin of the mixture, and after some minutes more, there is a quite distinct granular and crystalline deposit. With the sodium reagent, granules and crystals appear within about four minutes, and there is soon a very satisfactory de- posit. 6. YoVo gi'^iii of the chloride, with acid tartrate of sodium : in about five minutes, crystals are just perceptible; and in about ten minutes, the deposit is quite distinct, but confined to the border of the drop. The crystals have the forms illustrated above, some of them being quite large. From the above statements it is obvious that the chloride of potassium is the most favorable form of the alkali for the application of either of the above reagents. Pettenkofer placed the limit of the reaction of free tartaric acid, for solutions of the acetate of potassium, at one part of the anhydrous alkali in from 700 to 800 parts of water, after standing from twelve to eighteen hours. Fallaey. — These reagents also produce similar crystalline pre- cipitates from solutions of ammonia and its salts. The absence of this alkali may be established in the manner indicated under the preceding test. 80 POTASSIUM OXIDE. — POTASH. 3. PicriG Acid. A strong alcoholic solution of Picric or Carbazotic acid, when added in excess to solutions of caustic potash and of potassium salts, produces a yellow precipitate of picrate of potassium, KCgH2(N02)30, which is insoluble in excess of the precipitant and in alcohol. The precipitate contains the equivalent of 17.66 per cent, of anhydrous potassium oxide. 1. gL grain of potassium oxide in the form of chloride or nitrate, yields an immediate amorphous precipitate, which in a few moments becomes converted into a mass of long, regular, yellow crystalline needles, some of which extend entirely across the drop of liquid. 2. Yoo gi"9'i^ • crystals immediately begin to form, and in a very little time the drop becomes a mass of very long, slender, yellow needles, Plate I., fig. 4. 3. 2^0" graiii '• i^^ ^ few moments, crystals begin to form, and after a little time, a very good deposit of long needles. 4. g-^ grain : much the same results as in 3. From the nitrate of potassium the precipitate is not so prompt to form, nor is it as abundant as in the case of the chloride. 5. YTo gi'^iii ill the form of chloride, yields after a little time a per- fectly satisfactory crystalline deposit. 6. Y^Vo gi^ain : after a few minutes, crystalline needles appear along the margin of the drop ; after about fifteen minutes, the deposit becomes quite satisfactory, especially when examined by the microscope. In applying this reagent it should be added in large excess. Thus, ten grains of a l-500th solution of potassium oxide, when acted upon by a drop or two of the reagent, yield no precipitate, at least for some time ; but if an equal volume of the reagent be added, it produces a precipitate within a few moments. Fallacies. — Picric acid also throws down from solutions of ammo- nia and very strong solutions of caustic soda yellow crystalline pre- cipitates. The microscope, however, will readily enable us to distin- guish the potassium precipitate by its crystalline form from that of either of these substances. (Compare figs. 5 and 6, Plate I.) The reagent also produces yellow precipitates, some of which are crystal- SPECIAL CHEMK AI, IMIOPERTIES. 81 line, with many organic substances, especially the vegetable alkaloids. So, also, it occasions ])recipitates with certain other metals ; but the absence of these, as already })oiiited out, should he estal)lishod before apply iuii- the test. Ill applyinu' this test it must be remembered that a very strong alcoholic solution of the reagent, when added in certain projiortiou to pure water y may yield a yellow crystalline precipitate of free picric acid. The forms of these crystals, however, readily distinguish them from the potassium compound. In a l-500th or stronger solution of tiie alUali, this distinction is very apparent to the naked eye; and in more dilute solutions, it is readily established by the microscope. Other Reactions of Potassium Compounds. — L. de Koninck has recently shown that if a solution of a potassium compound be treated with excess of about a ten per cent, solution of Sodium Ni- trite containing a little Cobaltous Chloride and Acetic Acid, the potassium is precipitated as the double nitrite of j^otassium and cobalt, the reaction being more sensitive than that of platinic chlo- ride. {Zeit.f. Anal Chem., 1881, 390.) We find that a drop of a 1— 100th solution of potassium oxide in the form of a salt yields with a drop of this reagent an immediate, bright yellow, granular or crystalline precipitate.- With a l-oOOth solution the precipitate will appear in a very little time; and it may be obtained after a time from even a 1— 1000th solution of tlie alkali. The precipitate is insoluble in hydrochloric acid, even when added in large excess ; it is also insoluble in sulphuric and nitric acids. This test is simply a modification of the well-known reaction for cobalt by potassium nitrite. The composition of the precipitate, ac- cording to Prof. Sadtler, is GKNO^; Co^GNOg + Aq. The reagent produces a similar, but less sensitive, reaction with salts of ammo- nium. The reaction is not interfered with by the presence of salts of calcium, magnesium, iron, aluminium, or of zinc. Hydrofluosilicic Acid in excess produces in strong solutions of potassium compounds a transparent gelatinous precipitate of the silicofluoride of potassium, which is insoluble in hydrochloric acid. In concentrated solutions this reaction is very satisfactory. A 1— 50th solution of the alkali in the form of chloride yields, after a time, only a slight flocculent deposit. Perchloric Acid produces in similar solutions a white erystal- 6 82 POTASSIUM OXIDE. — POTASH. line precipitate of potassium perchlorate. So, also, a concentrated solution of Sulphate of Aluminium, when added to concentrated solutions of the alkali previously acidulated with hydrochloric acid, precipitates crystals of the double sulphate of aluminium and potas- sium, or common alum : K2S04,Al23S04+24H20. As a delicate reagent for the precipitation of potassium salts, M. Carnot recommends to dissolve one part (0.5 gramme) of SuBNi- TEATE OF Bismuth in a few drops of hydrochloric acid ; and, on the other hand, about two parts (1 gramme) of crystallized Hyposul- phite OF Sodium in a few cubic centimetres of water. The second solution is added to the first, and then strong alcohol added in large excess. This mixture, or reagent, produces in solutions of potassium salts a yellow precipitate of the double hyposulphite of bismuth and potassium: Bi^SSPsj 3KSA+2H2O. {Chem. News, Sept. 1876, 85, 120.) This reaction, it is said, is not interfered with by the presence of other bases. Spectrum Analysis. — This, as first applied by Professors Kir- choff and Bunsen, is by far the most delicate method yet discovered for the recognition of potassium, — as well as of sodium and many other volatile metals. It consists in introducing a small portion of the caustic alkali, or any of its salts containing a volatile acid, into the flame of a Bunsen gas-burner and allowing the rays of the col- ored flame to pass through a prism. The refracted rays are then examined by means of a small telescope, when, in the case of potas- sium, two distinct lines, one having a red color and the other indigo- blue, will be observed, which are characteristic of this metal. The authors of this method estimated that it would reveal the reaction of the 65,000th part of a grain of potassium, and the 195,000,000th part of a grain of sodium. (For the details of this method, see Quart. Jour. Chem. Soc, Oct. 1860; also, Fresenius's Qualitative Analysis, London, 1877.) Although spectrum analysis has very largely extended the scope of chemical research, enabling us in a few seconds to detect the pres- ence of the most minute traces of many metals, and bringing to light substances of which heretofore we had no knowledge ; yet, as it gives no indication whatever as to the quantity of the substance present, it is still doubtful whether it will be of any practical value in chemico- legal investigations, at least for the detection of the fixed alkalies, SEPARATION FKOM OR(;ANIC MIXTURES. 83 since thoi•. Nh.0. 1.428 ;W.22 1.37a 2(;.o9 1.327 22.% 1 208 20.5r) 1.277 18.73 1.257 l"i-92 1.228 14.50 „ ., Percentage op- ^'■- NiuO. 1.194 12.00 1.1(;8 10.87 1.123 8.40 1.094 0.04 1.007 4.83 1.033 2.41 T.OlO 1.20 The mits of sodium are colorles.s, unless containing a colored acid. They are readily soluble in water, and more disposed than the corresponding compounds of potassium to unite with water of crystallization. The crystallized normal carbonate {protoearbon- aie), as also several other salts, contains ten molecules of water of crystallization. Many of its salts speedily effloresce wdien exposed to the air. Special Chemical Properties.— When caustic soda, or any of its salts, is heated in the inner blow-pipe flame, it communicates a strong yellow color to the outer flame, even when only a minute quantity of the alkali is present. The presence of potassium com- pounds, even in large quantity, does not obscure this reaction. The same coloration is developed when an alcoholic solution of the alkali is burned. By spectrum analysis, as already indicated, the reaction of the merest traces of sodium may be recognized. On account of the free solubility of the compounds of sodium, there are but few reagents that precipitate it even from concentrated solutions. In fact,— besides the coloration of flame,— antimoniate of potassium and Polarized Light are about the only tests at pre.sent known whereby small quantities of this alkali can be recognized. In the following investigations solutions, of pure caustic soda were employed. The fractions refer to the fractional part of a grain of the anhydrous alkali, NaP, in solution in one grain of water; and the results, to the behavior of one grain of the solution. 1. Ifetantimonate of Potassium. A solution of this reagent is prepared by supersaturating warm water with the pure salt and filtering the liquid when perfectly cold. The solution should always be freshly prepared when required for use. Metantimonate of potassium throws down from somewhat con- 86 SODA. centrated solutions of caustic soda and of its neutral salts a white crystalline precipitate of sodium metantimonate, XaSbOg. The forms of the crystals produced depend very much upon the strength of the solution. If the solution has an acid reaction, it should be carefully neutralized with potassium carbonate before the addition of the reagent, since otherwise free metantimonic acid or acid metanti- monate of potassium may be precipitated. The reaction of the re- agent is not prevented by the presence of moderate quantities of salts of potassium, except the carbonate, in which the sodium compound is more readily soluble than in pure water. 1. -^ grain of sodium oxide, in one grain of water, yields with the reagent au immediate deposit of small granules and rectangular plates ; at the same time irregular and tooth-shaped crystals, as represented in the upper left portion of Plate II., fig. 1, float upon the surface of the mixture. 2. 1 grain yields an immediate crystalline precipitate, consisting principally of small elongated rectangular plates, as represented in the lower portion of Plate II., fig. 1. 3. _^_ grain : an immediate deposit, consisting chiefly of small octa- hedral crystals, as illustrated in the right-hand portion of fig. 1, Plate il. 4. .^4-g- grain : almost immediately very small granules appear, and soon there is a quite good crystalline deposit of small plates and octahedrons. 5 _i^ o-rain : after a little time, small crystals can be seen with the microscope ; after several minutes, a very satisfactory deposit to the naked eye. If the mixture be stirred with a glass rod, it yields lines of granules along the path of the rod, and a more copious deposit. 6. yJ=j5-q grain : on stirring the mixture, crystals become perceptible to the microscope in about five minutes ; in about fifteen min- utes, they become quite obvious to the naked eye; and after about half an hour, there is a perfectly satisfactory crystalline deposit. Metantimonate of potassium fails to precipitate potassium com- pounds and ammonia, even from concentrated solutions ; but it pro- duces precipitates in solutions of many other metals : the absence of these, therefore, must be established before concluding that the pre- cipitate consists of the sodium compound. SPKCIAI. CHHMK'AT- PROPERTIES. 87 2. Polarized Light. Tliis test, which was tirst suggested by Prof. Andrews {Chemical Gaz.f X. 378), is founded upon the fact that platinic chloride, and also tlio doul)le chloride of potassium and i)latinuni, when placed in the dark Held of the polariscopc, have no depolarizing action, whereas the double chloride of sodium and platinum possesses this property in a remarkable degree. To apply this test, its author recommended the following method. Having removed other bases by the ordinary methods and converted the alkalies into chlorides, a drop of the solution is placed on a glass slide and a very small quantity of a dilute solution of the chloride of platinum added, avoiding as far as possible an excess. This mix- ture is evaporated by a gentle heat till it begins to crystallize, then placed in the field of a microscope furnished with a good polarizing apparatus. On turning the analyzer till the field becomes perfectly dark, and carefully excluding the entrance of light laterally, the crystals remain invisible if only the potassium compound or the re- agent alone be present, while the presence of the slightest trace of sodium is at once indicated by the beautiful display of color of its platinum double salt, 2NaCl ; PtCl^. Prof. Andrews states that in this manner he obtained a distinct reaction from a quantity of chloride of sodium representing only about the l-825,000th of a grain of the anhydrous alkali. In applying this method, instead of evaporating the mixture by the application of heat, it is best to allow it to evaporate sponta- neously, as it thus yields much larger crystals of the double sodium salt. 1. Yrro gi'ain of sodium oxide in the form of chloride, in one grain of water, when treated with a very small quantity of the reagent and allowed to evaporate spontaneously, leaves a good deposit of long, irregular crystals of the double salt, Plate IL, fig. 3. This deposit, under the polariscope, furnishes a beautiful display of prismatic colors. 2. y-ofoTo grain ' quite a number of fine crystals, which in the field of the polariscope yield very satisfactory results. 3. rooTool) grain: usually yields several quite distinct and satisfactory crystals. Sometimes the deposit is in the form of thread-like groups, which, when broken up by the point of a needle, form 88 SODA. small crystalline plates. In this manner, these thread-like masses may readily be distinguished from depolarizing shreds of dust, which are sometimes present. 4. -goT-ToT g'^^ii • with the least possible quantity of reagent, yields a few small depolarizing crystalline plates. Even the 1-1, 000,000th of a grain of the alkali will sometimes yiekl quite distinct results. Before applying this test, the examiner should be certain that any potash present is entirely converted into chloride, otherwise he may be led into error. Picric Acid. — It is usually stated by writers on this subject that this reagent produces no precipitate even in concentrated solutions of sodium hydrate, whereby this alkali is distinguished from potassium hydrate; but this is not the fact. Thus, one grain of a l-25th so- lution of the former alkali yields with the reagent, within a little time, a quite copious crystalline deposit, Plate I., fig. 6 ; and a similar quantity of a 1-lOOth solution yields, after a time, a quite distinct crystalline reaction. Solutions but little stronger than the first men- tioned become converted into a mass of crystals by the reagent. The crystalline form of the sodium precipitate will usually serve to distinguish it from the potassium compound, as also from that produced in solutions of ammonia. Tartaric Acid produces in very coneentrated solutions of the alkali, especially if the mixture be stirred, a white crystalline pre- cipitate of acid tartrate of sodium. In one grain of a 1-lOth solu- tion of the alkali the reagent produces, on stirring the mixture, after a few minutes, a mass of groups of bold crystals, Plate II., fig. 2. One grain of a l-25th solution, under the same circumstances, yields, after ten or fifteen minutes, a quite satisfactory crystalline deposit. If this mixture be not stirred, it fails to yield a precipitate even after several hours. Solutions but little more dilute than this fail to yield a precipitate under any condition whatever, even after many hours. Platinic Chloride fails to precipitate even the most concen- trated solutions of sodium compounds. As a micro-chemical test for sodium, A. Streng has recently ad- vised (1883) to treat a drop of the solution with Uranium Acetate, when either immediately, or on spontaneous evaporation of the liquid, yellow tetrahedral crystals of uranium sodium acetate are formed. AMMONIA. 89 Tlu>se crystals contain only G.6 per cent, of sodium, and are readily distini:;uislicd from the rhombic crystals of uranium acetate by their action on polarized lii^ht. {Jour. Cheni. Soc. Abstr., March, 1884, 366.) We have found this method serve for the detection of very minute quantities of sodium salts. Separation from Organic Mixtures. — Caustic soda may be separated from organic mixtures in the same manner as already directed for the recovery of caustic potash (ante, 83). Since, according to the researches of E. Donath, commercial caustic soda sometimes contains minute quantities of arsenic, even to the extent of 0.16 per cent, of arsenic acid, this contamination might sometimes give rise to embarrassment in poisoning by the caustic alkali. {Jour. Chem. Soc. Abstr., 1881, 856.) Section III. — Ammonia. General Chemical Nature. — Ammonia, in its pure state, is a gaseous compound of Xitrogen and Hydrogen, XHg, having a very pungent odor and powerfully alkaline reaction. The gas is readily absorbed by water, which is thereby increased in volume and dimin- ished in density ; at a temperature of 10° C. (50° F.), according to Davy, this fluid takes up about 670 times its volume of the gas, and then has a density of 0.875. A solution of this kind constitutes common aqua ammonise, and is usually regarded as a hydrate of ammonium, XH^jHO. According to Sir H. Davy, the following table exhibits the percentage by weight of ammonia gas in pure aqueous solutions of different specific gravities : STRENGTH OF AQVEOUS SOLUTIONS OF AMMONIA. Sp.Gr. Percentage g^ g^_ Per^^ntage 0.875 32.30 0.938 15.88 0.885 29.25 0.943 14.53 0.900 26.00 0.947 13.46 0.905 25.37 0.951 12.40 0.916 22.07 0.954 11.56 0.925 19.54 0.959 10.17 0.932 17.52 0.963 9.50 Aqua ammonise, when pure, is colorless, has a peculiar powerfully pungent odor, and a strong alkaline reaction, immediately restoring the blue color of reddened litmus-paper ; on warming the blued paper, the red color reappears, from the dissipation of the alkali. 90 AMMONIA. On heating a solution of ammonia, the gas is rapidly expelled with effervescence; when the liquid is evaporated to dryness it leaves no residue, unless foreign matter be present. The salts of ammonia, usually named ammonium salts, are color- less, and readily volatilized upon the application of heat. With few exceptions, they are freely soluble in water. The fixed caustic al- kalies readily decompose them, with the evolution of free ammonia. ^ Special Chemical Properties. — Solutions of free ammonia are readily recognized by their peculiar odor. The salts of this base, when heated on platinum foil, are completely dissipated, unless they contain a fixed acid or foreign matter, in which respect they differ from the salts of the fixed alkalies. When their solutions are treated with potassium or sodium hydrate, or with hydrate of lime, and the mixture gently warmed in a test-tube, the presence of the ammonia eliminated by the decomposition may be recognized by its odor ; as also by its alkaline reaction upon moistened reddened litmus-paper ; and also by the production of white fumes of ammonium chloride when a glass rod moistened with dilute hydrochloric acid is held over the mouth of the tube. By suspending a slip of moistened reddened litmus-paper within the tube and closing its mouth, the presence of very minute traces of the alkali may, at least after a time, be recognized. The behavior of solutions of ammonia and of some of its salts, when treated with nitrate of silver and corrosive sublimate, has already been pointed out [ante, 73). When the alkali is added in excess to solutions of salts of copper, the liquid assumes a charac- teristic blue color. In the following investigations of the reactions of ammonia, so- lutions of pure chloride of ammonium were employed. The frac- tions refer to the amount of gaseous ammonia present in one grain of the solution, which was the quantity employed for each reaction, unless otherwise stated. 1. Plaiinio Chloride. This reagent produces in neutral and slightly acid solutions of ammonia a yellow octahedral crystalline precipitate of the double chloride of ammonium and platinum, 2NH4CI ; PtCl^, which is but sparingly soluble in diluted mineral acids, and in the free alkalies. In appearance the precipitate closely resembles the corresponding SrEClAL CIIKMU.AL I'UOl'KUTI KS. 91 coinpoiiiul of potassliiin. A given quantity ofanitnonia in tlie form of c'lilorido yields with the reagent a larger (juantity ectively. But a case has already been mentioned in which a dose of two ounces did not prove fatal until after a period of eight days. And two in- 140 HYDROCHLORIC ACID. stances are recorded in which death did not occur until eight weeks had elapsed. (Orfila, Toxicol., i. 221 ; and Taylor on Poisons, 291.) Fatal Quantity. — In a case reported by Dr. Budd, half a fluid- ounce of the acid, taken with suicidal intent, proved fatal in eighteen hours to a woman aged sixty-three years. {Lancet, July, 1859, 59.) This seems to be the smallest fatal dose yet recorded. In this case the following symptoms were observed : vomiting, collapse, whiten- ing and abrasion of the lips, mouth, and fauces ; also, swelling of the throat and inability to swallow, with stridulous breathing and thick inarticulate voice, and intense epigastric pain. Death, without loss of consciousness until near the last, took place by exhaustion. On the other hand, Dr. Toothaker reports a case in which a man recovered after having taken, by mistake, one ounce of officinal muri- atic acid. It was immediately succeeded by violent burning of the mouth and fauces, a sense of suffocation, and spasms. After the administration of olive oil, followed by a mixture of milk and cal- cined magnesia, copious vomiting ensued. The strength of the patient became greatly reduced, and the extremities so cold as to re- quire the application of sinapisms. The next day there was pain and costiveness, but these were relieved by a dose of castor oil. After this, the patient very gradually recovered. [Boston Med. and Surg. Jour., XV. 270.) The following case of recovery is reported by Dr. Stevenson (Guy's Hosp. Rep., xiv. 270). A man drank half a wineglassful of strong hydrochloric acid, supposing it to be brandy. When taken to the hospital very soon after, the patient was almost asphyxiated, foamed at the mouth, and breathed with great difficulty. The mouth and fauces were clogged with tough, viscid mucus, and the tongue and adjacent parts appeared excoriated. His speech was thick and indistinct ; he complained of great dryness of the mouth and fauces, and of a severe burning pain in the throat, more particularly in the stomach. Vomiting had occurred several times on his way to the hospital. Olive oil was administered, and then several raw eggs, the latter with much relief. The next day only slight signs of the local action of the acid were visible about the mouth and lips; but he experienced great thirst, with a burning pain in the throat. Six days after taking the acid the pain in the throat had much diminished, and the next day the patient was discharged nearly well. In another case recovery took place after about a quarter of an ordinary tumbler- CIIKMICAI. I'ROl'KllTlKS. Ill fill of tlie commercijil acid luul l)oen tuki-n at a drau^dit by a woman. In this instance the lips, month, and t()ni.aie \v(!re deprived of their epithelinm, red, and inflamed; tlie iances and throat were mneh swollen, and upon the velum and pharynx there was an exudation closely resemblini!; the false mend)rane of diphtheria. Treatment. — The proper chemical antidote is either chalk or calcined magnesia, or a dilute solution of an alkaline carbonate. If neither of these substances be at hand, milk, white of egg, oil, or demulcents of any kind should be freely administered. In every respect the treatment is the same as in sulphuric acid poisoning {ante, 101). Post-mortem Appearances. — In acute cases, the mucous mem- brane of the mouth, throat, and oesophagus is usually more or less softened, and of a whitish or brownish color. The lining membrane of the stomach is generally highly inflamed, softened, and readily separated. In the case cited above which proved fatal in five hours and a half, the lower portion of the oesophagus had the appearance of being charred. The mucous membrane of the stomach jiresented black elevated ridges, as if charred, while the intervening furrows were of a scarlet-red color; similar appearances were observed in the duodenum and jejunum. In Dr. Budd's case, the mucous mem- brane of the mouth, fauces, and larynx was whitened and softened, the soft palate and tonsils were swollen, and a portion of the lining membrane of the larynx was entirely removed. In this case, the local action of the poison was chiefly confined to the parts just mentioned. In the case cited by Orfila which did not prove fatal until after a period of eight weeks, the lining membrane of the throat and oesophagus was thickened and in a state of suppuration. The stomach was entirely disorganized, softened, and presented several round perforations having thickened and inflamed edges; the py- loric orifice was thickened and contracted. In the small intestines, the mucous membrane throughout its extent was thickened, injected in patches, and of an arborescent appearance ; the large intestines were healthy, and contained a brownish, fetid liquid. Chemical Properties. General Chemical Nature. — Anhydrous hydrochloric acid is a gaseous compound of hydrogen and chlorine, HCl. It is a 142 HYDROCHLORIC ACID. colorless, powerfully suifoeating gas, having a density of 1.26 ; when it comes in contact with the air it produces white fumes, due to its strong affinity for water. Hydrochloric acid, or muriatic acid of the shops, is an aqueous solution of the gaseous compound, of which, according to Davy, water at a temperature of 4.5° C. (40° F.) will absorb 480 times its volume, increasing both in volume and in density. Such a solution has a specific gravity of 1.21, and contains nearly 43 per cent, of anhydrous acid. The solution is colorless, has a highly irritating odor, and yields dense white fumes when a rod moist- ened with ammonia is presented to it. If the solution be heated, a portion of the anhydrous acid is readily expelled in the form of vapor. The following table, according to E. Davy, exhibits the per- centage by weight of the anhydrous acid in pure aqueous solutions of different specific gravities : STRE^TQTH OF AQUEOUS SOLUTIONS OF HYDROCHLORIC ACID. Sp. Ge. 1 Percentage of Sp. Gr. Percentage op Sp. Gk. Percentage of HCl. HCl. HCl. 1.21 42.43 1.14 28.28 1.07 14.14 1.20 40.80 1.13 26.26 1.06 12.12 1.19 1 38.38 1.12 24.24 1.05 10.10 1.18 : 36.36 1.11 22.22 1.04 8.08 1.17 1 34.34 1.10 20.20 1.03 6.06 1 1.16 32.32 1.09 18.18 1.02 4.04 ! 1.15 30.30 ! ; 1.08 16.16 1 1.01 2.02 Hydrochloric acid as found in the shops has usually a density of about 1.15, and a more or less yellow color, due to the presence of free chlorine gas or chloride of iron, or both. It is also liable to be contaminated with sulphuric and sulphurous acids, arsenic, nitric acid, and some of the lower oxides of nitrogen, lead, and common salt ; occasionally other impurities are present. Liquid hydrochloric acid is readily decomposed by iron, zinc, and the stronger electro-positive metals, with the formation of a chloride of the metal and the evolution of hydrogen gas. But it is unacted upon by metallic copper, even at the boiling temperature : in this respect it differs from nitric and sulphuric acids. It is readily decomposed by the basic metallic oxides and their carbonates, with SPECIAL, CHEMICAL PROPERTII-IS. 1 to the Ibnnati^)!! of a cliloride ami water, and, in tlie case of a carbonate, the evolution of carbonic acid. The mils resulting from this acid, or chlorides as they are termed, are mostly colorless, and, with tiie exception of tiie chlorides of silver and lead and mercurous chloride, are freely soluble in water. Wlu-n heated with diluted sulphuric acid, the soluble chlorides, to- gether with w\ater, are readily decomposed, giving rise to a sul- phate and evolving hydrochloric acid gas; tjjus : 2NaCl + H2SO^ = Na2SO,-l-2HCl. Special Chemical Properties. — When hydrochloric acid is heated with black oxide of manganese, both compounds undergo de- composition with the formation of the chloride of the metal and the evolution of free chlorine ; thus: MnOo+ 4HCl = 2H20+ MnClg -j-Clo. The presence of the eliminated chlorine maybe recognized by its" peculiar odor, its bleaching properties, and, if not in too minute quantity, its greenish-yellow color. Its bleaching property is readily determined by exposing to it a slip of moistened litmus-paper, or a slip of paper moistened with a solution of indigo; if a slip of Btarch-paper be moistened with a solution of iodide of potassium and exposed to the gas, it immediately acquires an intense blue color, which after a time, under the continued action of the gas, is partially or wholly discharged. If the evolved gas be brought in contact with a drop of a solution of nitrate of silver, or be conducted into a solution of this salt, it produces in the first instance a white film, and in the second a white precipitate, of chloride of silver, having the properties to be presently described. When a soluble chloride is mixed with black oxide of manganese and heated with sulphuric acid, previously diluted with about an equal volume of water, the whole of the chlorine is eliminated in its free state. The reactions in this case, taking chloride of sodium as the type, are as follows: 2XaCl -f MnO.+2H.SO, = MnSO,+ Na,SO/-^ 2HoO -f CI,. The presence of the evolved chlorine may be determined by the methods just indicated. If this decomposition be conducted in a thin watch-glass covered by an inverted glass containing slips of the moistened test-papers, the fractional part of a grain of the salt will yield satisfactory results. Since the compounds resulting from hydrochloric acid are, with very few exceptions, freely soluble in water, there are but few re- agents that precipitate it from solution. In the following investiga- 144 HYDEOCHLORIC ACID. tions in regard to the behavior of solutions of hydrochloric acid, pure aqueous solutions of the free acid were chiefly employed. The fractions indicate the amount of the anhydrous acid in solution in one grain of liquid, and the results, the behavior of one grain of the solution. 1. Silver Nitrate. IS^itrate of silver throws down from solutions of hydrochloric acid, of chlorides, and of free chlorine a white amorphous precip- itate of chloride of silver, AgCl, which is readily soluble in ammo- nia, but insoluble in nitric and sulphuric acids ; it is also readily soluble in cyanide of potassium, but insoluble in the fixed caustic alkalies. When exposed to light, chloride of silver soon acquires a purple color ; on the application of heat, it readily fuses, without decomposition, to a yellowish liquid, which on cooling solidifies to a hard, compact, nearly colorless mass. 1. yi-g- grain of anhydrous hydrochloric acid, in one grain of water, yields a very copious, curdy precipitate, 2. Y^oT gi'^iii • luuch the same results as 1. 3. xo'.'ooT gi'ain yields a very good flocculent precipitate. The solur tion strongly reddens litmus-paper. 4. 5-o,Toir gi'ain : a very satisfactory deposit. The solution, after a time, slightly reddens litmus-paper. 5. T-Q-o-iWo" g^^^'ii • i^ ^ fsw moments, a distinct cloudiness, which soon becomes well marked. 6. -5-0-0/roT grain yields, after a little time, a slight opalescence. Nitrate of silver also produces in solutions of hydrocyanic acid, even when strongly acidulated, a white precipitate of cyanide of silver, which, like the corresponding chlorine compound, is soluble in ammonia (although less freely), and insoluble in nitric acid. But the cyanide of silver, when dried and heated in a reduction-tube, readily undergoes decomposition, with the evolution of an inflamma- ble gas, in which respects it differs from the chlorine salt. A more ready method of distinguishing between these acids is to treat a portion of the suspected solution with the mercury reagent described below. In neutral solutions, nitrate of silver produces precipitates with several other acids or elements. All of these precipitates, however, except that from hydrocyanic acid, unlike the chloride of silver, are readily soluble in nitric acid, at least in its concentrated state. So, SPECIAL CHEMICAL PROPERTIES. 145 again, the rea<;('nt is readily decomposed, with the production of a white precipitate, by a great variety of organic substances ; these pre- cipitates, however, like those just mentioned, are soluble in nitric acid. The chlorine may be recovered in a soluble form from the chloride of silver, by fusing the latter with a mixture of sodium and potassium carbonates, when the chlorine will be transformed into an alkaline chloride, readily soluble in water. 2. 3Iercurous Nitrate. This reagent produces in solutions of free hydrochloric acid and of chlorides a white amorphous precipitate of mercurous chloride, or calomel, HgjClg, which is insoluble in concentrated nitric acid. The precipitate is readily decomposed by the caustic alkalies, with the formation of a black compound of mercury. 1. _l_ grain of the anhydrous acid yields a very copious precipitate. 2. YW^ grain yields much the same results as 1. 3. Yo-.Vuir grain : a quite good precipitate. 4. ^u-.Vdit grain : a very satisfactory deposit. 5. ToiLTDTr grain yields, after a little time, a very distinct turbidity. ]\Iercurous nitrate also produces white precipitates in solutions of several other substances. When the reagent is added to a solu- tion of free hydrocyanic acid, as well as of a cyanide, one-half of the mercury is thrown down in its finely divided state as a dark- grav precipitate, while the other portion remains in solution in the form of cyanide of mercury. This reaction, as intimated above, readily serves to distinguish between hydrochloric and hydrocyanic acids, as well as between their salts. 3. Lead Acetate. Acetate of lead produces in solutions of hydrochloric acid and of its salts, when not too dilute, a white precipitate of chloride of lead, PbCL, which is somewhat less soluble in diluted nitric acid than in pure water. The precipitate is rather freely soluble in boiling water, from which on cooling it separates in its crystalline state. 1. Yw^ grain of hydrochloric acid, when treated with the reagent, crystals immediately begin to separate, and in a little time there is a quite good crystalline deposit, Plate III., fig. 1. 2. "2^ grain : on agitating the mixture with a glass rod, it yields, 10 146 HYDEOCHLORIC ACID. after a few minutes, some few crystals of chloride of lead, which are chiefly confined to the margin of the drop. Acetate of lead also produces white precipitate — usually, how- ever, amorphous — in solutions of several other acids, especially if the mixture be neutral. Moreover, the reagent is readily decomposed by various organic substances, with the production of a white amor- phous precipitate. Separation from Organic Mixtures. Suspected Solutions. — If the solution has a strong acid reaction, and is tolerably free from organic matter, a small portion of the liquid may be treated with a few drops of a strong solution of nitrate of silver. If this produces a white precipitate, which when washed in diluted nitric acid is insoluble in the stronger acid, there is little doubt of the presence of chlorine. If this examination indicates the presence of chlorine, it then becomes necessary, even should the solu- tion have a strong acid reaction, to determine whether it existed in the form of free hydrochloric acid or as a chloride. For this pur- pose, a portion of the solution is evaporated to dryness and gently ignited, when if it leaves no saline residue it is quite certain that the acid was uncombined. Should, however, it leave such a residue, this is dissolved in water and tested for chlorine. If this element be absent, it is most probable that the acid was free : however, a mixture of a chloride, as common salt, and excess of sulphuric acid would, as heretofore pointed out in the consideration of the re- covery of sulphuric acid, yield upon evaporation a residue entirely free from chlorine. Whether these conditions really existed could be readily determined by treating a portion of the suspected solution with chloride of barium, when if it failed to yield a precipitate, or gave one readily soluble in nitric acid, the absence of sulphuric acid would be fully established. Should the suspected liquid on evaporation leave a residue con- taining a chloride, it then becomes necessary to ascertain whether the whole of the hydrochloric acid may have existed in that form. To effect this, a given portion of the liquid is neutralized by pure sodium carbonate, evaporated to dryness, the incinerated residue dissolved in water containing a little nitric acid, the chlorine precipitated by nitrate of silver, and the precipitate collected, washed, dried, and weighed : an equal volume of the liquid, without the addition of carbonate of SEPARATION FROM ORGANIC MIXTURES. 147 sodium, is then evaporated to dryness, the residue incinerated, and tlie chlorine precipitated, as in the previous operation, by nitrate oi' silver. It' the weight of the precipitate obtained by the former of these methods exceed the weiglit of that obtained by the latter, then a portion of the acid existed in its free state : the exact quantity of the acid thus present may, of course, be readily deduced from tiie ditference thus observed. For the separation of free hydrochloric acid from complex mix- tures containing organic solids, it has been proposed to heat the mix- ture, after the addition of water if necessary, to near the boiling temperature, then filter, and distil the filtrate at a gentle heat to the consistency of a thin syrup, the distillate being collected in a proper receiver. The liquid thus collected is then examined by the silver test. As, however, hydrochloric acid strongly adheres to organic matter, none of the acid, unless present in comparatively large quan- tity, may pass over into the receiver. Under these circumstances, Orfila recommended to treat the residue in the retort with a solution of tannin, filter, and then distil the filtrate, as before, to near dryness. From w^hat has already been stated, it is obvious that if the mixture thus distilled contained a chloride and free sulphuric acid, it would give rise to hydrochloric acid, which would appear in the distillate. This objection could, of course, be answered by testing a portion of the residue with chloride of barium. Contents of the Stomach. — Any solids present are cut into small pieces, and the mass, after dilution with distilled water if necessary, kept at near the boiling temperature for half an hour or longer, then strained, the strained liquid filtered, and then submitted to the process of distillation described above. If, however, an alkaline or earthy antidote has been administered, and the mixture has a neutral reaction, then a given portion of the filtered liquid is evaporated to dryness, the incinerated residue dissolved in water, and any chlorine present estimated in the form of chloride of silver. In these investi- gations it must be borne in mind that the gastric juice contains not only alkaline chlorides, but also, it is said, free hydrochloric acid ; and, moreover, that common salt, or chloride of sodium, is almost universally present, at least in minute quantity, in articles of food. The gastric juice, however, according to most observers, normally contains only the merest trace of the free acid ; but the chlorides exist in very notable quantity. 148 HYDROCHLORIC ACID. From the facts just stated, it is obvious that the detection of a mere trace of free hydrochloric acid, or of a chloride in minute quan- tity, would not in itself be any evidence of poisoning by this acid. If it be shown that the base of the chloride present corresponds to that of the antidote alleged to have been administered, this fact may materially assist in forming an opinion as to the true nature of the case. When the whole of the acid has been converted into a chloride by the administration of an antidote, it may be recovered in its free state by first evaporating the mixture to dryness, then distilling the incinerated residue with strong sulphuric acid, and collecting the evolved acid in a small quantity of water contained in a well-cooled receiver. For the detection of free hydrochloric acid in the contents of the stomach, L. Bouis advises {Ann. d'Hyg., 1874, i. 457) to add a small quantity of binoxide of manganese, and gently heat the mixture, when any hydrochloric acid present, but not common salt or a chloride, will evolve free chlorine, which may be recognized by its bluing action upon paper moistened with a solution of potassium iodide and starch paste. Or, the suspected contents may be heated with a little nitre, when any free hydrochloric acid present will give rise to aqua regia, while with common salt or a chloride no such change will take place. The presence of any aqua regia thus formed may be deter- mined by its solvent action upon gold-leaf, and from the amount of gold dissolved the amount of free hydrochloric acid can be calculated. By the latter method, L. Bouis states that he recognized a few centi- grammes of hydrochloric acid in the presence of a large quantity of liquid. From organic fabrics. — Stains produced by hydrochloric acid on articles of clothing, and like substances, may be examined by gently boiling the stained portion with pure water for some minutes, and testing the filtered liquid in regard to its reaction upon litmus-paper, and with a solution of nitrate of silver. When chlorine is thus dis- covered, it should be determined, in the manner already pointed out, whether it exists in the form of the free acid or simply as a chloride. As hydrochloric acid is volatile, it sooner or later entirely disappears from stains of this kind. Quantitative Analysis. — The quantity of free hydrochloric acid, or its equivalent in the form of a soluble chloride, is most QUANTITATIVK ANALYSIS. ] iU readily determined by precipitating it as chloride of silver. The solution is treated with a solution of silver nitrate as long as it yields a precipitate, and the niixtiire gently heated until the whole of the precipitate has deposited ; the precipitate is then collected on a small filter, thoroughly washed, dried, and weighed. Every one hundred parts, by weight, of chloride of silver thus obtained correspond to 25.43 parts of anhydrous hydrochloric acid, or about 81 parts of liquid acid of specific gravity 1.15; one fluid-drachm of the latter acid weighs about sixty-five and a half grains. 150 OXALIC ACID. CHAPTER III OXALIC ACID, HYDKOCYANIC ACID, PHOSPHORUS. Section I. — Oxalic Acid. History. — Oxalic acid, in its crystalline state, is an organic com- pound of the elements carbon, hydrogen, and oxygen, combined with water, its composition being C2H204,2H20. It is found in the common rhubarb-plant, wood-sorrel, and several other plants, and is occasionally met with in human urine, only, however, as an ab- normal product. For commercial purposes it is usually obtained by the action of nitric acid upon starch or sugar. In its uncombined state it is a white crystalline solid, having an intensely acid taste. From its close resemblance to sulphate of magnesium, or Epsom salt, it has on several occasions been fatally mistaken for that substance. Either alone, or in combination in a soluble form, it is a powerful poison, and has in several instances been administered as such ; but it has much more frequently been taken for the purpose of self- destruction. Symptoms. — The symptoms produced by oxalic acid depend not only on the quantity taken, but also, somewhat, on the degree of concentration under which it exists. When swallowed in large quantity and in a concentrated state, it produces an immediate burn- ing pain in the mouth and throat, succeeded by vomiting and intense pain in the stomach, and, as the case advances, great muscular pros- tration, with hurried respiration, pale and anxious countenance, cold and clammy skin, small and feeble pulse, and, in some instances, delirium and convulsions. The vomited matters have not unfre- quently contained blood. When the dose is not large or is much diluted, nothing more than a strongly acid taste may be experienced in the mouth and throat, and the pain in the stomach, as well as the vomiting, may be PHYSIOLOGICAL EFFECTS. 161 imu'h ilehivcd. Although early and continuous vomiting is a com- mon symptom, yet it has in some cases been entirely absent. In a case quoted by Dr. Christison, a man swallowed half an ounce of the i)()ison, dissolved in ten parts of water, without experiencing any p;iiii in the abdomen for six hours, and there was no vomiting for seven hours, except when emetics were administered. In most of the instances in which no vomiting occurred, tiie dose was either small or greatly diluted; but this symptom has been absent when the jioison was taken in large (quantity and in a concentrated state. A man, aged twenty-one years, swallowed with suicidal intent about an ounce of the poison. He instantly felt a burning sensation in the mouth, throat, and oesophagus, and intense pain in the stomach. He soon vomited, and when taken to the hospital complained of a burn- ing sensation along the course of the oesophagus and in the stomach ; there were lividity of the face and extremities, relaxation of the mus- cles, and the surface was cold and clammy ; the heart's action was irregular, and the sounds somewhat distant; respiration was natural; pulse extremely feeble ; tongue large, oedematous, and covered with thick, woolly fur; conjunctivae dusky; pupils natural. An emetic removed from the stomach a large quantity of green-looking fluid. After a time the patient appeared much better, and continued to im- prove until the fifth day, when he arose to relieve his bowels, and died almost immediately. {Lancet, Nov. 1860, 509.) In another case, a woman, aged twenty years, to destroy herself took a quantity of oxalic acid, and died from its effects within about twenty minutes. In a protracted case reported by Dr. C. T. Jackson {Boston Med. and Surg. Jour., xxx. 17), the following symptoms were ob- served. A man, aged thirty years, took in solution about one ounce of crystallized oxalic acid, mistaking it for Epsom salt. He imme- diately perceived, by the strong acid taste and burning sensation in the throat, that he had made a mistake, and he drank a large quantity of warm water to excite vomiting, which produced the desired effect. He also took, by the advice of a physician, ipecacu- anha and antimony in emetic doses, and castor oil. The matter first vomited was of a dark chocolate color. In twelve hours after the occurrence the patient was in a state of complete prostration : face, lips, throat, and tongue swollen and livid ; pulse almost extinct, fluttering and irregular; heart in a continual fluttering palpitation; great jactitation and distress ; with incessant vomiting. The matter 152 OXALIC ACID. vomited was a thick, grumous, and jelly-like fluid, of a yellow color, mixed with white flocculi. He complained of no pain at the epigas- trium, or over the bowels, on pressure. Carbonate of lime was now administered, but rejected. On the second day the face was tumid, and of a livid color; tongue swollen and livid; pulse 130; and the urine entirely suppressed. The vomiting continued for two or three days, with great distress and anxiety ; the tongue became covered with a brown coating, the tip of the organ being red and dry ; and there was great thirst, but no pain. On the sixth day his mind began to wander, and petechise appeared on the face, chest, and other parts of the body, which appeared as if sprinkled with blood. He continued to fail, and died on the tenth day after the poison had been taken. In several of the reported cases there was great irritability of the bowels, with frequent purging, and the discharged matters in some instances contained blood. Oxalic acid is equally poisonous in the form of an alkaline oxalate as when taken in its free state. A woman swallowed some of the acid oxalate of potassium. In two or three minutes she threw up her arms and fell down insensible. In half an hour an emetic was given, but without inducing vomiting. Half an hour later she had partially recovered consciousness. The mucous membrane of the mouth and pharynx was injected, and the tonsils were enlarged, but there was no loss of membrane. Chalk mixture was administered, and afterward vomiting was induced. The next day she complained of slight tenderness of the abdomen, and soreness of the throat and mouth, and there were some slight excoriations on the inner side of the lips. Two days later the patient was discharged as convalescent. {Ghiy's Hosp. Rep., 1874, 416.) Period when fatal. — Much the larger proportion of the recorded cases of poisoning by oxalic acid proved fatal ; and among these, death in most instances, perhaps, occurred in less than an hour after the poison had been taken. In a case quoted by Dr. Taylor, an unknown quantity of the poison caused death in about three min- utes. {On Poisons, 312.) Dr. Christison refers to two cases which proved fatal in about ten minutes ; and in another, death ensued in from fifteen to twenty minutes. In a case mentioned by Dr. Pereira, death occurred in twenty minutes. Death also occurred within a similar period in an instance in which the patient vomited almost immediately after the poison had been taken. In an instance in FATAL QUANTITY. 153 which the taUint:; of tliree-quarters of an ounce of oxalic acid was quickly folh)wecl by voinitin^r, and death in about ten minutes, only two grains of the poison were ibund in the stomach after death. The fatal period luus, however, been delayed for many hours, and even days. Two instances are reported in which death did not occur until thirteen hours had elapsed ; and another, in which it was delayed until the fifth day. In Dr. Jackson's case, already men- tioned, life was prolonged until the tenth day. The most protracted case yet recorded is, perhaps, that mentioned by Dr. Beck {Med. Jur., ii. 499), in which a woman died from the secondary effects of the poison after a period of some months. Fatal Quantity. — The effects of given quantities of oxalic acid, like those of most other poisons, have been far from uniform. In one of the cases just referred to, that proved fatal in thirteen hours, half an ounce of the poison, largely diluted with water, had been taken. Dr. Taylor quotes a case in which a boy, aged sixteen years, ate about one drachm of the solid acid, and it proved fatal within nine hours ; and another, in which a woman, aged twenty-eight years, swallowed three drachms of the crystallized acid, and was found dead in one hour afterward. These are the smallest fatal doses yet re- ported. Serious symptoms, however, have followed the taking of much smaller quantities of the poison. In a case reported by Dr. Babington, two scruples of the acid, taken in combination with car- bonate of sodium, caused severe symptoms, from which the patient did not entirely recover until some weeks afterward. On the other hand, complete recovery has taken place after very large quantities of oxalic acid had been taken. Not less than six instances of this kind are reported, in each of which half an ounce of the acid had been swallowed : in most of these, however, early treatment was employed. A like result has also been observed in several instances in which an ounce of the poison had been taken. In a singular case quoted by Wharton and Stille {3Ied. Jur., 496), a woman dissolved two large tablespoonfuls of oxalic acid, by mistake for Epsom salt, in a small quantity of water, and took it on an empty stomach. Some twenty minutes afterward she vomited, at first the solution she had taken, and then a dark-colored, bloody fluid, in which were numerous white flakes. Ipecacuanha and afterward prepared chalk were administered, and in about an hour she was found quiet and nearly free from the intense burning pain in her stomach and 154 ■ OXALIC ACID. throat. She subsequently vomited again, and matters similar to those vomited were discharged from the bowels by purging. Soon after this she entirely recovered. If this case is correctly reported, the quantity of the poison taken was about one ounce and a quarter. Teeatmext. — Powdered chalk, magnesia, or its carbonate, sus- pended in water or milk, or a solution of the acid carbonate of mag- nesium, should be administered as speedily as possible. Either of these substances will completely neutralize oxalic acid, with the ])ro- duction of an insoluble compound. After thus neutralizing the poison, if there is not free vomiting, an emetic should be admin- istered. Large draughts of warm water may be given to aid the vomiting. One or other of these chemical antidotes has in several instances been employed with great advantage. When, however, the symptoms have once fully manifested themselves, they usually ter- minate fatally in spite of any treatment. If neither of these earthy compounds is at hand, an emetic should be given, and its exhibition followed by large quantities of tepid ^vater. The stomach-pump may sometimes be employed with advan- tage. As the alkaline carbonates form with the acid soluble poison- ous salts, they will not serve as antidotes in this kind of poisoning. Post-mortem Appearaxces. — These are subject to considerable variation. In rapidly fatal cases, the mucous membrane of the mouth and throat is generally more or less disorganized, and of a white appearance. The lining membrane of the oesophagus is some- times much softened, and easily detached, and the blood-vessels congested with dark blood. The stomach has been found much contracted in size, and its external coat highly inflamed. The con- tents of this organ are usually thick, highly acid, and of a dark color, due to the presence of altered blood. The mucous membrane is pale or of a brownish color, injected, softened, and sometimes corrugated. In a few instances the coats of the stomach presented a dark or nearly black appearance ; and they have been so much softened as to be lacerated by the slightest pressure. In a case mentioned by Dr. Christison, the coats of the stomach were perfo- rated. The small intestines have in several instances shown signs of irritation ; and the liver and spleen have been found in a highly congested state. In this connection, it is important to bear in mind that oxalic acid, even when taken in large quantity, has in some few instances destroyed life without leaving any well-marked morbid GENERAL CHEMICAL NATURE. 155 changes, or in fact any ahiiunnal appearance whatever, in the dead body. In a case suddenly fatal on the fourth day after a quantity of oxalic acid had been taken, the walls of the stomach wca'c found somewhat congested, and the organ contained a (juantity of bloody fluid ; otherwise it was natural. In a case in which an ounce of oxalic acid had been taken by a man, on an empty stomach, and proved fatal under continued vomit- ing and purging in twenty-jive minutes, on inspection the brain, heart, lungs, and kidneys were found healthy. The mucous membrane of the stomach was found highly congested, and curiously corrugated, as if the muscular coat had been irritated and contracted. No ulcer- ation or softening was observed. [Lancet, Dec. 1860, 593.) In a case which proved fatal in thirteen hours, the lining mem- brane of the throat and oesophagus presented an appearance similar to that of having been scalded, and could be easily separated. The stomach contained a pint of thick, dark-colored fluid ; and its mucous coat was pulpy, in many points black, and in others highly inflamed ; its outer coat was also inflamed. Similar appearances, but in a less degree, were observed both externally and internally in the small intestines. The lining membrane of the trachea was also very red. In the protracted case reported by Dr. Jackson, the stomach contained a yellow fluid, and was remarkably corrugated ; its mu- cous membrane was much thickened, soft, of a bright red color, and contained numerous small ulcers. The lining membrane of the duodenum was also thickened, red, and studded with ulcers ; and that of the other portions of the small intestines congested. The large intestines, and other abdominal organs, were healthy. The heart was empty, except a small quantity of blood in the right side. In a case that proved fatal on the twenty-third day, the lining membrane of the oesophagus and stomach was completely destroyed, and in places entirely removed ; and the muscular coat, throughout the gullet and stomach, was much thickened, highly injected, and presented a dark appearance. Chemical Properties. General Chemical Nature. — Oxalic acid, when pure, forms colorless, transparent, odorless, four-sided crystalline prisms, which contain two molecules of water of crystallization, C2H204,2Aq. It 156 OXALIC ACID. is the strongest of the vegetable acids. The crystals are perma- nent at ordinary temperatures ; but when ex})osed to warm air, they part with their water of crystallization and become opaque. Oxalic acid is readily soluble in water at ordinary temperatures. The extent to which the acid dissolves in this fluid has been variously stated at from eight to fifteen times its weight of the liquid. And, in fact, either of these extremes will equally express its solubility, unless some exact temperature be specified. As the mean result of three very closely accordant experiments, we have foimd that when excess of the pure crystallized acid is kept in contact with pure water for five hours at a temperature of 15.5° C. (60° F.), and the solution then filtered, the filtrate contains one part of the acid in 9.5 parts of water. It is more freely soluble in warm water ; and boil- ing water, it is said, will take up its own weight of the acid. Berze- lius met with a sample of the crystallized acid which was so strongly impregnated with nitric acid, used in its preparation, that it required only two parts of cold water for solution. The pure acid is also freely soluble in alcohol, but insoluble in ether, and very sparingly soluble in chloroform. When one grain of the pure crystallized acid is dissolved in one hundred grains of w^ater, and the solution violently agitated, for a few moments, with an equal volume of pure chloroform, this liquid extracts one-twentieth of a grain of the acid. The oxalates, or salts of this acid, are usually colorless and crystallizable, and for the most part, except those of the alkalies, insoluble in water. They are all decomposed by heat, the acid being resolved into carbonic acid and carbonic oxide. Special Chemical Properties. — Oxalic acid, when pure, is entirely dissipated at a temperature of about 177° C. (350° F.). In this respect it diifers from the sulphate of magnesium, which it closely resembles in appearance, and which leaves a fixed residue, even at high temperatures. When the acid is heated with strong sulphuric acid, it is resolved, without charring, into carbonic acid and carbonic oxide gases, which escape : tartaric and other organic acids when thus heated are speedily charred. Solutions of the acid have a strongly acid taste and reaction, even when much diluted, and fail to be precipitated by the alkaline carbonates : a solution of Epsom salt has a bitter taste, is neutral in its reaction, and yields a white precipitate when treated with sodium carbonate. Pure aqueous solutions of oxalic acid, when slowly evaporated to SPECIAL CHEMICAL PROPERTIES. 157 dryness, leave the acid in the form of long crystalline priBnis. When one o;rain of a l-l()()th .solution of the acid is allowed to evaporate spontaneously, it leaves a comparatively large mass of crystals ; when the solution contains the 1-lOOOth of its weight of the acid, it yields a quite good deposit, the crystals having the forms represented in Plate III., fig. 2; the l-10,000th of a grain of the acid, under similar circumstances, yields a very satisfactory deposit of small prisms and cross lets. In the followino; details in regard to the behavior of solutions of oxalic acid, the fractions indicate the fractional part of a grain of the pure crystallized acid in solution in one grain of water; and the results refer to the reactions of one grain of the solution. 1. Silver Nitrate. Solutions of free oxalic acid, and of its alkaline salts, yield with nitrate of silver a white amorphous precipitate of oxalate of silver, ^?,2^2^ii which is slowly soluble in cold nitric acid, but readily soluble in the heated acid; it is also readily soluble in solutions of ammonia, but insoluble in concentrated solutions of acetic, tartaric, and oxalic acids. When the dried precipitate is heated on platinum foil, it is decomposed and dissipated in slightly detonating puffs, being resolved into metallic silver and carbonic acid gas; thus: AgAA=Ag2+2C02. 1. YW^ grain of oxalic acid, in one grain of water, yields a very copious precipitate, which, in the mixture, requires about three drops of strong nitric acid for complete solution. When dried and heated, it is dissipated in the manner peculiar to this salt. 2. ydVo g'ain yields a rather copious precipitate, which, when dried and heated, is rapidly dissipated, but not in distinct puffs. 3. x"(5-Voir g'^'^in : a very good deposit. 4. -j-g-.Vrro gi'ain yields an immediate turbidity, and, in a very short time, a quite satisfactory deposit. 5. YuiKoiro grain: an immediate opalescence, and, after a little time, a quite distinct deposit. 6. 3-0-^,15-oir g^ain yields, after some minutes, a distinct cloudiness. Fallacies. — Nitrate of silver is also readily decomposed, with the production of a white precipitate, by a great variety of organic principles. And it also produces similar precipitates with several other acids, especially from neutral solutions. Thus, it occasions 158 OXALIC ACID. precipitates in neutral solutions of the carbonates, tartrates, phos- phates, borates, citrates, chlorides, and cyanides, and also, in most instances, with the free acids of these salts. All these precipitates, however, except those from the chlorides, cyanides, and their free acids, are soluble in acetic acid, in which respect they diifer from the oxalate of silver. So, also, the chloride and cyanide of silver — produced by the reagent from solutions of chlorides and cyanides or their free acids — are readily distinguished from the oxalic acid precipitate, in that they are insoluble in nitric acid. Moreover, the chloride of silver, when dried and heated, quietly fuses without decomposition ; and the cyanide, under similar circumstances, is decomposed with the production of a fixed residue and the evolution of an inflammable gas. The precipitates produced from the car- bonates, tartrates, phosphates, borates, and citrates, when dried and heated, also, unlike the oxalic acid deposit, leave a fixed residue. 2. Calcium Sulphate. Sulphate of calcium throws down from solutions of free oxalic acid, and of soluble oxalates, a white granular precipitate of oxalate of calcium, CaC20^,2Aq, which is readily soluble in nitric and hydrochloric acids, but insoluble, or very nearly so, in acetic and other vegetable acids. As sulphate of calcium is soluble only to a limited extent in water, its solution does not precipitate the whole of the oxalic acid from somewhat concentrated solutions, unless the reagent solution be added in very large quantity. From such solu- tions the whole of the acid may be readily precipitated, as calcium oxalate, by employing as the reagent a solution of chloride of calcium or any of the other more soluble salts of lime. 1. yl^ grain of free oxalic acid yields with a drop of the calcium sulphate solution a very good, granular precipitate. A small drop of chloride of calcium solution produces a much more copious deposit, which is in the form of small rectangular and notched plates, somewhat larger than the granules produced by the sulphate of calcium. 2. Y^oT g^'ai" • ar" immediate cloudiness, and soon a quite good granular deposit. Chloride of calcium produces much the same reactions, but the precipitate consists chiefly of small plates and octahedral crystals, which vary in size from the l-3000th to the l-7000th of an inch, Plate III., fig. 3. The precipitate oc- SPECIAL CHEMICAL PROPERTIES. 159 ciisioned by the sulplmte of calciiini is in tin; lonii ol" ^ a little time, granules, prisms, and octahedral crystals. SPECIAL CIIKMICAL IMIOPERTIES. 101 3. -jj-^jl^ grain: in a little time, a distinct turbidity, and >ooii a rather good granular precipitate. 4. p,yJ|y,Y grain: in a few minutes, a very distinct granular deposit. Tlie objections to the reactions of this test, and the methods of answering them, arc the same as pointed out under the preceding reagent. 5. Lead Acetate. Solutions of free oxalic acid, and of its soluble salts, yield with this reagent a white precipitate of oxalate of lead, which is insoluble in acetic acid, but readily soluble in nitric acid. 1 . .j_i_j. grain of the free acid yields a very copious precipitate, con- sisting of a mass of crystalline needles, Plate III., fig. 6. 2. y^\j-jj grain : a copious precipitate, which immediately begins to crystallize. 3. g^i^^ grain : a good deposit, which soon becomes changed into stellate crystalline groups. 4. yiy.^-oir gi'^i" '• ^^ immediate turbidity, and soon, stellate crystals. 5. YTJ.'^Wo grain : very soon the mixture becomes opalescent, and, in a little time, yields a satisfactory granular deposit. 6. 4^,^-^j-jj- grain : after some time, the mixture becomes slightly turbid. Fallacies. — Solutions of sulphuric acid and of sulphates, and strong solutions of hydrochloric acid and of chlorides, also yield, when treated by the reagent, white precipitates, which, however, are insoluble in strong nitric acid. The reagent also produces white precipitates in neutral solutions of carbonates, phosphates, and sev- eral other salts, and also with a great variety of organic substances. These deposits, however, at least for the most part, are readily soluble in acetic acid. The oxalic acid may be recovered in its free state from the oxalate of lead by suspending the latter in water and passing through the mixture a stream of sulphuretted hydrogen gas, as long as it causes any blackening of the mixture. By this means the oxalate of lead will be entirely decomposed, the metal being precipitated as black sulphide of lead, while the eliminated acid will remain in solution: PbCA 4- H,S = PbS + C2H A- On now warming the mixture, to facilitate the deposition of the precipitate and expel the excess of gas added, filtering, and concentrating the filtrate at a moderate temperature, the solution on cooling, if suf- ficiently concentrated, will deposit the acid in its crystalline form. 11 162 OXALIC ACID. The precipitate produced by the reagent from ten grains of a 1-lOOOth solution of the free acid, when washed and suspended in ten grains of water, then treated with sulphuretted hydrogen, and the solution filtered, will furnish ten grains of liquid, which when examined in separate drops by the preceding reagents will yield results not to be distinguished from those obtained from a 1-lOOOth solution of the pure acid. In other words, the 1-lOOth of a grain of the acid, when in solution in ten grains of water, may be pre- cipitated by acetate of lead and the acid recovered in its free state, without any appreciable loss. The presence of organic matter may, however, considerably modify these results. 6. Copper Sulphate. Sulphate of copper produces in solutions of free oxalic acid, when not too dilute, a precipitate of oxalate of copper, having a very light bluish or greenish color, the tint depending on the strength of the Solution. The precipitate is insoluble in acetic and oxalic acids, and dissolves to a very limited extent in even large excess of strong nitric acid ; it is also insoluble in salts of ammonia, but dissolves readily in the pure alkali. 1. Y^ grain yields a very copious flocculent precipitate. 2. -g-^ grain : after a little time, a granular precipitate, which for the most part floats on the surface of the mixture ; the addition of a few drops of strong nitric acid does not cause the granules to disappear. 3. Y^g-Q grain yields, after some time, a slight precipitate, which is dissolved on the addition of a drop of nitric acid. Fallacies. — Sulphate of copper also produces precipitates in neutral solutions of carbonates and of phosphates, and is also decomposed by certain kinds of organic matter with the production of a precipitate ; but all these deposits are distinguished from the oxalate of copper in being readily soluble in nitric and hydrochloric acids. Solutions of free sulphuric, hydrochloric, tartaric, and citric acids, and of their salts, fail to be precipitated by this reagent. Separation from Organic Mixtures. Suspected Solutions. — When the solution contains much organic matter, none of the preceding tests should be applied directly to the mixture, since under these conditions they are all liable to produce a SEPARATION FROM ORGANIC MIXTURES. 163 precipitate, evou in tlio absence of oxalic acid. If tlie solution is strongly acid in its reaction and contains mechanically suspended solids, the mixture, properly diluted with water if necessary, is di- gesteil at a moderate heat for fifteen minutes or longer, then filtered, the filtrate concentrated to a small volume, and, if neceasary, again filtered. As a preliminary stej), a drop of the liquid may now be examined by the sulphate of copper test. If this produces a faintly bluish precipitate, insoluble, or nearly so, in nitric or hydrochloric acid, there is little doubt of the presence of oxalic acid. If the precipitate thus produced is quite copious, and the liquid under examination nearly colorless, then the remaining portion, after further concentra- tion if thought best, is allowed to stand in a cool place for some hours, in order that the acid, in part at least, may crystallize out. Any crystals thus obtained are separated from the liquid, gently washed, then dissolved in a small quantity of pure w'ater, and the solution tested in the ordinary manner. On furtiier concentrating the liquid from which the crystals separated, a second crop may be obtained. If the crystals deposited in these operations are highly colored, they should be redissolved in a little warm water and purified by recrys- tallizatiou before being tested. Should, however, the preliminary examination by the copper test indicate the presence of only a minute quantity of the acid, or should the liquid be highly colored, then the remaining portion is treated with slight excess of a solution of acetate of lead, by which the whole of the acid will be precipitated as oxalate of lead, together with more or less organic matter. The precipitate thus produced is col- lected on a filter and thoroughly washed, first with water acidulated with acetic acid, then with pure water. The moist precipitate is then diffused in an appropriate quantity of w-ater and exposed to a stream of sulphuretted hydrogen gas until the whole of the white compound is thoroughly blackened, which may require an hour or longer. By this treatment, as already pointed out, any oxalate of lead present will be decomposed, the acid entering into complete solution, and the metal being thrown down as sulphide. The liquid is now separated from the precipitate by filtration, and kept at a moderate temperature until the odor of the sulphuretted gas has entirely disappeared. It is then, if colorless, examined by the usual tests; if, however, it is highly colored, any oxalic acid 164 OXALIC ACID. present is purified by crystallization, in the manner above described, and then tested. The methods now described would yield equal results whether the acid existed in its uncorabined state or in the form of a soluble oxalate in the original liquid, and, therefore, do not serve to dis- tinguish the state in which it was present. This, however, in medico-legal investigations, is rarely a matter of much importance. Should it be desired to determine this point, it may be approxima- tively done by evaporating the prepared filtered liquid to dryness on a water-bath, and extracting the residue with very strong alcohol, which will dissolve the free acid if present as such, together with more or less foreign matter, but only a trace of an alkaline oxalate, nearly the whole of the latter, unless present in only very minute quantity, remaining undissolved. The filtered alcoholic solution may now be evaporated to dryness on a water-bath, the residue digested with a small quantity of water, and the filtered liquid examined by either of the above-mentioned methods. The residue remaining undissolved by the alcohol, supposed to contain an alka- line oxalate, is stirred with distilled water, the solution filtered, and then examined in the usual manner. Contents of the Stomach. — If no chemical antidote has been administered, the contents of the stomach are collected in a porcelain dish, tested in regard to their reaction, and the inside of the organ well washed with distilled water, the v^^ashings being collected with the contents in the dish. The mixture, after the addition of more water if necessary, is heated to about the boiling-point for half an hour or longer, the cooled liquid strained, the solids on the strainer washed, and the united liquids filtered, then concentrated and again filtered. The liquid may now either be evaporated to dryness, and the residue thoroughly extracted by strong alcohol, as described above for suspected solutions, or it may be treated with slight ex- cess of acetate of lead, the precipitate collected on a filter, washed with water acidulated with acetic acid, and any oxalate of lead present subsequently decomposed by sulphuretted hydrogen gas. Instead of decomposing the oxalate of lead by sulphuretted hydrogen, it has been proposed to boil it for about half an hour in an appropriate quantity of highly diluted sulphuric acid, by which it will be resolved into insoluble sulphate of lead and free oxalic acid. The liquid is then filtered, exactly neutralized by ammonia, SEI'MJATION FFtOM OFtGANH' MIXTURES. 105 an<] tested. Uiulcr Llieso circiun.staiiccs, the poison would exist its oxiilatc of aninionia, mixed with more or less sulphate of amnio- nimii ; the latter being formed I'loiu the excess of sulphuric acid crn- ployed in the decom|)osition of the oxalate of lead. The j)resence of this sulphate would not interfere with the reactions of the silver, sulphate of cidcium, and copper tests; but it would yield with the barium, strontium, and load reagents white precipitates of the sulphates of these metals. Of these two methods of effecting the decomposition of the oxalate of lead, the former is much to be preferred. Should lime or magnesia have been administered as an antidote, the contents of the stomach, as well as any matters vomited prior to death, may have a neutral reaction, and contain the ])oison in the form of an insoluble oxalate of one or other of these bases. Under these circumstances, the suspected matters, especially all earthy solids, are collected in a dish, the mass made quite liquid by the addition of warm water, and thoroughly stirred ; any organic solids present are then washed in the liquid and removed, and the remain- ing solids allowed completely to subside. When this has taken place, the liquid is decanted, and the solids are again washed with fresh water; they are then diffused in a small quantity of pure water, a quantity of pure potassium carbonate, somewhat exceeding that of the earthy matter present, is added, and the mixture boiled for about half an hour, the liquid evaporated during the operation being re- l>laced by distilled water. The earthy oxalate will now be changed into an insoluble carbonate, while the oxalic acid will be in solu- tion in the form of potassium oxalate. This solution, after filtra- tion, is treated WMth decided excess of acetic acid, and the oxalic acid precipitated by a solution of acetate of lead. The precipitate thus produced is collected, washed, and decomposed by sulphuretted hydro- gen gas in the manner already described. In case of the discovery of oxalic acid in vomited matters or the contents of the stomach, it might be objected, in a medico-legal investigation, that the acid was a normal constituent of certain vege- table structures, some of which are sometimes used as articles of food or administered medicinally. Thus, it is present in common sorrel, in culinary rhubarb, or pie-plant, and in the rhubarb of the shops. In these substances, however, it exists only in minute quantity, and in its combined state, either as oxalate of potassium or of calcium. 166 OXALIC ACID. But should even only a minute quantity of the poison be discovered, the symptoms and other circumstances attending a case of poisoning by the acid would rarely leave any doubt wliatever as to its true nature. The Urine. — Oxalic acid, when taken either in its free or com- bined state into the stomach, soon appears in the urine, usually in the form of octahedral crystals of calcium oxalate. The forms of these crvstals readily distinguish them from all other urinary deposits ; thev are very similar in form to those of the oxalate of strontium, as figured in Plate III., iig. o. These crystals are often present in the urine at the time it is voided, but more frequently they do not separate until after some hours. For the purpose of making this examination, a small portion of the liquid is gently rotated in a watch-glass, until the sediment col- lects at the bottom of the fluid, when the clear liquid is decanted ; the sediment is then washed in a similar manner with pure water, which in its turn is decanted, and the deposit examined by the micro- scope, under an amplification of about one hundred and twenty-five diameters. If none of the crystals are thus found, and the urine is fresh, some ounces of it may be allowed to stand quietly for several hours, the clear liquid decanted, and the sediment collected, washed, and examined as before. In this connection, it must be borne in mind that these crystals also thus occur not only after the ingestion of certain articles of food, but not unfrequently as the result of disease, and sometimes even without any apparent cause. In fact, we have found the latter to be the case much more frequently than seems to be generally supposed. If it be desired to examine the urine for the presence of the free acid or of a soluble oxalate, the liquid, after the addition of a little acetic acid, may be evaporated to about one-fourth its volume, filtered if necessary, the filtrate treated with slight excess of acetate of lead, any precipitate thus produced decomposed by sulphuretted hydrogen, and the filtered solution tested by the usual reagents. QuANTiTATRT'E ANALYSIS. — From pure solutions oxalic acid may be estimated with considerable accuracy in the form of oxalate of lead (PbCaOj. The solution is treated with a little pure acetic acid, and a solution of acetate of lead added as long as a precipitate HYDROCYANIC ACID. 107 is produced ; wlicn the precipitate has completely subsided, it is collected ou a filter of known \vei»jht, well washed with pure water, dried at 100° O. (212° F.), and weighed. Everyone hundred parts l)v weight of oxalate of lead thus obtained correspond to 42.5 parts of crvstalli/.ed oxalic acid. If the acid has been jjrecipitated as oxalate of calcium, this is thoroughly washed and dried, then exjmsed for a few minutes to a very dull red heat. In this last operation the oxalate will be con- verted into calcium carbonate, every one hundred parts of which correspond to one hundred and twenty-six parts of the crystallized acid. Section II. — Hydrocyanic Acid. History and Composition. — This substance, also known as prussic acid, is a compound of the organic radical cyanogen (CN) with the element hydrogen, its composition being represented by the formula HON or HCy. In its pure state, hydrocyanic acid is a colorless, volatile liquid, having a peculiar odor, somewhat resembling that of bitter almonds. It is one of the most powerful and rapidly fatal poisons yet known ; and many of its compounds are about equally poisonous. It may be obtained from various vegetable substances, as bitter almonds, the kernels of peaches, plums, apricots, and cherries, apple-pips, the flowers of the peach and cherry-laurel, the bark of wild cherry, and the root of mountain ash. In many of these sub- stances, however, the acid does not exist as such, but is the result of the decomposition to which they are subjected in its preparation. For ordinary purposes, hydrocyanic acid is usually obtained by distilling one of its salts with dilute sulphuric or hydrochloric acid. The acid of the shops is a solution of the anhydrous acid, usually in water, but sometimes in alcohol, and varies in strength from 1 to 25 per cent., according to the directions of the Pharma- copoeia followed for its preparation. The United States Pharma- copoeia directs a strength of 2 per cent, of the pure acid ; and about the same proportion is directed by the British Colleges. The preparation known as Scheele's acid sometimes contains as much as 5 per cent, of real acid, but usually its strength falls very short of this. Of several specimens of commercial acid examined some years since, we found none to contain over 1.5 per cent, of anhydrous acid ; and one of the samples, which had not before been opened 168 HYDEOCYAXIC ACID. after havino- left the hands of the maniifactiu'er, did not contain even a trace of the acid. An aqueous solution of hydrocyanic acid, especially when exposed to the light, is prone to undergo spontaneous decomposition, with the formation of a brown deposit. This fact, in a measure at least, accounts for the difference observed in the strength of samples of the acid prepared after the same formula. This decomposition is much retarded by the presence of a minute quantity of a mineral acid, and for that purpose a trace of sulphuric acid is frequently added to the solution. According to J. Williams, aqueous solutions, even when containing 5 per cent, of the acid, may be preserved unchanged for long periods by the addition of 20 per cent, of glycerin. An aqueous solution of the acid, when pure, is perfectly colorless. In regard to its physiological effects, hydrocyanic acid belongs to the class of narcotic poisons. Symptoms. — These, both in respect to the time within which they appear and their character, depend upon the quantity of the acid taken. When taken in large quantity, it not unfrequently proves so rapidly fatal that no well-marked symptoms are observed. During the act of swallowing a large dose, the patient experiences a hot bitter taste, and is either immediately or at most within a very few minutes seized with complete loss of muscular power and of consciousness. The respiration becomes hurried, but often convul- sive, and sometimes stertorous, the pulse imperceptible, the extremi- ties cold, the eyes prominent, the pupils dilated, and in many in- stances there are convulsions. In a case reported by Hufeland, in which a man swallowed about fortv grains of the pure acid, in the form of an alcoholic solution, the patient immediately staggered a few steps, and then fell, appar- ently lifeless. When seen, almost instantly afterward, by a physician, the pulse was imperceptible and the respiration entirely suspended. After a short interval, the man made a very forcible expiration ; the extremities became cold, the eyes prominent, glistening, and insen- sible to light, and after a few convulsive expirations he died, within five minutes after the poison had been taken. The following case was reported to Professor A. Stille by Mr. Clay Hall. {Amer. Jour. Med. Sci., Jan. 1868, 277.) A gentleman with suicidal intent took about one hundred drops of diluted hydro- cyanic acid, purporting to contain 2 per cent, of the anhydrous acid. PHVSI<)I,()(iICAL KKFKCTS. Ifi9 When seen by Mr. Hall, williiii five; niiniitos after taking the j)ois()n, the man was fbnnd lying extended upon the floor, nnconseious. His muscles were relaxed and flaccid, with the exception of" the muscles of the jaw, this being firmly closed ; his hands were folded acroas his breast, as in repose; the eyes were fixed, but life-like, the pupils being normal; respiration was slow, but not labored; his pulse was about 50, becoming slower and less strong to the moment of death ; the veins of the neck and face were strongly congested. Not the slightest odor of the acid could be perceived in his expirations ; nor was any perspiration perceptible. His respiration became slower and slower, until intervals of over one minute intervened, and he quietly died in from fifteen to twenty minutes after taking the poison, the pupils dilating at the moment of death. It was formerly believed that when prussic acid was taken in rapidly fatal quantity it always produced immediate insensibilitv ; but this is by no means always the case. When taken in such quantity, the symptoms usually appear within a very few seconds, yet they have in several instances been delayed sufficiently long for the patient to ])erform a series of voluntary acts. In a case related by Dr. Sewell, a man swallowed seven drachms of Scheele's prepara- tion of the acid, believed to contain about twenty-one grains of the anhydrous poison, after which he walked to the door of his room, unlocked it, called for assistance, then walked to a sofa and stretched himself upon it; in a very little time after this he was found in an insensible state, with stertorous breathing, and soon died. (Boston Med. and Surg. Jour., xxxvii. 322.) The following remarkable case is related by Mr. Hickman. [Lancet, 1866, i. 310.) A man, by mistake for some medicine, swallowed half an ounce of the diluted acid, containing, as was afterward determined, something over three grains and a half of the pure acid. After taking the dose, he ran up-stairs to the house- surgeon, traversing a distance of twenty-five or thirty paces, and ascending thirty-two steps. When he reached the surgeon's room he said, " Come down directly ; I have taken half an ounce of prussic acid." He then ran all the way back to the dispensary, where he was found standing unsupported in the middle of the room. He moved his hand impatiently, and said, "Be quick; give me some- thing." Some solution of ammonia was given him, followed by some tincture of the sesquichloride of iron. He drank both these, 170 HYDROCYANIC ACID. and then, being directed, put his finger in his throat to induce vomit- ing. This caused one or two slight but abortive efforts, after ^yhich he suddenly fell flat on his back, completely insensible. His face, previously jmllid, now became much congested ; the eyes were fixed and half closed ; the pupils were somewhat dilated ; no pulse could be felt ; the breathing became slow, faint, and gasping ; a frothy mucus exuded from between the lips ; one or two of the respirations were accompanied by a slight stertorous sound. Xo convulsions occurred. Death took place in about ten minutes after he first ap- peared at the house-surgeon's room. When the dose is not sufficiently large to produce rapid insensi- bility, the first symptoms usually experienced are giddiness and a sense of great weakness ; these effects are soon succeeded by irritation in the throat, an increased flow of saliva, nausea, difficult and spas- modic respiration, and loss of voluntary motion ; the pulse becomes small or imperceptible, the face livid, and the eyes glaring, the pupils generally being dilated. These cases are frequently attended with tetanic convulsions. The following case of recovery is quoted in detail by Dr. Stille. {Mat. Med., ii. 210.) A French physician swallowed a dessert- spoonful of the medicinal acid, prepared by a chemist of Paris. He almost immediately afterward fell down as if struck by lightning. Among the symptoms observed were loss of consciousness and sensibility ; trismus ; a constantly increasing dyspnoea ; cold extrem- ities; a noisy and rattling respiration; the characteristic odor of the acid upon the breath ; distortion of the mouth ; and a thready pulse. The face was swollen and dusky, and the pupils fixed and dilated. The trismus increased, and was soon accompanied by opisthotonos. At the end of an hour a violent convulsion occurred, the whole trunk grew stiff, and the arms were twisted outwards. After two hours passed in this condition, the patient began to regain his consciousness, and in several hours afterward he was able to walk without assistance ; but it was a fortnight before he entirely recovered. In a non-fatal case reported by Mr, W. H. Burnam, in which a dose containing 2.4 grains of the anhydrous acid was taken by mis- take, insensibility did not occur until two minutes after the poison had been swallowed. In the mean time, however, the patient, having almost immediately discovered his mistake, took as an antidote half PHYSIOLOGICAL EFFECTH. 171 an ounce of aromatic spirits oi" ammonia, with a little water; and he told what had occurred : lie spoke hurriedly, and breathed deeply. A solution of sulphate of iron was then administered. The respira- tion became deeper and slower. In four minutes after the poison was taken, the cold douche was freely employed, and an additional quantity of the iron solution with spirits of ammonia administered. Yomitino: took place; and there was a slight convulsive shudder. In twenty minutes the patient began to exhibit signs of returning consciousness; and in about fifteen minutes later he was able to walk up-stairs to bed. {Brit, and For. Med.-Chir. Rev., April, 1854.) In a case of recovery reported by Mr. Garson, in which a teaspoonful of the acid, of unknown strength, had been taken, the symptoms were delayed for about fifteen minutes. The individual was then found in a state of insensibility, and this continued for about four houi-s, although active remedies were employed. This is the most protracted case, in regard to the appearance of the symp- toms, yet recorded. Several instances are reported in which the inhalation of the diluted vajior of hydrocyanic acid caused most alarming symptoms ; and Dr. Christisou quotes a case in which the liquid acid applied to a wound in the hand caused death in an hour afterward. In a case related by Dr. J. A. Post {New York Med. Jour., April, 1876), the inhalation of the vapor evolved from cyanide of potassium used by a jeweller with gold as an alloy caused his death, under symptoms of congestion of the brain, in about half an hour after he was first seen by the physician. Hydrocyanic acid is also equally poisonous, with the production of similar symptoms, when taken into the system in the form of an alkaline cyanide. Since the introduction of cyanide of potassium into the arts for photographic and other purposes, numerous in- stances of poisoning by it have occurred. In a case of poisoning by this salt related by Dr. Schauenstein, of Vienna, occurring in a young man, death took place almost instantly, without any striking symptoms. In another case, reported by the same writer, strong tetanic spasms came on directly after the poison had been taken, and death ensued in less than an hour. {Amer. Jour. Med. Sei., Jan. 1860, 279.) In a case in which we were consulted in 1864, a man took, with suicidal intent, about sixteen grains of the salt in solution; immediately after swallowing the poison he walked 172 HYDEOCYAISriC ACID. about six steps, then fell insensible, and death ensued in about five minutes. The following case of recovery after a quantity of this salt had been taken is reported by Dr. Mueller- Warnek. {London Med. Record, May, 1878.) A man was heard to fall in his room, and quickly after was found lying on the floor in an unconscious state, holding in one hand a letter, and in the other a bottle containing a solution of cyanide of potassium. About an hour later, vomiting having occurred, the man was in a state of profound coma. The skin was cold and clammy ; the extremities cold ; face greatly cya- nosed ; eyeballs projecting, and directed upwards ; pupils much dilated, and insensible to light ; the lower jaw fixed ; frothy saliva, tinged with blood, issued from the mouth, and at each expiration there was a strong odor of hydrocyanic acid. The muscles of the extremities were relaxed, and there was entire loss of sensibility. Under the free use of the stomach-pump, and artificial respiration and stimulants, the patient slowly recovered, but it was several days before he was able to leave his bed. A remarkable series of cases of poisoning by cyanide of potas- sium is reported by Dr. A. B. Arnold, of Baltimore [Amer. Jour. Med. Sci., Jan. 1869, 103), in which a solution of potassium chlorate had been prescribed for a child. In filling the prescription, the druggist used the last portions of potassium chlorate in the bottle from which he dispensed it. A teaspoonful being given to the child, it was almost instantly seized with convulsions, and quickly died. Dr. Arnold then tasted small portions of the solution, and he soon experienced violent symptoms, and narrowly escaped with his life. Finally, the druggist, to show, as he said, that he had made no mis- take, took a portion of the prescription, and in a few minutes after- ward fell down dead. It was subsequently learned that the bottle from which the chlorate had been dispensed had previously contained cyanide of potassium. Period when Fatal. — The fatal period in poisoning by hydro- cyanic acid is subject to considerable variation ; yet it is extremely limited when compared with that of the action of most other poisons. Several instances are recorded in which death took place in from five to ten minutes, and it has occurred in two minutes, and perhaps even within a shorter period. On the other hand, death has been delayed for nearly an hour, even when the quantity of poison taken PHYSIOLOGICAL EFFECTS. 173 was siiffioicntly great to produce almost immediate insensibility. In fatal cases, however, life is rarely prolonged beyond half an hour: those who survive this j)eriod usually entirely recover, in an accident that occurred in one of the hospitals of Paris, by which seven epileptic j)atients were fatally jjoisoned by ccpial quantities of hydrocyanic acid, the fatal period varied from fifteen to forty-five minutes. Dr. Fao-o-e relates the case of a medical student who took about a drachm and a half of Scheele's acid, and was thereby immediately rendered insensible; but he did not die from its effects until from one hour and a quarter to one hour and a half after it had been taken. {Guys Hosj). Rep., 18G8, 259.) This is the most protracted case in this respect yet reported. Fatal Qaantitij.— That similar quantities of prussic acid do not always produce the same result is well illustrated in the instance of the Parisian epileptics just mentioned. The quantity of the poison taken by each of these patients is stated by most toxicological writers, on the authority of Orfila, to have been equivalent to about two-thirds of a grain of the anhydrous acid ; but it appears from more recent statements (Braithivaite's Retrospect, xii. 125) that the quantity actually taken by each was equivalent to five grains and a half of the real acid. An instance in which about two grains of the acid caused death has already been cited. In a case reported by Mr. Hicks, a solution containing nine-tenths of a grain of the pure acid proved fatal to a healthy woman, aged twenty-two years, in from fifteen to twenty minutes. This seems to be the smallest fatal quantity yet recorded. Smaller quantities have, however, in ses^eral instances produced most dangerous symptoms. Several cases are reported in which doses of only about five grains of cyanide of po- tassium caused death. On the other hand, Mr. Bishop has related a case in which a man entirely recovered after having taken at a dose forty minims of a solution containing one grain and a third of anhydrous prussic acid. {Lancet, London, Sept. 1845, 315.) In this case the patient, according to his own account, remained sensible for at least two minutes after taking the poison. When first seen by Mr. Bishop, about ten minutes after the occurrence, he was senseless, the counte- nance ghastly pale, face swollen and covered with perspiration, the respiration slow and labored, the eyes fixed and glazed, the pupils 174 HYDROCYANIC ACID. dilated, and the whole body in a rigid state. The treatment con- sisted in cold aflfusion, ammonia, emetics, and bleeding. So, also, Dr. Christison has reported a case in which a gentleman recovered after having taken a solution equivalent to between a grain and a half and two grains of the anhydrous acid. And in a case already cited, that reported by Mr. Burnam, recovery followed even after 2.4 grains of the pure acid in solution had been swallowed. In this case, how- ever, as well as in that reported by Dr. Christison, active remedies were almost immediately employed. Treatment. — On account of the rapid action of hydrocyanic acid when taken in poisonous quantity, it rarely happens that treat- ment can be resorted to in time to be of much service. The reme- dies consist chiefly in the exhibition of stimulants; but certain chemical antidotes have also been advised. The exhibition of the vapor of ammonia has been highly recom- mended, and several instances are reported in which its use was attended with great advantage. It has also been proposed to admin- ister a solution of ammonia diluted with water ; but in this form, according to Orfila, it is of no service. Chlorine, administered either in the form of vapor or taken internally, has also been strongly advised. It may be used in the form of a weak solution of hypochlorite of lime or of the corresponding sodium salt. The gas is readily obtained by acting on either of these salts with diluted hydrochloric or acetic acid. From experiments on inferior animals, Orfila was led to believe that chlorine was the most efiicient antidote yet proposed. It need hardly be added that great caution should be exercised in its administration. Cold affusion, first recommended by Herbst, has perhaps on the whole been found the most efficient remedy hitherto employed in the human subject. Its use should be accompanied by the exhibi- tion of the vapor of chlorine or ammonia. In several instances of recovery, in which this treatment was employed, it was apparently the means of averting death. Artificial respiration was strongly insisted on by the late Dr. Pereira. He successfully employed it in experiments on animals. Stimulating injections, as well as blood-letting, have also been advised. The latter should be resorted to with great caution. In Dr. Warnek's case of recovery, one hour after a large dose of cyanide of potassium had been taken, the stomach was repeatedly washed by means of the stomach-pump POST-MORTEM APPEARANCES. 175 with tepid water, until the \vashiii<; no longer had tlie odor of tlie poison. As a chemical antidote, it has been suggested by Messrs. Smith, of Edinburgh, to administer a sohition of a mixture of the sulphates of tlie protoxide and sesquioxide of iron (ferrous and ferric sul- phates), quickly followed by a solution of carbonate of potassium. A mixture of this kind produces with hydrocyanic acid Prussian blue, which is inert, being insoluble. In experiments on animals, this treatment was quite successful. Even if this antidote be at hand, it should never be relied on to the exclusion of stimulants and cold atiusion. As a physiological antidote in poisoning by hydrocyanic acid, Preyer has strongly advised the hypodermic injection of atropine. He found that rabbits to Avhich atropine had previously been ad- ministered exhibited a surprising immunity to the action of hydro- cyanic acid. But Prof. Boehm and A. Knie, from experiments chiefly on cats, deny the antidotal action of this substance. Post-mortem Appearances, — These will, of course, depend somewhat on the length of time the individual survived after taking the poison, and also the period that has elapsed since death. The face is usually pale, but often livid, the eyes glistening and staring, the lips blue, the jaws firmly closed, and the extremities soon become rigid. The blood throughout the body is fluid, and generally of a dark or bluish color, but sometimes cherry-red; the venous system is turgid ; the arteries are nearly empty ; the liver, and in some in- stances the lungs, much congested. The stomach, other than so far as cadaveric changes have taken place, is generally natural. It need hardly be observed that neither of these appearances is peculiar to death from hydrocyanic acid. In poisoning by hydrocyanic acid, the blood exhibits no char- acteristic spectrum, but simply that of oxyheemoglobin. (C. A. Mac- Munn, The Spectroscope in Medicine, 1880, 89.) If, however, hydro- cyanic acid or an alkaline cyanide be added directly to the blood, and the mixture gently warmed, it presents under the spectroscope, as observed by Preyer, a single broad absorption band somewhat simi- lar to that of reduced haemoglobin, only that it extends somewhat nearer to the violet end of the spectrum, and this portion of it is the darkest. One of the most striking characters in death from this poison is 176 HYDROCYANIC ACID. the exhalation of the peculiar odor of the acid. This is sometimes emitted from the corpse, even before any dissections are made, and, at least in recent cases, is nearly always exhaled when the stomach or thoracic cavity is opened ; and it is often detected in the blood throughout the body. As, however, hydrocyanic acid is very volatile, and also readily undergoes decomposition, it may in a little time so far disappear from the body that its odor can no longer be recognized. Moreover, the odor of the acid is liable to be masked by the presence of other odors. In a singular case related by Prof. Casper, however, in which a woman had poisoned herself with a mixture of prussic acid and a variety of essential oils, and the body diffused a sweet odor, on opening the stomach such a powerful aroma of bitter almonds came forth as almost to stupefy every one present. In several reported instances in which this character was not observed in the stomach, a subsequent chemical analysis revealed the presence of very notable quantities of the poison, in one case even so much as one grain of the anhydrous acid. In Dr. Sewell's case, in which seven drachms of the medicinal acid had been taken, he failed to detect the odor of the poison upon applying his nose to the mouth of the deceased, very soon after death. And in the case related by Mr. Hall, he failed to observe the slightest odor of the poison, even in the most forcible expirations of the patient, only some six or eight minutes after about two grains of the acid had been taken, followed by death in less than twenty minutes. In a very profound but non-fatal case recently reported by Dr. G. W. Maser {Med. Record, June, 1884, 711), the odor of the acid was observed in the breath of the patient for several days after the poison had been taken. In the case reported by Hufeland, already mentioned, the body exhaled the odor of the acid on the day following death. The coun- tenance was pale and composed, the eyes glistening, spine and neck stiff, and the back livid. The blood was fluid, bluish in color, and throughout the body emitted a very strong odor of the poison. The vessels of the brain, as well as the liver and lungs, were gorged with blood ; the arteries were empty, the veins distended, and the mucous membrane of the stomach and intestines reddened. In the cases of the seven Parisian epileptics, no odor of the poison was perceived in any part of the body twenty-four hours after death. The lips, face, and head were bloated and of a violet GENERAL CHEMICAL NATURE. 177 cH^Ior; the back livid; iVotliy l)loo<] esca|>e(l from the month and nostrils; the eyes wen; closed, and the btnly rij^id. The stomach was highly injected ; the liver, s|)k'en, and kidneys much j^orged with black bUxxl ; the arteries empty, and the veins turgid. In Mr. Hicks's case, in which only nine-tenths of a grain of the acid was taken, the 0(ior of the poison was plainly perceived on opening the chest, and was also strongly emitted from the contents of the stomach, although the examination was not made until ninety hours after death. In a case examined by M. Buchner {Amer. Jour. Phann., 1869, 465), the blood was of a clear cherry-red color, and preserved this tint for several days. At the end of five days it was still perfectly liquid, and some weeks elapsed before it gelatinized. When pre- served in stoppered bottles, it resisted putrefaction for a long time, but the red corpuscles were destroyed in a few days. It presented 710 odor of prussic acid, but when diluted with water and distilled, the first portions of the distillate possessed a distinct odor of the poison, and gave positive results witli the u.-ual tests. By this means the acid was detected even after the lapse of fifteen days. Chemical PeopePwTies. General Chemical Nature. — Anhydrous hydrocyanic acid (HCy) is a colorless, very volatile, inflammable liquid, .of a peculiar odor. It readily mixes in all proportions with alcohol and water. The pure acid has a specific gravity of 0.706, and boils at 26.6° C. (80° F.), yielding a combustible vapor. The medicinal acid is usually obtained by distilling, at a moderate heat, a solution of ferrocyanide of pota.ssium, K^FeCyg, with dilute sulphuric acid, and collecting the product in water, contained in a cooled receiver. The reaction is as follows: 2K^FeCyg-|- 6H2SO^^ 6KHSO^H-K2Fe2Cy6+6HCy. The commercial acid, when pure, has a very feeble acid reaction, and a density varying with its strength; when it contains about three per cent, of the acid, its spe- cific gravity is about 0.998. When hydrocyanic acid is brought in contact with a solution of an alkaline hydrate, both the acid and alkaline compound undergo decomposition, with the formation of a salt, or cyanide, of the metal, and the production of water; thus: KHO-f- HCy=KCy-fH20. These salts are freely soluble in water; they are readily decomposed by acids, with the evolution of free hydrocyanic acid. When ex- 12 178 HYDROCYANIC ACID. posed to the air, either in their solid state or in solution, they slowly absorb carbonic acid, and thus become changed into carbonates, the eliminated prussic acid being dissipated in the form of vapor. The cyanides of the metals proper, unlike those of the alkalies, are for the most part insoluble in water; but many of them are freely soluble in a solution of an alkaline cyanide, with the formation of a double salt. Special Chemical Properties. — It has been claimed by sev- eral toxicological writers that the odor of hydrocyanic acid serves to detect the presence of smaller quantities of the poison than can be recognized by any of the chemical tests ; but this is an error, even in regard to the vapor from perfectly pure solutions of the acid. Nevertheless, under certain conditions, extremely minute quantities of the acid may thus be recognized. We have found, in repeated experiments, that when ten grains of a l-50,000th solution of the pure acid (=-g-^^ grain HCy) are enclosed for some time in a small test-tube, and the tube then opened, the peculiar odor of the poison is sufficiently marked to be described by persons entirely ignorant of the true nature of the solution. With a similar quantity of a l-100,000th solution an odor is perceptible, but its peculiar char- acter is lost. It need hardly be repeated that the odor from even strong solutions of the poison may be entirely disguised by the pres- ence of other odors. There are but few chemical tests to which we resort for the detec- tion of hydrocyanic acid, but these are so characteristic and delicate in their reactions as to leave nothing more to be desired in this respect. Moreover, they are equally applicable for the detection of the vapor of the poison. In the following examination of these tests, the fractions employed indicate the quantity of anhydrous prus- sic acid in solution in one grain of pure water. The results, unless otherwise stated, refer to the behavior of one grain of the solution. 1. Silver Nitrate. Nitrate of silver throws down from solutions of free hydrocyanic acid, and of soluble cyanides, a white amorphous precipitate of cy- anide of silver, AgCy, which is insoluble in the fixed caustic alka- lies, and only sparingly soluble in ammonia, but readily soluble in the alkaline cyanides. Cold nitric acid fails to dissolve it, but it is soluble in the hot concentrated acid ; hydrochloric acid decomposes i^lIA'ER TEST. \7U it with the fonuiitioii of chloiidc of silver and tlic cvolutidn oC hyilrocyaiiic acid. 1. yItg grain of Ijydroeyanic acid, in one trrain of water, yields a very copious precipitate, which does not entirely disappear wIkii the mixture is heated with several drojis of strong iiitri<; acid. 2. yo^yo grain yields a (copious precipitate, which readily dissolves on the addition of a drop of strong ammonia; but dissolves with difficulty, in the mixture, in several droj)s of warm nitric acid. 3. TTf.VoT g'*^i" '• '1 quite good flocculent precipitate. 4. ^s^.VuTF grain yields no immediate precipitate, but in a very little time the mixture becomes turbid, and soon there is a very satisfactory deposit. 5. ^ly.oinr grain : after a little time a very distinct opalescence, and soon a very perceptible deposit. ^' TinF.lFinF grain : in a few minutes the mixture becomes very dis- tinctly turbid. Fallacies. — Nitrate of silver also produces white precipitates in solutions of free hydrochloric acid, of chlorides, carbonates, phos- phates, tartrates, and some other salts, and also with various kinds of organic matter. These precipitates, however, except that from chlorine, are readily soluble in strong nitric acid, in which they differ from the cyanide compound. The chloride of silver readily darkens when exposed to light, whereas the cyanide remains unchanged in color ; again, the former salt is readily soluble in ammonia, whilst the latter is not, unless present only in very minute quantity. Tol- erably strong solutions of iodides and bromides, and of their free acids, yield with nitrate of silver yellowish-white precipitates; from dilute solutions, however, these precipitates, in regard to color, might readily be mistaken for the cyanide compound, especially when they are obtained from organic mixtures : like the cyanide deposit, they are nearly insoluble, or dissolve with difficulty, in cold nitric acid. The cyanide of silver is readily distinguished from all other pre- cipitates produced by this reagent, in that when thoroughly dried and heated in a narrow reduction-tube it undergoes decomposition with the evolution of cyanogen gas, which, when ignited, burns with a rose-colored flame. If this decomposition be effected in a small tube, which after the introduction of the dried cyanide has been drawn out into a very narrow capillary neck, beginning something 180 HYDROCYANIC ACID. less than an inch above the cyanide compound, the 1-lOOth of a grain of the salt will yield satisfactory results. For the success of this experiment it is essential that the cyanide be thoroughly dried before being introduced into the tube. Vapor of Hydrocyanic Acid. — When the vapor of prussic acid is received on a drop of nitrate of silver solution, the latter becomes coated with a white film of cyanide of silver, which, especially from dilute solutions of the acid, is crystalline, and most abundant along the margin of the drop. In its behavior with reagents this deposit has the properties already described. This test may be applied by placing a drop of the acid solution in a watch-glass, and covering the latter with a similar inverted glass, containing a small drop of the silver solution. By this method one grain of the acid solution yields as follows : 1. y^ grain of hydrocyanic acid, in one grain of water: an imme- diate cloudiness is observed in the silver solution, and in a very little time there is a quite copious white deposit. Under the microscope, the deposit has the appearance of an amorphous mass, but if broken up with the point of a needle it will be found to consist of very small but distinct crystals. If the watch-glass containing the poison be first placed on the stage of the microscope and then covered by the glass containing the silver solution, the formation of the crystals may, at least for a time, be observed. 2. YFTo gi'ai" '• 8^11 immediate cloudiness appears in the reagent solu- tion, and soon there is a quite good, white film. If its formation be observed under the microscope, the crystals will be found to form more slowly and become somewhat larger than in 1. 3. Yo.Voo" g'^^i'i • ii^ ^ little time a cloudiness appears, and after a few minutes there is a quite good deposit, which consists principally of irregular crystals, varying from the 1-lOOOth to the l-2000th of an inch in length, of the forms illustrated in Plate IV., fig. 1. Usually, small granules, prisms, and needles form along the margin of the drop. 4. 2T,Wo graio : after a little time the margin of the silver solution becomes white, and soon there is a good crystalline deposit. 5. -g-o.Wo gr^iii '• when a very small drop of the reagent solution is employed, crystals appear in less than two minutes, and before long there is a very satisfactory deposit. IltON TRST. IHI 6. ^^ ^^^^ grain : after a few inimitos crvHtals can be seen with the microscope, and after .some minutes they are qnite evident to the nuked eye. The deposit is confined to the niai-^in of the drop, and chiefly consists of grannies, small prisms, and needles, Plate IV., fig. 2. So far as the evidence of the presence of hydrocyanic acid is concerned, this qnantity furnishes as un- equivocal results as any larger amount. The formation of the deposit is much facilitated by applying the warmth of the hand to the watch-glass containing the acid solution. It need lianlK- be observed that if the silver solution becomes nearly dry from evaporation, ciystals of nitrate of silver may sepa- rate; but these have a very different form from those of the cyanide, and, moreover, they immediately disappear on the addition of a very small drop of water, whilst the cyanide crystals are almost wholly insoluble in this liquid. The vapors of chlorine, bromine, and iodine, and of their hydro- gen acids, also yield white or nearly white films with a solution of nitrate of silver. The deposits from all these substances, however, are amorphous; whereas the cyanide compound is always crystalline, even when obtained from complex organic mixtures of the acid, pro- vided sulphuretted hydrogen, or some other gaseous substance which also produces a deposit with the reagent, is not present. The odor of these substances, as well as that of hydrocyanic acid, would gen- erally suffice to determine the true nature of the film produced by these various vapors, even without the aid of the microscope. The deposits produced by the vapors of bromine and iodine have a faint yellowish-white color. It may be remarked that the vapors of chlo- rine and of hydrochloric acid generally cause the dispersion of the silver solution, so that it trickles down the inside of the inverted watch-glass; and the films produced by them are quite thin, even wljen occasioned by the pure gases. 2. Iron Test. "When a solution of free hydrocyanic acid is treated with a solution of potassium or sodium hydrate, and then with a solution of ferrous sulphate which has been exposed to the air and contains some feriic sulphate, it yields a precipitate of Prussian blue, Fe^SFeCyg, mixed with more or less monoxide and sesquioxide of iron : this mixture may have either a yellowish-brown, greenish, or bluish color, the hue 182 HYDROCYANIC ACID. depending upon the relative quantities of the iron compounds present. On treating this mixture with a few drops of hydrochloric or sul- phuric acid, the oxides of iron dissolve, while the Prussian blue re- mains in the form of a deep blue deposit, it being insoluble in the acid. Should the hydrocyanic acid already exist in the form of an alkaline cyanide, the addition of the potassium or sodium solution should be omitted. In a solution of free prussic acid, the iron com- pounds alone produce no change. The object of the addition of the free alkali in the above process is to convert the free hydrocyanic acid into an alkaline cyanide. When this salt is then treated with the ferrous and ferric sulphates, a double decomposition takes place, in which the alkaline cyanide becomes changed into potassium sulphate, and the iron sulphates into cyanides of iron; thus: 18KCy + 3FeS04+2Fe23SO^=9K2S04 + 3FeCy2 + 2Fe2Cy6 ; the elements of the iron cyanides then coalesce to form Prussian blue (SFeCyg + 2Fe2Cy6=Fe43FeCy6). It is thus obvious that the presence of both the iron salts is necessary for the production of the blue compound. The oxides of iron precipitated by any excess of the alkali employed are dissolved by the hydro- chloric or sulphuric acid added, as chlorides or sulphates of iron. In very dilute solutions of hydrocyanic acid, the test fails to pro- duce an immediate precipitate ; but the liquid, after the addition of the mineral acid, immediately acquires a greenish color, and after a time deposits flakes of the blue compound. Such solutions also re- quire a proper adjustment of the alkali and iron solutions. A large excess of the alkali will decompose the Prussian blue, while a similar excess of the iron mixture produces with hydrochloric acid a yellow liquid which may hold in solution a small quantity of the blue com- pound. When, therefore, the addition of hydrochloric acid produces a yellow solution from which no Prussian blue separates, even after a time, the experiment should be repeated with a less quantity of the iron solution before pronouncing hydrocyanic acid entirely absent. There is no difficulty in the application of the test, except in very dilute solutions of the poison. In no case should any inference be drawn from the color of the precipitate prior to the addition of the mineral acid, since it may have a bluish color even in the absence of prussic acid. When one grain of a solution of hydrocyanic acid is treated as above, it yields the following results : IRON TRST. 183 1. y^ «]jr:\iii of tlx" |)in-o ju-id yic^lds :i very copious deposit of Prus- sian 1)1 IK'. 2. jTjVir J?''=i'" '■ '^ ^'*''y ^ood deposit. 3. t^jVc" S^^'" • ^ i^reeiiisli-hluo, flocculent j)r('cipitate and a greenish solution ; after a time, the deposit increases in quantity and ac- quires a deeper blue color, Sohitions dilute as this, especially when only a single drop is operated upon, require a proper ad- justment of the reagent solutions: when these are very strong, only a very small drop of each should be employed. 4. x^.VuTJ" grai" : with a very small quantity of the reagent solutions, yields a quite perceptible greenish-blue, flocculent precipitate, with a greenish solution ; after the mixture has stood some little time, the result is perfectly satisfactory. 5. yj.VuT g''f^in yields just perceptible greenish flakes, and, after a few hours, a quite distinct deposit, which, when examined by a hand-lens, has a well-marked blue color. The production of a blue precipitate insoluble in hydrochloric acid by this test is perfectly characteristic of hydrocyanic acid, or at least of a cyanide. At the same time, the reaction is not interfered with bv anv substance at all likelv to be met with in medico-lesfal investigations. Vapor of Hydrocyanic Acid. — In the application of this test for the detection of the vapor of the poison, the vaj)or is received for some minutes on a drop of potassium hydrate solution, by which it will be absorbed as potassium cyanide, without, however, any visible change ; the solution is then treated with the iron mix- ture and hydrochloric acid, in the manner above described. The vapor from one grain of a l-5000th solution of the poison will, when the manipulations are conducted with great care, yield quite satisfactory results. This, however, is about the limit of the vapor reaction. This method may be employed to confirm the nature of the cyanide of silver produced by the preceding reagent. For this pur- pose the washed deposit, placed in a watch-glass, is treated with a drop of hydrochloric acid, and the vapor of the hydrocyanic acid thus eliminated absorbed by a drop of potassium hydrate solution, in the manner just pointed out. By this process the true nature of a much less quantity of the silver precipitate may be fully established than by the method of reduction, heretofore described. 184 HYDROCYANIC ACID. 3. Sulphur Test. When a solution of free hydrocyanic acid or of an alkaline cyanide is treated with a solution of yellow sulphide of ammo- nium, and the mixture gently heated, it gives rise to sulphocya- nide of ammonium, NH^CyS, which, when treated with a ferric salt, yields a deep blood-red solution of sulphocyanide of iron, FcgGCyS. This reaction was first pointed out in 1847, by Prof. Liebig. In applying this test, a few drops of the prussic acid solution, placed in a small white dish or watch-glass, are treated with a drop of the ammonium sulphide, and the mixture evaporated at a moderate temperature on a water-bath to near dryness. Should the residue have a yellow color, it is moistened with a drop of water and again evaporated. The cooled residue — consisting of ammonium sulpho- cyanide, often in its crystalline state, and a white film of sulphur — is then treated with a drop of a colorless solution of ferric sulphate or of ferric chloride, when the mixture will immediately assume, unless very dilute, a very deep blood-red color. If the excess of ammonium sulphide added has not been entirely decomposed or vola- tilized, the iron reagent will produce a black precipitate of sulphide of iron ; this, however, is readily dissolved by a drop of dilute hydro- chloric acid, without interfering with the red color of the mixture, unless it is very feeble. 1. YTo gi'^iii of hydrocyanic acid, when treated as above, yields a beautiful blood-red solution. 2. YFTo gi'sii^ yields an orange-colored mixture. 3. 37o',Wo g^'^'in ' the final solution has a very satisfactory light orange hue. 4. 2T.V0T g^^i^^ yields a mixture having a distinct reddish tint. The color of this mixture is quite well marked when compared with that of the reagents alone. 5. s-o.VoT gi'3'ij^ yields a just perceptible coloration. The red color produced by this test is immediately discharged by corrosive sublimate, and by nitric acid ; but it is unaffected by even very large excess of strong hydrochloric acid, except from very dilute solutions, when it is readily destroyed by an excess of this acid. It is also discharged, to a faint reddish hue, by an alkaline acetate, but immediately restored upon the addition of hydro- SULPHUR TEST. 185 chloric acid; ammonia causes it to disappear, with llic precipitiitioii of sesquioxide of iron. Fallacies. — Ferric salts also strike a deep l)lo()(l-red color with solutions of iiieconic acid. This color, however, is not discharged by corrosive sublimate, nor is it affected by an alkaline acetah;, and it is readily changed to yellow or reddish-yellow hy an excess of hydrochloric acid. The reagent also changes very drong solutions of the alkaline acetates to a deep dark-red color, due to the formation of ferric acetate: this color, however, is immediately discharged to a faint yellow tint by even a very small quantity of hydrochloric acid. In this connection it may be remarked that both meconic acid and the alkaline acetates are destitute of odor. The objections just mentioned are the only ones that can reason- ably be urged against the sulphur test, and they are readily answered. When, therefore, a susjiected solution yields with the test a strong red color, unaffected by large excess of hydrochloric acid, there is no doubt of the presence of a sulphocyanide ; yet, should the color be only faint, its disappearance on the addition of the acid would not prove the entire absence of the poison. Vapor of Hydrocyanic Acid. — The sulphur test may also be ap- plied for the detection of the vapor of the acid, as iirst suggested by Dr. A. Taylor. For this purpose, a drop of the ammonium sulphide solution, contained in an inverted watch-glass, is exposed to the evolved vapor for some minutes, and then examined in the manner above described. The vapor evolved from the 1-1 0,000th of a grain of prussic acid, in one grain of water, will after this method, providing the ammonium solution has been exposed to the vapor from ten to fifteen minutes, yield a very distinct coloration; but the result could hardly be claimed to be satisfactory. It need hardly be added that when the sulphur test is applied in this manner it is free from the fallacies that hold in its direct application to a suspected liquid. The sulphur test may also be employed to confirm the precipi- tate ])roduced by the silver reagent. For this purpose, the washed precipitate is treated with a few drops of sulphide of ammonium, and the mixture evaporated, at a gentle temperature, to dryness. In this operation, the cyanide of silver will be decomposed by the ammonium compound, with the formation of silver sulphide and ammonium sulphocyanide. On now treating the dry residue with a 186 HYDROCYANIC ACID. little water, the ammonium salt will dissolve, and the solution, after filtration and concentration, will yield the usual blood-red color when treated with a persalt of iron. So, also, this test may be applied to the vapor evolved, when the cyanide of silver is decomposed by a drop of strong hydro- chloric acid. Relative Delicacy of the foregoing Tests. — In regard to the relative value, in this respect, of the Silver and Iron tests, it may be observed that when they are applied to the vapor of the poison the former is much the more delicate, while for solutions the latter is much the more susceptible. It is true that the silver test will produce a precipitate with a much less quantity of the poison than the iron test will reveal ; yet the silver deposit cannot in itself be regarded as peculiar until it yields an inflammable gas when heated in a reduction-tube, for which purpose it requires, with the greatest care, the precipitate corresponding to at least the l-500th of a grain of the poison, and even the deposit from this single quantity could by no means be collected and confirmed : but the iron test produces a characteristic reaction with one grain of a 1-1 0,000th solution of the poison. On the other hand, when applied to the vapor of hydrocyanic acid, the iron reaction has its limit with about the 1— 5000th of a grain of the acid, whilst the silver test yields a satisfactory result with the l-100,000th of a grain, in one grain of water. In other words, for solutions the iron test is about twenty times more delicate than the silver test, while for the vapor of the poison the silver reaction is about twenty times more delicate than the iron test. In regard to the Sulphur test, when applied to solutions of the acid, it is somewhat more delicate than the iron reaction, and so also in regard to the detection of the vapor, but in the latter respect it is very much inferior to the silver method. From a review of these tests, it is obvious that should a suspected solution fail to yield a precipitate with silver nitrate, it would be useless to apply either of the other tests ; yet it should be remembered that a solution which only yields a faint reaction with the silver reagent may evolve a vapor that will yield with it very satisfactory results. The comparative value of these tests may be approximatively exhibited as follows : SEPARATION FROM OROANFC MIXTURES. 187 Silver test, witli Snlutions, ^^„ t^raiii ; with Vupor, xisj/.Tiffiy i^''"'"- Iron test, " " jo.ooo f^'""'" i " " Wcff g^aiii. Sulplnir test, " " ^^.V^^ grain ; " " rJS.hs gi^a'"- It need hardly be observed that these results are based ii|)on the assumption that the poison is in solution in one (jr a in of pure water, and, it may be added, manipulated with care by experienced hands. Other Tests. — For the detection of hydrocyanic acid, Lassaigne advised to precipitate it by a solution of Copper Sulphate, as copper cyanide ; but in every respect this test is inferior to those already mentioned. Mercurous Nitrate produces in solutions of free hydrocyanic acid, and of alkaline cyanides, a dark gray or nearly black precipitate of finely divided metallic mercury. This reaction serves to distinguish hydrocyanic acid and its simple salts from hydrochloric acid and its compounds, which yield with the reagent a white precipitate of mer- curous chloride, or calomel. The application of this test, for this purpose, would of course be unnecessary if the iron or sulphur test has been applied. Schonbein's Test. — This consists in moistening a slip of guaiacum- paper with a solution of copper sulphate, and exposing it to the action of hydrocyanic acid, when it will immediately assume a deep blue color. The guaiacum -paper is prepared by steeping filtering-paper in about a three per cent, solution of guaiacum resin, and drying it. For the copper solution, one part of the sulphate may be dissolved in five hundred parts of water. At the moment of use, the test- paper is moistened with the copper solution and then exposed to the hydrocyanic acid, either diffused in the air as vapor or dissolved in water. M. Schonbein states that the delicacy of this reaction is such that even one part of the vapor of the acid in 120,000,000 parts of air will yield the blue coloration. This reaction, however, is not peculiar to hydrocyanic acid, since ozone, chlorine, and several other vapors produce a similar coloration. Separation from Organic Mixtures. As hydrocyanic acid is liable to be rapidly dissipated in the foriu of vapor, and even to undergo spontaneous decomposition, the examination of a mixture in which its presence is suspected should not be delayed. The same method of research will apply equally to 188 HYDROCYANIC ACID. suspected articles of food or medicine, the matters vomited, and the contents of the stomach. Before resorting to the application of any chemical test, the suspected mixture should be carefully examined in resrard to its odor : but it must be borne in mind that mixtures of this kind may contain a very notable quantity of the poison without emitting its peculiar odor. Examination for the Vapor. — For this purpose, the suspected mixture is placed in a glass jar or any similar vessel, and the mouth of the vessel then covered by an inverted watch-glass in which has been previously placed a drop of nitrate of silver solution. Sooner or later, even if only a minute trace of the vapor is being evolved from the mixture, the silver solution will acquire a white incrustation of cyanide of silver. Any deposit thus produced is then examined under the microscope : at the same time, the mouth of the bottle should be closed by a cork, or by another Avatch-glass containing a drop of the silver reagent. Should the microscope reveal the presence of crystals of the forms already described, these will fully establish the presence of the poison, since there is no other substance that will yield similar results. Should, however, the deposit be amorphous, it may still, in part at least, be due to the cyanide; but it might be due to the presence of chlorine, or possibly to the vapor of bromine or of iodine. Under these circumstances, the true nature of the deposit, if cyanide of silver, may be established either by the iron or the sulphur test in the manner already indicated. One or both of these latter tests should also be applied directly to the suspected mixture, even in case the silver reaction is satisfactory. Should the silver solution, after an exposure of several minutes, fail to indicate the presence of the poison, the suspected mixture should be occasionally agitated by shaking the bottle, and the appli- cation of the reagent be continued for half an hour or longer. If there is still no evidence of the presence of the poison, it is not likely that it would be detected by this method, even if applied for several hours ; yet it must not be concluded that the poison is entirely absent even in its free state, since it may be strongly retained by organic substances. In case the silver reagent should fail to receive a deposit, it would of course be useless to apply either of the other tests for the vapor. Method hy simple Distillation. — After testing the suspected liquid in regard to its reaction and setting apart a small portion, for future SEPARATION FROM OIKJANIC MIXTURES. ' 180 exnniination if necossarv, tlio renminiiij^ portion is placed in a retort liavin- toms giadiKiily subsided, and after several days the patient was (juite well. (Ainer. Jour. Med. >Sei., Jan. 1853, 131.) In a ease eoinniu- nicatcd to me by Dr. R. Denig, a woman re<;overed in a few days after taking fully sixty grains of the salt in solution. Within ten minutes after taking the dose the i)atient experienced great distress and burning pain in the stomach, accompanied by retching and vomiting. A case is recently reported in which recovery took place after one hundred and seventy grains of the salt had been taken. (Med. Rec, New York, 1883, 401.) It is well known that in certain inflammatory diseases tartar emetic may be administered in very large doses without producing any of its ordinary effects. Treatment. — If there is not alreadv free vomiting;, it should be promoted by the administration of large draughts of warm water; or the stomach may be emptied by means of the stomach-pump. As a chemical antidote, various vegetable astringents, such as a strong infusion of Peruvian bark, green tea, nut-galls, or oak bark, have been highly recommended; and instances are reported in which their exhibition was apparently attended with very great advantage. It has, however, been denied that these substances serve to neutralize the poison. After the poison has been expelled from the stomach, opium may be administered to check the excessive vomiting. For this purpose a strong decoction of coffee has also been highly recommended. Post-mortem Appeaeanges. — In the case cited from Orfila, which proved fatal in about four days, the mucous membrane of the stomach, except near the gullet, where it was healthy, was red, tumefied, and covered with a viscid coating, which was easily sepa- rated ; the duodenum Avas in a similar condition, but the other intestines were healthy. The intestines were entirely empty. The brain was congested and softened. The organs of the chest were healthy. In the case related by Dr. Lee, in which fifteen grains of the poison had been taken, the mucous membrane of the stomach was red and softened, and on holding it up to the light it appeared of a bright crimson color. The stomach contained a small quautitv of slimy mucus, and, like the mucous membrane, Avas softened. The texture of the cardiac orifice seemed more changed than that of the 222 AXTIMONY. pyloric. The duodenum was of a deep brown color, almost livid, and contained the same kind of substance as found in the stomach. The inflammation extended no farther than the colon. The vessels of the scalp, as well as those of the brain, and the right side of the heart, were distended with blood. The ventricles of the brain were half filled with fluid, and there was effusion between the pia mater and the arachnoid membranes. In Dr. Ellis's case, thirty-nine hours after death, the body was quite rigid, and there was considerable bluish discoloration about the back of the neck and the hands. The stomach contained a quantity of gruel-like, acid liquid, in which a considerable quantity of anti- mony was found. No well-marked morbid appearances were detected in any of the abdominal organs. The brain was not examined. Chemical Properties. General Chemical Nature. — Tartar emetic, as found in the shops, is usually in the form of a white amorphous powder. In its pure state it crystallizes in large, transparent, odorless octahedrons having a rhombic base. The crystals are slightly efflorescent at or- dinary temperatures, and when heated to 100° C. (212° F.) become anhydrous. When heated in a reduction-tube, by the flame of a spirit-lamp, tartar emetic readily blackens, from the decomposition of the organic acid, and is soon reduced to a mixture of charcoal and metallic anti- mony. It undergoes a similar change when heated upon platinum- foil, quickly destroying the platinum in contact with the heated mass. Heated on charcoal before the blow-pipe flame, the charred mass burns with the production of a widely diffused incrustation, the thicker portions of which have a whitish color, while the thinner ones have a bluish appearance; at the same time it yields globules of metallic antimony, which boil and are slowly dissipated by the continued action of the het^t. If the globules are allowed to cool^ they will be found exceedingly brittle. According to R. Brandes, tartarized antimony is soluble in from twelve to fourteen parts of water at the ordinary temperature, and in less than three parts of boiling water. From a warm saturated solution the salt separates on cooling in beautiful bold crystals, Plate IV., fig. 4. The same crystals separate when one grain of a 1-lOOOth or stronger solution of\the salt is allowed to evaporate \ \ \ SULPHURETTED lIYDR(XiEN TEST. 223 spontaneously to dryness ; from more dilute solutions the residue is usually destitute ot" any well-deiined crystals. Aqueous solutions of tartar emetic are colorless, have a nauseous, metallic taste, and a feeble acid reaction, even when the liquid contains only the 1-lOOOth of its weight of the salt. These solutions after a time undergo decomjxj- sition, the organic acid giving rise to a filamentous growth : we have found tliis formation make its appearance, after several days, in solu- tions containing even less than the l-50,000th of their weight of the antimony compound. Tartar emetic is insoluble in alcohol. If this liquid be added to an aqueous solution of tartar emetic containing even something less than the 1-lOOth of its weight of the salt, the latter is precipitated in the form of plumose crystals ; sometimes, however, the precipitate also contains octahedral crystals. Special Chemical Properties. — When tartar emetic in its solid state is moistened with a solution of sulphide of ammonium or of sulphuretted hydrogen, it immediately acquires an orange-red color, due to the production of a sulpliide of antimony. This reaction is peculiar to antimony, and will manifest itself with the least visible quantity of the salt. Even the residue left on evaporating one grain of liquid containing only the 1-1 0,000th of a grain of the pure salt will yield a very satisfactory coloration. In the following investigations in regard to the special reactions of reagents with solutions of tartar emetic, pure aqueous solutions of the salt were employed. The fractions employed indicate rlie amount of sesqaioxide of antimony, SbgO,, present in one grain of the solution. The amount of crystallized tartar emetic represented in these cases may be readily obtained by multiplying the fractions by 2.28. 1. Sulphuretted Hydrogen. From somewhat strong normal solutions of tartar emetic this reagent throws down a deep orange-red precipitate of sesquisulphide of antimony, or antimonious sulphide, Sb2S3 ; in more dilute solutions it produces an orange-red turbidity, but no precipitate, at least for several hours. The formation of the precipitate from dilute solutions is much facilitated by heat. From solutions acidulated with hydro- chloric acid, however, even when very dilute, the reagent produces an immediate precipitate. The precipitate is insoluble in diluted hydrochloric acid, but 224 ANTIMONY. soluble in the concentrated acid, even at ordinary temperatures, and still more readily under the action of heat, with the formation of trichloride of antimony and the evolution of sulphuretted hydrogen gas. Fuming nitric acid converts it into a white insoluble compound of antimony. It is readily soluble in the fixed caustic alkalies, but insoluble in ammonia : at least we find that when one part of the moist precipitate is frequently agitated for some days with 10,000 parts of ammonia solution it does not entirely disappear, and that one part with even 25,000 parts of ammonia requires some hours for solution. When dried and fused with sodium nitrate, it gives rise to sodium metantimoniate and sulphate. In the following examination in regard to the limit of this test, Jive grains of the antimony solution, placed in a small test-tube, were acidulated with hydrochloric acid, and then treated with the reagent. 1. 1-lOOth solution of sesquioxide of antimony (=^ grain SbgOg) yields a very copious, light orange-red precipitate. Solutions of tartar emetic as strong as this require about half their vol- ume of hydrochloric acid to redissolve the precipitate first pro- duced by the acid. When tartaric acid is employed as the acidi- fying agent, the precipitate produced by the sulphur reagent has a much deeper red color than when produced in the presence, of hydrochloric acid. 2. 1-lOOOth solution : an immediate precipitate, which very soon becomes quite abundant. A normal solution of tartarized anti- mony of this strength yields with the reagent a deep orange solution, but no precipitate, even after standing twenty-four hours. 3. 1-1 0,000th solution : an immediate turbidity, and, after a little time, a good deposit. If the mixture be warmed, the precipitate sejjarates almost immediately. When the solution is acidulated with tartaric acid, the precipitate requires several hours for its separation, 4. l-25,000th solution : in a very little time the mixture acquires an orange tint ; and after several hours there is a satisfactory deposit. 5. l—50,000th solution : in a little time the liquid assumes a yellow tint, then a reddish hue, and after several hours yields a quite perceptible orange-yellow deposit. 6. l-100,000th solution : after some minutes the liquid acquires a LEAD AND ZINC TESTS, 225 faint yullow tint, hut undergoes no further change for at Ica.'^t several hours. The reaction of this reagent, as already intimated, is quite char- acteristic of antimony. If the precipitate be dissolved in hot hydro- chloric acid, and the solution after cooling treated with several times its volume of water, it yields a white precipitate, consisting of ses- quioxide and trichloride of antimony, which after a time becomes crystalline, and is readily soluble in tartaric acid. Sulphide of Ammonium, also, throws down from comparatively strong normal solutions of tartar emetic a precipitate of sesquisul- phide of antimony, which is soluble in excess of the reagent. In five grains of a 1-lOOOth solution of sesquioxide of antimony the reagent produces a good yellow-orange deposit. In more dilute solutions it fails to produce a precipitate, but communicates to the liquid an orange or yellowish-red color. In the presence of a free acid, however, it precipitates even highly dilute solutions of the salt. 2. Acetate of Lead. This reagent produces in normal solutions of tartar emetic a white amorphous precipitate of the double tartrate of antimony and lead, . Pb(SbO)2CsH80i2, which is readily soluble in acetic and tartaric acids, and decomposed by nitric acid with the production pf a white floccu- lent deposit. 1. YW^ grain of sesquioxide of antimony, as tartar emetic, in one grain of water, yields a very copious precipitate. 2. Y^jj-jj grain : a very good flocculent precipitate. 3. i-g-.Voir grai" yields a very satisfactory deposit. 4. 2T,Voi7 grain : after a little time the mixture becomes quite turbid. Acetate of lead also produces white precipitates in solutions of various other substances. But the antimony deposit diflfers from all these in that when washed and moistened with sulphide of ammo- nium it immediately assumes an orange-red color; after a little time, however, this color changes to a dark brown or nearly black hue. 3. Metallic Zinc. When a drop of a solution of tartar emetic is placed on a piece of platinum-foil and acidulated with a small drop of hydrochloric acid, the addition of a fragment of zinc causes the separation of 15 226 . ANTIMONY. metallie antimony, which adheres to the platinum covered by the liquid, forming a black or brownish stain (Fresenius). The deposit is readily soluble in nitric acid, especially if warmed, but only sparingly soluble in concentrated hydrochloric acid ; when washed and dried, it is easily dissipated by heat. 1. YoT gJ'ain of sesquioxide of antimony, in solution in one grain of water, when treated in the above manner, yields a very copious, deep black deposit. 2. YWU^ grain : a very good deposit. 3. 3 Q^Q Q grain : after a very little time there is a very satisfactory dark-brown stain. 4. Yo'.Too" g^^i"^ • after a few minutes a very distinct brownish stain makes its appearance. The antimonial nature of these deposits may be shown by moist- ening the washed stain with nitric acid, and evaporating to dryness at a gentle heat, when the residue, on being touched with sulphide of ammonium, will assume an orange-red color. Under the action of this test solutions of arsenic yield no de- posit ; whilst solutions of tin yield a deposit upon the zinc, but none upon the platinum. 4. Metallie Copper. When a solution of tartar emetic is acidulated with hydrochloric acid, and boiled with a slip of bright copper-foil, the antimony com- pound undergoes decomposition with the deposition of metallio anti- mony upon the copper, in the form of a violet or gray coating, the color depending upon the thickness of the deposit. It is obvious that the thickness of the deposit produced by a given quantity of the metal will depend upon the size of the copper-foil employed in the experiment. When one grain of the tartar emetic solution, placed in a thin watch-glass, is acidulated and heated with a very minute portion of the foil, it yields as follows : 1. yl-g- grain of sesquioxide of antimony: the copper immediately assumes a violet color, and soon receives a thick, dark-gray coating. 2. YiroT gi'ain yields much the same results as 1. 3. Yir.Wo gi*ain : in a little time the copper presents a beautiful violet color. HYDROGEN TEST. 227 4. ^tj-.Vfc S'"*'^''' yields u very distinet reaction. 5. -nn/.TnriT S'"''" • ^^'''en the liquid is evaporated to near dryness, the copjjer acquires a perceptible violet tai-ui.sh. The j)roduction of a metallic deposit ui)on copper under tlie aln)ve conditions is common to antimony, arsenic, mercury, and some few other metals. The violet color of the antimony deposit is rather peculiar; hut the deposit from this metal does not always present this color, and, moreover, very thin deposits of arsenic may present a similar hue. When the coated copper is washed, dried, and heated in a narrow reduction-tube, the antimony deposit, if not in too minute quantity, yields a sublimate which forms quite near the heated slip of copper, and is generally amorphous, or at most granular, in form, but it may contain well-defined octahedral crystals of antimonic oxide, and sometimes crystalline needles. The arsenic deposit under like conditions is vaporized at a lower temperature, and yields, under proper conditions, a sublimate fully half an inch above the copper, and consisting wholly of octahedral crystals. The sublimate from mercury appears in the form of minute metallic globules. The other metals referred to fail to yield a sublimate when thus treated. The true nature of the antimony deposit may be shown, as first advised by Mr. Watson, by boiling the coated copper in a dilute solution of caustic potash, the coated metal being occasionally with- drawn from the liquid and exposed to the air to favor the oxidation of the antimony, when, after a time, the deposit will be entirely dis- solved as antimoniate of potassium. On now removing the copper- foil, and acidulating the liquid with hydrochloric acid, concentrating to a small volume, and then treating it with sulphuretted hydrogen gas, pentasulphide of antimony, SbgSs, of an orange-red color, will be precipitated. This method will serve to identify even very small deposits of the metal. 5. Antimonuretted Hydrogen. When a solution of tartar emetic, or of any of the soluble salts of antimony, is mixed with zinc and sulphuric acid, in the propor- tion to evolve hydrogen, the salt is decomposed and the antimony evolved as antimonuretted hydrogen gas, SbHj. This decomposi- tion may be effected in the apparatus of Marsh, first devised for the detection of arsenic. Fig. 3. 228 ANTIMONY. Pure zinc and sulphuric acid, previously diluted with about four volumes of water, are placed in the flask A, which is furnished with a drying-tube, c, and a reduction-tube, d, the latter of which is of hard glass and made to terminate in a drawn-out point. The drying-tube should be loosely filled with fragments of calcium chloride. When only a minute quantity of antimony solution is to be examined, the glass flask may be replaced by a test-tube. After the apparatus has become completely filled with hydrogen, a small quantity of the an- PlG. 3. Apparatus for the detection of antimony . timony solution is introduced into the flask by means of the funnel- tube a, when in a few moments the evolved gas will contain anti- monuretted hydrogen, the presence of which may be shown by three different methods. 1. If the gas as it escapes from the end of the reduction-tube be ignited, it burns with a bluish flame, and, unless the amount of antimony present is very minute, evolves white fumes of sesqui- oxide of antimony. If these fumes be received upon a cold surface, as a piece of porcelain, they yield a white amorphous deposit, which irYDUOQEN TEST. 229 immediately acquires an orange-red color when moistened with sul- pliide of ammonium. If a piece of cold porcelain, held in a hori- zontal position, be brought in contact with the flame, the antimony will condense in the form of a black, nearly circular spot or stain, which is usually surrounded by a grayish ring; as soon as a spot has thus formed, the Hame should be received upon a fresh portion of the porcelain. If the experiment be performed in a small apparatus, fifty grains of a fluid mixture containing the l-10,000th of its weight of sesqui- oxide of antimony (=^J^ grain Sb^) will yield quite a number of spots of the metal. Antimony and arsenic are the only metals that under the above conditions will yield metallic spots upon a cold surface. The spots from these two metals generally differ somewhat in regard to theu- ])hysical appearance, those from antimony being usually dull, whereas those from arsenic have generally a bright metallic lustre. They differ greatly, however, in regard to some of their other properties. Thus, the antimony-stains are slowly and with difficulty dissipated by the flame of a spirit-lamp, whilst those from arsenic are readily volatilized. Again, the antimony spots readily dissolve in yellow sulphide of ammonium, and the solution,- even from very small stains, when gently evaporated to dryness, leaves a red or orange-red residue of sulphide of antimony, which is soluble in strong hydrochloric acid, but insoluble in ammonia; whereas the arsenic-stains dissolve but slowly in yellow sulphide of ammonium, and the solution leaves upon evaporation a yellow residue of arsenious sulphide, insoluble in hydrochloric acid, but readily soluble in ammonia. Moreover, the antimony-stains are insoluble or dissolve with great difficulty in a solution of sodium or calcium hypochlorite, whilst the arsenic spots readily disappear when touched with a solution of this kind. 2. When a portion of the reduction-tube is heated to redness, the antimonuretted hydrogen passing through the tube is decomposed with separation of metallic antimony, which, when only in small quantity, is deposited within the tube wholly on the inner side of the part to which the flame is directly applied, but when in larger quantity, on both sides of the flame. Arsenic under like circum- stances yields a somewhat similar deposit; but in this case tlie whole of the metal is deposited in the tube on the outer side of the part to which the flame is applied. 230 ANTIMONY. A much smaller quantity of antimony will in this manner fur- nish a deposit that will produce spots from the ignited jet upon porcelain. Fifty grains of a solution containing the 1-50, 000th of its weight of sesquioxide of antimony (= yfto gi^ain SbgOg), when treated in a small apparatus, will yield a very good brownish-black deposit; and a similar quantity of a l-500,000th solution, a very distinct brownish stain, within the heated tube. Deposits of the metal produced by this method exhibit the same chemical reactions as those produced on porcelain by the ignited gas. 3. If the antimonuretted hydrogen be conducted into a solu- tion of silver nitrate, the whole of the antimony is precipitated as antimonide of silver, AggSb, in the form of a black powder. The chemical reaction in this case is as follows: SbH3-l-3Ag]S[03 = AggSb + 3HNO3. When only a minute trace of antimony is pres- ent, the whole of the precipitate collects in the lower end of the delivery-tube, in the form of a black ring. This reaction is extremely delicate, and the method can be applied with a much smaller quantity of fluid than either of those just men- tioned. When the operation is performed in a small test-tube and the evolved gas conducted into a few drops of the silver-solution, five fluid-grains of a 1-1 0,000th solution of the antimony oxide will produce a quite large, black deposit, much of which remains in the end of the delivery-tube. A similar quantity of a l-50,000th solution produces after several minutes a very satisfactory deposit ; and a l-100,000th solution will produce in about fifteen minutes a very distinct reaction. Solutions of arsenic, of sulphides, and of several other substances will also under similar conditions evolve gaseous compounds, which produce black precipitates in a solution of silver nitrate. In the action of the arsenical compound, the precipitate consists alone of metallic silver, the arsenic being oxidized into arsenious oxide, which remains in solution. The true nature of the antimony precipitate, or antimonide of silver, may be shown by collecting the deposit on a filter, washing with warm water, and boiling with dilute hydrochloric acid, in which the antimony will dissolve, while the silver will remain in an in- soluble form. If the quantity of precipitate present is too minute to be separated from the filter, the portion of the latter containing the deposit is boiled in the dilute hydrochloric acid. When the CHEMICAL PROPERTIES. 231 acid mixture lias cooled and llu; deposit completely subsided, it is transferred to a filter wliicli has previously been moistened with water, and the filtration repeated if necessary until the filtrate is perfectly elear. On now treating; the solution with sulphuretted hydrogen, sesquisulphide of antimony, of its peculiar color, will he tiirown down. Professor ITofraann has recommended to boil the washed anti- monide of silver with a solution of tartaric acid, in which the antimony readily dissolves, while the silver remains unchanged; the solution is then filtered and treated with sulphuretted hydro- gen. {Quart. Jour. Chem. Soc, April, 1860, 79.) By either of the methods now considered, an exceedingly minute quantity of anti- mony may be recovered from the silver precipitate. From what has already been stated, it is obvious that the method under consideration will serve to detect antimony in the presence of arsenic, and the latter in the presence of the former. And this may be effected even when the metals are present in very minute and disproportionate quantities. Antimonuretted hydrogen is also decomposed by an alcoholic solution of potassium hydrate, with the production of a black precipitate. Arsenic under similar conditions fails to produce a precipitate. Other Reactions of Tartar Emetic— A'iV/'fc acid produces in somewhat strong solutions of tartar emetic a white amorphous precipitate, which, according to Geiger, consists of a basic nitrate of antimonic oxide. The precipitate is soluble only in very large excess of the acid, but is readily soluble in tartaric acid ; in solutions con- taining free tartaric acid, therefore, the reagent fails to produce a precipitate. When the washed precipitate is touched with sulphide of ammonium, it immediately assumes an orange-red color. One grain of a 1-lOOth solution of sesquioxide of antimony when treated with a drop of the acid yields a quite copious deposit, which does not disappear on the further addition of several drops of the reagent. One grain of a 1-1 00th solution yields with a small drop of the acid a very fair precipitate. Hydrochloric acid occasions in concentrated solutions of the salt a white precipitate, which is much more readily soluble in excess of the reagent than in the preceding reaction; it is also very readily 232 ANTIMONY. soluble in tartaric acid. One grain of a 1-lOOth solution of sesqui- oxide of antimony yields with a drop of the reagent a quite good precipitate, which disappears when the mixture is stirred. This acid also produces white precipitates in solutions of silver, of lead, and of mercuroas combinations. The silver precipitate is readily soluble in ammonia, and that from mercury is turned black, whilst the pre- cipitates from lead and antimony are unchanged by this reagent. Sulphide of ammonium causes the antimony precipitate to assume an orange-red color, whilst it turns the lead-deposit black. The antimony precipitate is the only one of these that is soluble in tar- taric acid. Sulphurie acid throws down from similar solutions a white amor- phous precipitate, which becomes orange-red when touched with sulphide of ammonium. The production of a white precipitate by this acid is common to solutions of several other metals. Ammonia precipitates from solutions of tartar emetic white sesquioxide of antimony, which is insoluble in excess of the pre- cipitant. One grain of a 1-lOOth solution of the antimony oxide yields a very good precipitate; and a similar quantity of a 1-1 000th solution yields a quite fair, granular deposit, especially if the mix- ture be stirred. Ammonium carbonate fails to produce a precipitate even in concentrated solutions of the antimonial compound. Potassium and Sodium hydrates produce in quite concentrated solutions of the salt white amorphous precipitates, which are readily soluble in excess of either reagent. The carbonates of these alkalies, however, throw down white precipitates that are insoluble in excess of the precipitant; the limit of these reactions is about the same as that of ammonia. When a solution of tartar emetic is treated with sufficient excess of potassium hydrate to redissolve the precipitate first produced, and a solution of silver nitrate then added, it produces a brownish-black precipitate, consisting of a mixture of suboxide and monoxide of silver, while the antimony remains in solution as potassium anti- raoniate. If the precipitate thus produced be treated with ammonia, the monoxide of silver is dissolved, while the suboxide remains as a dense black powder. One grain of a 1-1 0,000th solution of anti- mony sesquioxide, when treated after this method, will yield a very satisfactory black deposit ; and the reaction is visible when a similar quantity of even a l-25,000th solution of the antimony compound SEPARATION FUOM OROAXIC MIXTURES. '233 is tMiiployecl. Nitrate ol" silver alone inoiliices in solutions of the antimony salt a white precipitate. Corrosive sublimate slowly tiirows clown from solutions of the salt, even when quite dilute, a white floeculent precipitate. C'hro- mate and dichromatc of potassium impart to very strong solutions a greenish color, and throw down a slight, greenish precipitate. Ferro- i\iu\ ferri-ci/a)ude of jjotassium fail to produce a preci[)itate even in concentratetl solutions of the antimony com})ound. Separation from Organic Mixtures. Suspected Solutions. — The same method of analysis is equally apjdicable for the examination of suspected articles of food or drink, vomited matters, aud the contents of the stomach. The mixture, after the addition of water if necessary, is acidulated with hydro- chloric acid, a little tartaric acid added, and the whole exposed to a gentle heat for about fifteen minutes. When the mixture has cooled, it is thrown upon a muslin strainer, the strained liquid filtered, and the filtrate, after concentration if necessary, exposed to a current of sulphuretted hydrogen gas as long as a precipitate is produced, and then allowed to stand in a moderately warm place for several hours, in order that the precipitate may completely subside. If antimony is present in comparatively large quantity, the pre- cipitate thus obtained will have a more or less orange-red color ; if, however, the metal is present in only minute quantity, or the deposit contains much organic matter, it will present a yellow or brownish appearance. The precipitate is now collected upon a filter, washed with water containing a little hydrochloric acid, and then heated with strong hydrochloric acid, when any sesquisulphide of antimony present will be decomposed and the metal dissolved as trichloride. After solution has taken place, the heat should be continued until the odor of the sulphuretted hydrogen, evolved by the decomposition, has entirely disappeared. A small portion of the clear liquid may now be examined by the zinc and copper tests in the manner already described, except that it is not necessary to add hydrochloric acid, since this is already present. Another portion of the liquid may be treated with large excess of water, when the antimony, unless present in only very minute quan- tity, will be precipitated as white oxychloride (5Sb203 ; 2SbCl3), the 234 ANTIMONY. true nature of which is fully established by its assuming an orange- red color when moistened with sulphide of ammonium, as well as by its ready solubility in tartaric acid. Should these tests yield posi- tive reactions, a given portion of the solution, properly diluted, may be treated with sulphuretted hydrogen gas, and from the amount of antimony sesquisulphide obtained, the quantity of tartar emetic determined in the manner hereafter described. If it is desired to reconvert the antimony present in the hydro- chloric acid solution into tartar emetic, it may be precipitated, by addition of water, as oxychloride, and the precipitate collected, washed, and then agitated for some time with a very dilute solution of sodium carbonate. In this operation the oxychloride of anti- mony will be entirely converted into sesquioxide of the metal, the chlorine being taken up as chloride of sodium : care should be taken to employ only a very dilute solution of the sodium salt, since other- wise more or less of the antimorly compound might be dissolved. The precipitate is now collected, washed, and digested at a moderate heat with a little water containing an appropriate quantity of potas- sium tartrate, or cream of tartar, when it will be dissolved as tartar emetic, the presence of which may be determined by the usual tests. Should the precipitate produced from the original solution by sulphuretted hydrogen have a dark color, it should not be con- cluded, from this circumstance alone, that the metal is entirely absent; since it might be present even in very notable quantity, and yet the peculiar color of its sulphide be entirely masked by the presence of organic matter. Under these circumstances, the washed precipitate, placed in a thin porcelain dish, may be treated with a few drops of concentrated nitric acid, and the mixture cautiously evaporated to dryness, the operation being repeated, if necessary, until the organic matter is well destroyed. Any antimony present will now exist as an oxide of the metal. The residue is then moistened with a few drops of a strong solution of potassium hydrate, the liquid expelled by a moderate heat, and the dry residue very gradually heated to fusion. The cooled mass is stirred with a little water, the mixture acidulated with tartaric acid, then boiled for some minutes, and the solution filtered. The whole of the antimony will now be present in the filtrate, which, if the operations have been conducted with care, will be perfectly colorless. A portion or the whole of the solu- SEPARATION FROM OKOANIC MIXTURES. 235 tion may now be treutcd with a lew (lro|)s of liydrocliloric acid and exposed to a current of sulphuretted hydrogen gas, when any sulphide of antimony thrown down will exhibit its characteristic color. By this method the sulphide of antimony produced from the 1-1 00th of a grain of the sesquioxide of the metal may be recovered from a very complex organic mixture without any apparent loss. Should the final solution obtained by the above method be highly colored, then, instead of treating it with sulphuretted hydrogen, it may be mixed with zinc and diluted sulphuric acid in the aj)i)aratus of Marsh, and the evolved gas conducted into a solution of silver nitrate, as long as a black precipitate is produced. Any antimonide of silver thus obtained is collected on a small filter and well washed ; the point of the filter is then pierced, and the precipitate washed, by means of a jet of water from a wash-bottle, into a small dish, then boiled with a little tartaric acid, the solution filtered, and, after con- centration if necessary, examined in the usual manner. The sulphide representing the 1-lOOth of a grain of sesquioxide of antimony may be carried through both these processes and still yield perfectly satis- factory results. If it be desired, in case the investigation for antimony should fail, to provide for the detection of other poisonous metals whose sulphides are also precipitated from acidified solutions by sulphuretted hydrogen, such as arsenic, mercury, lead, and copper, the following method may be pursued. The filter containing the washed and still moist precipitate is spread out in a dish, the deposit well stirred with a solution of yellow sulphide of ammonium, and the solution filtered. As the sulphides of antimony and arsenic are readily soluble in sul- phide of ammonium, these metals if present would be in the filtrate, while the sulpirides of mercury, lead, and copper, being insoluble in this menstruum, would remain on the filter, which should therefore be reserved for future examination if necessary. The ammoniacal filtrate is now evaporated to dryness, and the residue treated with nitric acid anc\ potassium hydrate in the manner already described. Any arsenic present would now exist as arsenate of potassium, and the solution when treated with sulphuretted hydrogen would yield a yellow precipitate of pentasulphide of arsenic. If this metal was not present, and the mixture contained antimony, the results already described would of course be obtained. Should these two metals 236 ANTIMONY. occur in the same solution, they may be separated by treating the mixture with zinc and sulphuric acid and receiving the evolved gas in a solution of silver nitrate, in the manner heretofore pointed out. From the Tissues. — The investigations of Orfila and others have shown that antimony, when taken into the stomach, is rapidly absorbed by the blood and deposited in the tissues, and that the absorbed poison may be entirely eliminated from the living body within a very few days, the elimination taking place chiefly through the urine. Of the different tissues of the body, the liver and kidneys usually contain the largest proportion of the absorbed poison. About one-third of the liver, cut into very small pieces and placed in a porcelain dish, may be made into a thin paste with water containing about one-fifth of its volume of pure hydrochloric acid. The mixture is then exposed to a moderate heat, with frequent stir- ring and the occasional addition of small quantities of powdered potassium chlorate, until the organic solids have become entirely disintegrated. The cooled mixture is transferred to a muslin strainer, and the organic matter left upon the cloth well washed with water, the washings being collected with the first-strained liquid ; the solution is then filtered, the filtrate concentrated, allowed to cool, and if necessary again filtered. The solution is now ex- posed for several hours to a slow stream of sulphuretted hydrogen gas, after which it is allowed to repose for about twenty-four hours, in order that the precipitate may fully subside. Any precipitate thus obtained is collected, heated with nitric acid, then fused with potassium hydrate, and the residue examined in the manner described above. For the recovery of absorbed antimony, Orfila recommended to decompose the organic matter by nitric and sulphuric acids. The tissue, cut into small pieces, is boiled with nitric acid, the homoge- neous mixture evaporated to dryness, and the residue well charred with concentrated sulphuric acid. The dry carbonaceous mass is then boiled with hydrochloric acid containing a few drops of nitric acid, when any antimony present will be dissolved as chloride. The solution thus obtained is introduced into the apparatus of Marsh, and the evolved gas examined in the usual manner. Absorbed antimony may also be recovered by boiling the finely divided tissue with pure hydrochloric acid diluted with about six volumes of water, and introducing into the boiling mixture separate SEPAKATION FROM ORGANIC MIXTURES. 237 slips of" briglit copper-foil as long as they continue to receive a metallic coating. Only a small slip of the copper should at first be employed. Should this after several minutes fail to receive a de- posit, it is removed from the mixture, and the boiling continued until the organic tissue is entirely disintegrated. The cooled mix- ture is then strained, and the strained liquid again boiled with a fresh slip of copper, the heat being continued if necessary until the liquid is evaporated to near dryness. It may be remarked that this method would not apply to organic mixtures which had been pre- pared by means of potassium chlorate, since the products of this salt would prevent the deposition of the antimony. Froni the Uinne. — Evaporate one thousand grains of the urine to a thick syrup; treat the residue on a water-bath with fuming nitric acid, portions at a time, until the urea is entirely destroyed, then evaporate to dryness. Moisten the residue with concentrated sul- phuric acid, and heat on a sand-bath until the mass is dry and fumes of the acid no longer escape. Heat the powdered residue with about one hundred and twenty-five grains of water containing a few drops of hydrochloric acid until the soluble matter is ex- hausted ; filter, and concentrate tlie filtrate to about eighty grain- measures. Treat the liquid with sulphuretted hydrogen, and gently warm the mixture: if the urine contained l-250th grain or more of antimony, the precipitate produced will have a strongly marked red color. Collect the precipitate on a small filter, and wash it with water, small portions at a time, until any calcium sulphate and other salts that may have separated are dissolved. Separate the portion of the filter containing the deposit from any unstained portion, and spread it in a porcelain dish; add a few drops of hydrochloric acid, and heat until the deposit has dissolved, then add a little water, squeeze and wash the paper. Filter, and treat the filtrate with sulphuretted hydrogen, when any antimony present, even if only in very minute quantity, will be precipitated as sulphide of its characteristic color. By this method we have recovered the 1-lOOOth of a grain of antimony from one thousand grains of urine (1 : 1,000,000) without any very marked loss. In a series of experiments on the elimination of this metal by means of the urine, conducted in the University laboratory by Dr. Wm. R. Hock ( Thesis), single doses of ten milligrammes (about one- 238 ANTIMONY. sixth grain) each of antimony in solution were taken or adminis- tered. In one instance the urine voided within jive minutes after the dose had been taken furnished satisfactory evidence of the pres- ence of the metal ; and in several instances it was detected in from ten to fifteen minutes after being taken. The greatest elimination seemed to take place within from one to two hours, after which it gradually diminished, but traces were still found as late as ninety- six hours after the dose had been taken. Quantitative Analysis. — The pure solution, acidulated with hydrochloric acid, is treated with sulphuretted hydrogen gas as long as a precipitate is produced, and the mixture gently warmed until the supernatant liquid has become perfectly clear. The precipitate is then collected on a filter of known weight, washed, thoroughly dried on a water-bath, and weighed. Every one hundred parts by weight of sesquisulphide of antimony thus obtained correspond to 85.88 of the sesquioxide, or 196.47 parts of pure crystallized tartar emetic. Al^SKMC. 2.'i9 CHAPTER Y. ARSENIC. I. Metallic Arsenic. History and Chemical Nature. — By the term arsenic the chemist understands a certain simple or elementary form of matter, having metallic properties; this term, however, is popularly applied to an oxide of tiie metal, — nrsenious oxide. The symbol for arsenic is As; and its atomic weight 75. Arsenic is found in nature in certain localities in its free state; in combination it is widely distributed, being found in certain minerals and ores, and in minute traces in many mineral waters and their ferruginous deposits. The state- ment formerly made by Orfila, that arsenic occurred as a normal constituent in the bones and muscles of animals, was afterward retracted as incorrect. In its pure state arsenic has a steel-gray color, a bright metallic lustre, and a density of about 5.8 ; it has a crystalline structure, and is readily reduced to powder, being veVy brittle. It remains un- changed in dry air; but in the presence of moisture it slowly absorbs oxygen and assumes a dull dark-gray appearance. When heated, it volatilizes, without fusing, into a colorless vapor, which on coming in contact with the air emits a garlic-like odor; if strongly heated in the open air, it takes fire and burns with a bluish flame and the evolution of dense white fumes of arsenious oxide. It is generally stated that arsenic volatilizes at a temperature of about 182° C. (360° F.), but, according to Dr. Guy, when in small quantity, it sublimes at 110° C. (230° F.). Hot sulphuric and nitric acids oxi- dize and dissolve the metal, the former as arsenious and the latter as arsenic acid. Hydrochloric acid has no action upon it; but free chlorine converts it into chloride of arsenic. 240 AESENIC. Physiological Effects. — Metallic arsenic, when taken into the sys- tem, is capable of acting as a powerful poison ; but perhaps only in so far as the metal becomes oxidized and converted into arsenious acid. From the experiments of Bayen and Deyeux, and others, it would appear that the metal in its uncombined state is inert. The substance sold in the shops under the name of fly-powder consists essentially of a mixture of metallic arsenic and arsenious oxide, the latter usually being present, it is said, in the proportion of about five per cent. Numerous instances of poisoning by this substance have occurred, chiefly, however, as the result of accident. In a case of criminal poisoning by fly-powder, in which we were consulted, death took place in thirty-six hours ; and although there had been almost incessant vomiting for over thirty hours, a quantity of ar- senic equivalent to forty-two grains of arsenious oxide remained in the stomach at the time of death. The symptoms and morbid changes produced by this substance are much the same as those occasioned by arsenious oxide. Special Chemical Properties. — There is little difficulty in recog- nizing metallic arsenic. When volatilized in a narrow reduction- tube it condenses in the cooler portion of the tube, forming a very characteristic sublimate. This sublimate usually consists of two well-defined but conjoined parts, the lower of which has a steel-like appearance, and when viewed on the in- FiG. 4. side presents a crystalline structure, re- A sembling somewhat that of fractured iron; the upper part of the deposit, when viewed exteriorly, is destitute of lustre, and of a dark color, which grad- ually fades into a light-gray margin, in Tubes for sublimation of arsenic. which crystals of arscnious oxidc are sometimes found. When the sublimate is quite thin it presents a brown appearance. On the application of heat, the sublimate is readily chased up and down the tube, and sooner or later becomes converted into white, octahedral crystals of arsenious oxide ; this conversion is much hastened if the closed end of the tube has been separated. These reactions are peculiar to arsenic. If metallic arsenic be dissolved, by the aid of heat, in strong nitric acid, and the solution evaporated to dryness, it leaves a white ARSENIOUS OXIDE. — ARSENIOUS ACID. 241 residue of arsenic oxide, whicli, when moistened witli a strong solu- tion of" silver nitrate, assumes a brick-red color. A portion of" the arsenic oxide obtained by this method may be dissolved in water and submitted to the liquid' tests for this acid, mentioned hereafter; or, the solution may be saturated with sulphurous oxide gas (SOg), the excess of the gas expelled by heat, and the solution then examined for arsenious acid. Compounds of Ai'senic. — Arsenic forms with oxygen two well- defined oxides, — namely, arsenious oxide, AsgOj, and arsenic oxide, AsoO.. The hydrates of these oxides are known respectively as (irscnious acid and arsenic acid. A lower, or suboxide, has been described, but its existence is doubtful. Arsenic unites with sulphur in several proportions; the most important of these compounds are disulphide of arsenic, or Bealgar, As^^i which has a ruby-red color; sesquisulphide of arsenic, or Orpiment, AS2S3, having a bright yel- low color; and pentasulphide of arsenic, AsgSg, the color of which closely resembles that of orpiment. With hydrogen the metal forms arsenuretted hydrogen, or hydrogen arsenide, AsHg, which is a colorless, highly poisonous, gaseous compound. With chlorine it forms trichloride of arsenic, AsClg. Arsenic also enters into various other combinations. All the soluble compounds of this metal, and such insoluble combinations as undergo decomposition when taken into the system, are poisonous. As a general rule, their activity in this respect is in proportion to their solubility. Some of the insoluble compounds as usually met with not unfrequently contain arsenious oxide. This is the only compound of the metal that will be considered in detail; in its consideration, however, the chemical properties of several of the other compounds will be very fully described. II. Arsenious Oxide. — Arsenious Acid. Arsenious oxide, commonly called white arsenic, and also known as ratsbane, is a compound of two atoms of arsenic with three of oxygen, AsgOg ; its molecular weight is 99. It is readily obtained by volatilizing metallic arsenic in a free supply of air. For commer- cial purposes, it is usually prepared by roasting some one of the ores of the metal in a reverberatory furnace communicating with large chambers, in which the oxide condenses. Arsenious oxide is found in the shops under two different forms, 16 242 AESENIC. — either as a white or dull white, opaque powder, or in the form of large, hard masses. If recently prepared, these masses are colorless and transparent ; but on exposure to the air they become opaque and of a white or yellowish-white color. This change from the transparent to the opaque state has been ascribed to the absorption of moisture. The powder, as found in the shops, when examined under the microscope, is sometimes wholly amorphous, consisting of very fine dust and small fragments, it being prepared simply by pulverizing the large masses. At other times it consists in part or wholly of miimte octahedral crystals, these ranging in size from about l-250th to l-5000th of an inch in diameter. Hence the microscopic char- acter of the powder — as to whether crystalline or not, the relative proportion of crystals to amorphous matter, and the prevailing size of the crystals or lumps — may in some instances enable us to de- termine with great certainty that a given sample was not derived from a certain source or supply. It has been found by several observers that great uniformity generally exists among samples of the powder taken from the same source, as from different and distant parts of the same keg. For examinations of this kind, it is best to mount a small portion of the powder in Canada balsam.* Arsenious oxide, whether in the solid state or in solution, seems to be nearly or entirely destitute of taste. At least, it has frequently been swallowed in large quantity without any marked taste being perceived ; in other instances, however, its taste has been variously described as sweetish, rough, hot, acrid, or metallic. Symptoms. — These are subject to great variation. Sooner or later after a large dose of the poison has been swallowed there is usually a sense of heat and constriction in the throat, with thirst, nausea, and burning pain in the stomach. The pain becomes excruciating, and is attended with violent vomiting and retching ; the matters vomited present various appearances, being sometimes streaked with blood, and at other times of a bilious character; the pain in the stomach is increased by pressure. As the case progresses, the pain extends throughout the abdomen, and there is generally severe *For a very full consideration of -the microscopic differences observed in samples of commercial arsenic, we would refer the reader to a valuable paper by Prof. E. S. Dana, of New Haven. {Pamphlet, 1880.) PHYSIOLOGICAL EFFECTS. 243 pur^'ingaiul tenesmus; tlic matters j)assed from the bowels not unfre- qiiently contain blood. Tlic thirst usually becomes very intense; in some instances there is i»;reat (iilliciilty of swallowing. Tije features are collapsed and expressive of great anxiety ; the pulse is quick, small, and irregular; the eyes red ; the tongue dry and furred; the skin cold and clammy, but sometimes hot; the respiration difficult; and sometimes there arc violent cramps of the legs and arms. The urine is frequently diminished in quantity, and its passage attended with great pain. Stupor, delirium, paralysis, and convulsions have also been observed. In many instances death takes place calmly, and the intellectual faculties remain clear to the last. Such are the symptoms usually observed in poisoning by arsenic; but cases are reported in which the abdominal pain, thirst, vomiting, and purging were either very slight or entirely absent. In these instances the symptoms are usually not very unlike those commonly observed in poisoning by a narcotic. There is generally great pros- tration of strength, and faintness, or even actual syncope; often convulsions, and sometimes delirium or insensibility. It was for- merly believed that well-marked gastric symptoms were absent only when a very large dose of the poison had been taken ; but this is by no means always the case. In a case of arsenical poisoning mentioned by Dr. Christison, an individual expired in five hours without at any time having vomited, although emetics were administered. The following case of this kind is reported by Mr. Fox. [Lancet, London, Nov. 4, 1848.) A stout, healthy young man took a teaspoonful of arsenious oxide, mistaking it for flour. No marked symptom of the action of the poison appeared for nearly six hours afterward, when purging suddenly supervened, and he vomited two or three times. He then became drowsy; countenance sunken and livid; pulse rapid and extremely feeble ; surface of the body cold, and watery stools of a greenish hue passed involuntarily. He answ^ered questions ration- ally, and did not complain either of pain, tenderness of the abdomen, tenesmus, or any of the usual irritative symptoms of arsenical poison- ing. Soon afterward he complained of dimness of sight, lay down on the bed, and in a few minutes expired. In most cases of acute poisoning by this substance the symp- toms steadily run their course ; yet sometimes there is a remission or even an entire intermission of the more prominent symptoms. This 244 AESENIC. remission may extend through a period of several hours, and the symptoms then return with increased violence. The remission has even been repeated several times in the same case. The following singular case is related by Dr. C. U. Shepard, of South Carolina. {Pamphlet, 1878.) An intemperate man purposely swallowed, towards evening, about an ounce of arsenic. Imme- diately after taking the draught he vomited considerably, and during the night at intervals. The next morning he went into the street, having up to that time experienced little or no pain. About an hour later, however, he was seized with severe pains in the epigastrium, and fell on the pavement in great agony. After a few hours the pain subsided, and he was comparatively well. But several hours later he was again seized with violent pain in the stomach, and with excessive vomiting and purging. Wild delirium and general con- vulsions then supervened, and terminated fatally about twenty-four hours after the poison had been taken. Considerable variety has also been observed in regard to the time within which the symptoms first manifest themselves. In most instances, however, they appear in from half an hour to an hour after the poison has been taken. In the case just related, there was, according to the statement of the patient, immediate vomiting. And in a case cited by Dr. Beck, a woman, who had swallowed a quantity of the poison mixed with wine and an egg, experienced extreme dis- tress immediately after taking the mixture. [Med. Jur., ii. 595.) In another instance, quoted by the same writer, twelve persons in one family were seized with symptoms immediately after eating some soup containing the poison. Dr. Christison quotes a case in which the symptoms appeared in eight minutes; and two others in which violent symptoms were present in ten minutes after the poison had been taken. On the other hand, instances are related in which the symptoms were delayed much beyond the usual period. A case of this kind, in w^hich they did not appear for nearly six hours, has already been cited. In a case related by Dr. Ryan, where half an ounce of arsenic was taken in porter, the first symptom, which was vomiting, did not occur until nine hours afterward. (Wharton and Still6, 31ed. Jur., 513.) A case is also quoted by Dr. Taylor, from Belloc, in which ten hours elapsed before any symptoms appeared. {On Poisons, 359.) And Dr. Wood mentions an instance {U. S. Dispensatory, 1865, 26), EFFECTS OF EXTERNAL APPLrCATIDN. 245 related l>v Dr. K. Hartsliornc, in wliidi at least a drachm of arseni- ous oxide had been swallowetl, and where the syniptoius of poisoning wore delayed for sixteen hours. This seeras to be the most protracted case, in this respect, yet recorded. The external application of arsenic to abraded surfaces has not unfrcquently been followed by fatal results. In a case reported by Dr. McCready, a wash composed of a mixture of arsenious oxide and i;in, applied to the head of a child two years old, affected with porrigo favosa, caused death in about thirty-six hours. The most prominent symptoms were swelling of the face, purging and tenesmus, and paralysis of the lower extremities. No local inflammation was produced. Two other children who were similarly treated suffered with redness and swelling of the face ; but they speedily recovered. [Am. Jour. Med. Sci., July, 1851, 259.) Dr. Christison cites an instance in which the stearine of a candle containing arsenic, applied to a blistered surface, produced local pain, nausea, pain in the stomach, great thirst, redness of the tongue, spasms of the muscles of the lower extremities, and weakness and irregularity of the pulse, fol- lowed by death within twenty-four hours after the application had been made. In a series of cases recently reported (1878), a mixture sold as violet poicder, containing nearly fifty per cent, of arsenic, — ignorantly substituted for gypsum, and this used instead of starch, — applied exter- nally to some twenty-eight infants, caused death in thirteen instances. All the children suffered more or less from the application. The symptoms were a reddened condition of the skin, which soon became blue or black, and vesicated ; there was great restlessness, with fits of screaming, followed by collapse and quiet death. The average duration of the fatal cases was from four to five days. Arsenic has also proved fatal when applied to the mucous mem- brane of the vagina and of the rectum, and when inhaled in the form of vapor. In a case reported by Dr. Mangor, a man poisoned three waves in succession by introducing arsenic into the vagina. In at least two of these instances the poison produced its usual symptoms and death in twenty-four hours. Within late years numerous in- stances of chronic poisoning by this substance have occurred from pereons occupying rooms hung with paper stained with Scheele's green, or arsenite of copper. From the examination of twenty-one cases of poisoning of this kind. Dr. Kirchgasser, of Coblentz, con- 246 ARSENIC. eludes that the deleterious eflFects are due to the mechanical suspen- sion of arsenical dust in the air of the apartment, rather than to the presence of a volatile arsenical compound, as some have supposed. {Sydenham Soc. Year-Booh, 1869, 446.) Period when Fatal. — In fatal poisoning by this substance, death usually occurs in from twelve to thirty-six hours after the poison has been taken. Numerous instances, however, are related in which death took place within a very few hours ; while, on the other hand, life has not unfrequently been prolonged for several days. The most rapidly fatal case yet recorded is that communicated to Dr. Taylor, in which a youth, aged seventeen, died from the eflFects of a large dose of the poison within twenty minutes after it had been taken. {Med. Jur., i. 256.) Dr. D. W. Finlay has recently reported a case fatal in one hour from the eflPects of a solution containing upwards of twenty-six grains of arsenious oxide. In this case there was profound collapse, with only slight symptoms of irritation. {Lancet, Dec. 1883, 943.) Not less than three instances fatal in two hours are reported. In a case related by Dr. Dymock, death occurred in two hours and a half; and Pyl relates another, which proved fatal in three hours. {Christison on Poisons, 240.) Ninety grains of the poison caused the death of a girl, aged fourteen years, in five hours. Several instances are reported in which the patients recovered from the primary action of the poison and died from its secondary effects very long periods afterward, even in one instance, related by Wepfer, after the lapse of three years. Fatal Quantity. — According to the observations of Prof. Lach&se, of Angers, a dose of from one to two grains of arsenious oxide may prove fatal to a healthy adult; a dose of from a quarter to half a grain may induce symptoms of poisoning ; and one-eighth of a grain may prove injurious. In a case quoted by Dr. Taylor, two grains of the poison, in the form of Fowler's solution, taken in divided doses during a period of five days, destroyed the life of a woman. The same writer cites another instance, reported by Dr. Letheby, in which two grains and a half killed a robust, healthy girl, aged nineteen, in thirty-six hours. {On Poisons, 377.) In a case mentioned by Dr. Christison, four grains and a half caused the death of a child, four years old, in six hours. On the other hand, recovery has not unfrequently taken place after very large quantities of the poison had been swallowed. In a ANTIDOTES. 247 case recorded by Dr. Pereira, a man swallowed half an ounce of powdered arsenics iinmediately after takin<^ his dinner, and the only effect produced was violent vomiting. {Mat. 3fed., i. 032.) So, also, Dr. A. Stillo {3fat. Med., ii. 707) quotes the case of a woman who .swallowed about a dessertspoonful of the poison immediately after a hearty meal, and although vomiting did not occur, nor were any remedies administered for an hour and a half, yet within five days complete recovery had taken place. The following remarkable case is reported by Dr. AV. C. Jackson. {Am. Jour. Med. Sci., July, 1858, 77.) A young man, aged twenty- eight vears, took on an empty stomach not less than ttvo ounces of the poison. Nearly two hours afterward there was slight vomiting, with some traces of the arsenic; but the greater part of the poison was retained in the body for six hours. Great irritability of the stomach then ensued, with a burning sensation in this organ and in the throat. This condition continued for about six hours, after which the patient rapidly recovered. In a case quoted by Prof. H. C. Wood {3fat. Med. and Toxicol., 1874, 320), a man swallowed an unknown quantity of arsenic in lumps, and received no treatment for sixteen hours, yet recovered after passing per anum one hundred and five grains of arsenic in two masses. Treatment. — This consists, in the first place, if there is not already free vomiting, in the speedy administration of an emetic, or the stomach may be emptied by means of the stomach-pump. As an emetic, sulphate of zinc or of copper may be employed ; if neither of these is at hand, powdered mustard or a mixture of salt and water should be administered, or vomiting may be induced by tickling the throat with a feather. The vomiting should be assisted by the free exhibition of demulcent drinks. For this purpose a mixture of milk and white of egg has been found very beneficial. If the poison has passed into the bowels, a dose of castor oil may be highly useful. Of the various chemical antidotes that have been proposed for arsenious acid, hydrated ferric oxide, known also as hydrated sesqui- oxide of iron, FcoOgjoHoO, is much the most important. Drs. Bun- sen and Berthold, in 1834, were the fii-st to assert the antidotal properties of this substance. When it is added to a solution of arsenious acid, the latter is rendered wholly, or very nearly, in- soluble in water. In support of this statement we may adduce the 248 AESEN-IC. following experiments: 1. One grain of arsenious oxide, in solu- tion, was agitated for a very little time with five grains of the iron preparation suspended in half an ounce of water, and the mix- ture quickly filtered. The filtrate was then examined and found to contain less than the 1-lOOth of a grain of the poison. 2. When ten parts of the iron preparation were employed, and the filtrate concentrated to one hundred fluid-grains, then acidulated with hy- drochloric acid, and saturated with sulphuretted hydrogen gas, it failed to yield any distinct evidence of the presence of the poison, even after standing at a moderate temperature for several hours. These experiments do not, of course, prove that the compound thus produced is insoluble in the acid secretions of the stomach ; yet the excess of the iron preparation administered might neutralize any free acid present. The antidotal action of this substance is due to the hydrated ferric oxide yielding a portion of its oxygen to the arsenious acid, whereby the latter is converted into arsenic acid, which in turn unites with a portion of the iron, forming arsenate of iron (Fe32As04), which being insoluble is inert. Thus : 2Fe203,3H20 + 2H3ASO3 = Fe32As04 + FeO + 9TI2O. Theoretically, therefore, one part of arsenious oxide in solution as arsenious acid requu'es 2.16 parts of pure hydrated ferric oxide to render it inert. The antidote should, however, be given in its moist state, and be administered in large excess. It is usually stated that about twelve parts of the moist compound are required for one part of arsenious oxide. The antidote has no action upon arsenious oxide in its solid state, but only when in solution. Hydrated ferric oxide may readily be prepared by treating tinc- ture of ferric chloride of the shops, or a strong solution of ferric sul- phate, with slight excess of ammonia, collecting the precipitate on a muslin strainer, and washing it with water until it no longer emits the odor of ammonia. A tablespoonful or more of the moist magma, mixed with a little water, may be given at a dose. The antidote should always be freshly prepared. In this connection, we may very briefly refer to some experi- ments, kindly undertaken by Dr. Wm. Watt, with this antidote upon poisoned dogs. (For details, see Ohio Med. and Surg. Jour., March, 1861.) The action of the poison alone was first determined upon five dogs of average size. To three of these, six grains of arsenious ANTIDOTES. 249 oxide, ill solution, were i^iven to euoli, and proved futiil in one hour and II half, five hours, and six hours respectively. To the otiier two, three grains each were administered, and caused death in six and eiglit hours respectively. A solution of the poison was then adminis- tered to twelve other dogs, and the dose followed — in some instances immediately, in others in ten minutes, and in others still not until symptoms of poisoning had manifested themselves — by a single dose of about two tablespoonfuls of the antidote, prepared in the manner just described. After vomiting, in some instances only once, but in others several times, all these animals recovered, at most within sev- eral hours, and without in any instance suffering severe symptoms. Two of these dogs received three grains; two, four grains; one, five grains ; three, six grains ; two, seven grains ; and two, eight grains each of the poison. In another experiment, six grains of the poison, in solution, were mixed with about fifteen parts by weight of the antidote, and the mixture, after standing twenty minutes, given to a dog; no appreciable effect whatever was observed, although the animal was closely watched for many hours. This experiment, therefore, indicates that the arsenate of iron is not readily decom- posed by the juices of the stomach. Numerous instances are reported in which there seems to be no doubt that this antidote was the means of saving life iu the human subject. Mr. Robson relates an instance of this kind, in which more than a drachm and a half of the poison had been swallowed, and the antidote was not administered until two hours after the poison had been taken. In this case, about an hour after the inges- tion of the poison, the stomach-pump was used, but unsuccessfully, on account of the instrument becoming choked with the remains of food. [U. S. Dispensatory, 1865, 29.) It need hardly be remarked that the antidote can have no effect upon any of the poison that has already entered the circulation. Instead of the above antidote, R. V. Mattison has advised [Am. Jour. Pharm., Jan. 1878, 23) a solution of dialyzed iron, followed immediately by the administration of common salt. According to E. Hirschsohn, of Dorpat, however, dialyzed iron is much less cer- tain in its action than the antidotum arsenici, which consists of a mixture of hydrated ferric oxide, magnesium sulphate, and magne- sium hydrate, being prepared by treating a solution of ferric sulphate with excess of magnesia. 250 ARSENIC. In four cases of arsenical poisoning reported by Dr. C. A. Leale, of New York [Am. Jour. Med. Sci., Jan. 1880, 80), he employed as an antidote the common subcarbonate of iron with good results, although in one instance fully one ounce of arsenious oxide, and in the others one-half ounce, one ounce, and two ounces respectively of Paris green had been taken. Post-mortem Appearances. — Great variety has been observed in the appearances after death from arsenic, even in cases in which the symptoms during life were very similar. The lining membrane of the throat and oesophagus has in some few instances been found highly inflamed. The mucous membrane of the stomach is generally more or less reddened and inflamed ; sometimes it has a deep crimson color, at other times it is of a deep brownish-red, and it has presented a dark appearance, due to the effusion of altered blood. This mem- brane is sometimes much softened, and easily separated ; and in some instances patches of it are entirely destroyed. In other instances, however, it is much thickened and corrugated. The inflammation rarely extends to the peritoneal covering of the stomach. When the poison has been taken in the solid state, small particles of it are fre- quently found adhering to the mucous membrane and covered with coagulated mucus. Ulceration of the stomach has been of rare occurrence, except in protracted cases ; however, Dr. Taylor observed it in a case that proved fatal in ten hours. In protracted cases, the intestines, particularly the duodenum and rectum, not unfrequently present signs of inflammatory action similar to those found in the stomach. The lungs are sometimes congested and inflamed ; congestion of the brain has also been observed. The blood throughout the body is usually liquid, and of a dark color. Not a few instances of poisoning by this substance are recorded in which after death no well-marked morbid appearances were dis- covered in any part of the body. This result has even been observed in cases in which there were violent symptoms and life was prolonged for many hours. In a case reported by Dr. A. R. Davidson {Buffalo Med. and Surg. Jour,, Oct. 1882, 117), in which an unknown quantity of the poison proved fatal in twelve hours, under the usual symptoms, to a boy aged six years, the mucous membrane of the stomach was slightly paler than normal, and wholly free from any appearance of inflam- matory action; nor was any morbid change observed in any part of PRI-isERVATIVE EFFECTS. 251 the body. Something over lialf a frpain of arsenious oxide was recovered from tlie liver and kidneys. When the inspection is made some time after decomposition has been established, the stomach and intestines may present patches of a more or less brigiit yellow color, due to the conversion of the arsenic into sulphide by the sulphuretted hydrogen evolved in the putrefaction. This appearance may manifest itself within a few days after death, as we have observed in poisoned animals; whilst, on the otiier hand, even when very notable quantities of the poison are present, it may be absent after even very long periods. Indeed, it has recently been shown by J. Assikovszky {Jour, prakt. Chem., 1880, 323) that during the process of putrefaction of organic bodies pure arsenious sulphide may be converted into arsenious and arsenic oxides. Antiseptic Properties of Arsenic. — The preservative power of arsenic when brought in direct contact with animal textures is well known ; and the poison seems to exert a similar action when carried by means of the circulation to the different tissues of the body. The bodies therefore of those who have died from the effects of this poison are not unfrequently found in a good state of preservation, even long periods after death. We have elsewhere reported a case, described by Dr. Douglas Day, in which this preservative action of the poison was well marked in a body that had been buried seventeen months. At this time the body was destitute of odor, and the flesh of the extremities had given place to a dark unctuous matter. The abdominal walls were in a surprising state of preservation, and of the color of old parchment; the integuments upon incision were firm, and the muscles of a pink hue, but very attenuated. The omentum was large and in place, and covered with saponaceous matter. The stomach and intestines were pale, comparatively dry, and appeared as though the convolutions had been pressed together; they were firm and allowed free manipu- lation, and exhaled a peculiar but not offensive odor. The liver, spleen, and pancreas appeared remarkably recent, and the posterior walls of the abdomen, the mesentery, and kidneys were well pre- served. The bladder also was in a good state of preservation. A very notable quantity of arsenic was detected in each of several of the abdominal organs : no other parts were submitted to chemical examination. {Ohio 3Ied. and Siwg. Jour., Xov. 1863.) 252 AESENIC, In another case in which we made the chemical examination in 1871, that of Peter Buffenbarger, of Ohio, the body when exhumed, at the end of three years and a half, " was found entire and in a remarkable state of preservation." " The tissues were quite firm and solid ; the liver entire, but easily broken up ; the stomach was fresh and parchment-like; the walls of the abdomen firm." Very satis- factory evidence of the presence of arsenic in minute quantity was obtained both from the stomach and the liver. These were the only organs furnished for chemical analysis. At a preliminary hearing of this case, it was urged by the defence that the poison had been injected into the body after death. It was clearly shown, however, that the vault in which the body was buried had not been disturbed from the time it was first closed ; and there was no evidence what- ever that the poison had been injected before burial. Dr. Christison quotes a case in which the body after being interred seven years was found entire. The head, trunk, and limbs retained their situation ; but the organs of the chest and abdomen were con- verted into a brown soft mass, in which a chemical analysis revealed the presence of a considerable quantity of arsenic. Although the bodies of those who died from the effects of this poison have thus been found in an unusual state of preservation, yet this is by no means always the case, even when the poison remains in the body at the time of death. In fact, in some cases of arsenical poisoning the process of putrefaction seemed to advance with in- creased activity. At the same time, it must be borne in mind that the body is sometimes unusually preserved in cases in which death resulted from ordinary disease or mechanical injury. Chemical Properties. General Chemical Nature. — It has already been stated that arsenious oxide, in its amorphous state, occurs under two varieties, known as the transparent and the opaque. The specific gravity of the transparent variety seems to be some little greater than that of the opaque, the density of the former, according to most observers, being about 3.75, and that of the latter about 3.65. These varieties also differ in regard to their solubility in water. According to most ob- servers, arsenious oxide volatilizes at about 191° C. (380° F.) ; but, according to Dr. Guy, it may be vaporized, especially if in minute quantity, at 138° C. (280° F.). The vapor is colorless and odorless, SOLUBILITY IN WATER. 253 and recondenses nnoIian(;e(l on cold surfaces, principally in the forn) of regular octahedral crystals. (For an excellent paper on the crystal- line ibrms of arsenious oxide, by Dr. Guy, see Quart. Jour. Micro. Science, July, 1861.) Arsenious oxide is soluble in water with the formation of arsenious acid, each molecule of the former assimilating the elements of three molecules of water to form two molecules of the acid; thus : AsgOgH- 3HoO := 2H3ASO3. This acid, which is tribasic, has, however, not yet been obtained in the free state. Arsenious acid has only feebly acid properties ; nevertheless it readily unites Avitli many of the metals, forming salts denominated arsenitcs. These salts are readily decomjiosed by most other acids. The arsenites of the alkali metals are freely soluble in water; but all other arsenites are either insoluble or only sparingly soluble in this menstruum. The latter salts are readily decomposed and dissolved by nitric and hydrochloric acids. Upon the application of heat, most of the arsenites undergo decomposition. In this operation the fixed alkali arsenites retain the greater portion of the arsenic, in the form of an arsenate. When ignited with a reducing agent, all ar- senites are decomposed, with the evolution of metallic arsenic in the form of vapor. Solubi/ity. 1. In Water. — The degree of solubility of arsenious oxide in water sometimes becomes a matter of considerable importance in medico-legal investigations. The results of observers in regard to this point have been extremely discordant. The exact quantity of the poison that will be taken up and retained in solution by a given quantity of water will depend upon a variety of circum- stances, among the principal of which are the following: 1. The physical state of the oxide ; 2. The relative proportions of the oxide and water present ; 3. The time they have been in contact ; 4. The temperature of the mixture ; 5. If the mixture has been boiled, the length of time the boiling was continued ; and, 6. The time that has elapsed since the mixture was heated. Among numerous experiments that might be cited showing the influence of these various conditions, the following may be mentioned : a. One part (50 grains) of finely powdered opaque arsenious oxide was boiled with ten parts (500 grains) of distilled water for one hour, the vaporized fluid being condensed and returned to the flask as rapidly as formed, and thus the volume of the fluid kept con- 254 ARSENIC. stantly the same. The solution was then filtered as rapidly as possible, and a given portion of the filtrate evaporated to dryness on a water- bath. The residue thus obtained indicated that one part of the oxide had dissolved in 13.10 parts of water. h. A similar experiment with the transparent variety of the oxide, taken from the same mass as employed in experiment a, gave a residue indicating that one part of the oxide had dissolved in 15.66 parts of water. According to Bussy, the transparent variety is more soluble than the opaque; Guibourt, however, states that the reverse is the fact. c. A similar experiment with the freshly sublimed crystallized oxide indicated that one part of the oxide had dissolved in 11.50 parts of water. d. On repeating the last experiment and concentrating the filter- ing solution to about half its volume, a white scum appeared upon the surface of the liquid. The clear liquid was then decanted and a given portion evaporated to dryness, when it was found that one part of the oxide had been held in solution by 6.72 parts of water. e. After boiling one part of the crystallized oxide, from the sam- ple used in experiment c, for one hour with ten parts of pure water, without loss of liquid by evaporation, the mixture was allowed to stand twenty-four hours. The solution then contained one part of the oxide in 58.68 parts of water. /. One part of the opaque oxide, from the sample used in experi- ment a, was boiled for one hour with forty parts of water, without loss of liquid by evaporation, and the solution quickly filtered. The filtrate contained one part of the oxide in 43.7 parts of the men- struum. It will be observed that in this experiment the conditions were the same as in experiment a, except in the relative proportion of oxide and water present. Even when one part of the oxide is boiled for an hour with one hundred parts of water, a portion of the poison will still remain undissolved. g. One part of the opaque oxide was treated w^ith twenty parts of boiling water and the mixture frequently agitated for twenty-four hours. The solution then contained one part of the oxide in 196 parts of water. h. On treating the transparent variety of the oxide in the same manner as in the last experiment, the solution contained one part of the poison in 93 parts of the menstruum. On comparing the experi- SOLUBILITY IN WATER. 255 nients q and /* with tliosc of a and b, it will he observed tliat under one set of conditions the transparent oxide dissolved more freely than the opaque variety, whilst under another the reverse was the case. i. One part of the crydallized oxide was frequently agitated during nine days, at the ordinary temperature, with twenty parts of pure water. The resulting solution contained one part of the oxide in 108 parts of water. j. An experiment similar to the last and conducted at the same time, with one part of the oxide and jive hundred parts of water, yielded a solution which contained one part of oxide in 810 parts of the menstruum. The experiments now cited serve to explain, at least in a measure, the discrepant statements of observers in regard to the solubility of this substance. Furthermore, it is obvious that unless something is known in regard to the conditions under which the oxide and liquid have been brought in contact, it will be impossible to state even approximately how much of the poison may have been dissolved, even by pure water. In general terms, if the mixture contained one part of the oxide to ten or twelve parts of water and has been boiled and concentrated, the liquid may hold in solution even as much as one-seventh of its weight of the poison ; whilst, on the other hand, if there was very large excess of water and the mix- ture was not heated, the liquid may not take up more than the 1-1 000th of its \Yeight of the oxide. Gmelin placed pulverized opaque arsenious oxide in various proportions of water in closed bottles, and set them aside in a cool place for eighteen years, with the following results. One part of the oxide in 1000 parts of water : perfect solution. One part of the oxide in 100 parts of water : the solution contained one part of oxide in 102 parts of water. One part of oxide in 35 parts of water : the solution contained one part of the oxide in 54 parts of water. {Hand-book of Chemistry, iv. 257.) According to most observers, the solubility of the poison is more or less diminished by the presence of most kinds of organic matter. In an ordinary decoction of coffee, to which during its prepara- tion white arsenic had been criminally added. Dr. C. Mclutire found one part of the oxide in solution in thirty-nine parts of the men- struum; and by experiment he found that one part of the oxide 256 ARSENIC. might be taken up by about twenty parts of the decoction. [Proc. Am. Chem. Soc, 1878, 56.) 2. In Alcohol. — One part of the crystallized oxide, in the state of powder, was frequently agitated for two days with twenty parts of alcohol of specific gravity 0.802 (= 97.5 per cent.). The solution thus obtained contained one part of oxide in 2000 parts of the men- struum. In a similar experiment with the most common kind of whiskey, one part of the oxide dissolved in 880 parts of the liquid. 3. In Chloroform. — On frequently agitating powdered arsenious oxide for two days with twenty parts by weight of pure chloroform, two hundred grains of the filtered liquid contained something less than the 1-lOOOth of a grain of the oxide. This experiment would, therefore, indicate that the oxide required more than 200,000 times its weight of chloroform for solution. Absolute ether, under the conditions just mentioned, failed to dissolve a trace of the poison. Arsenious oxide is readily soluble in solutions of the fixed caustic alkalies, but it is much less soluble in ammonia. It is also soluble in hydrochloric acid, and in certain of the vegetable acids ; sulphuric acid dissolves it only in minute quantity. Hot nitric acid oxidizes and dissolves it to arsenic acid. Op Solid Arsenious Oxide. 1. If a small quantity of solid arsenious oxide be thrown on a piece of ignited charcoal or heated on a charcoal support in the re- ducing blow-pipe flame, it is dissipated in the form of white fumes and emits a garlic-like odor. In this operation the arsenious oxide first gives up its oxygen to the carbon, forming carbon dioxide gas ; the metallic arsenic thus set free is then reoxidized by the air into arsenious oxide, which is evolved and gives rise to white fumes. The alliaceous odor emitted is due to the reoxidation of the metal, and is evolved only when the metal itself is being oxidized. It was formerly supposed that this odor was peculiar to arsenic, but it is now known that there are several other substances which evolve a similar odor. 2. When heated in a reduction-tube, arsenious oxide volatilizes without fusing and recondenses in the cooler portion of the tube, in the form of minute, octahedral crystals. Under the microscope, this sublimate is quite peculiar, and the crystals present the appearances UlODUCriON TKST. 257 illiistratod in Plate IV., i\\i;. 5. When only a very niimilo (jtiantity of till* poison is tlm.s snhlinieil, the erystals are exceedingly small, but still })erfectly characteristic. Under an amplification of one hun- dred dianu'ters, the angular iiatui-e of a crystal that does not ex- ceed the l-8000th of an inch in diameter may be readily recognized ; and with a power of two hundred and fifty, crystals measuring only tlie 1-1 5,000th of an inch in size may be satisfactorily determined. If suflicient sublimate be obtained, the portion of the tube containing it may be boiled in a small quantity of pure water, and the solution thus obtained, after concentration if necessary, examined by the liquid tests mentioned hereafter. In applying this test to only a minute quantity of arsenious oxide, the bore of the reduction-tube should not exceed the 1-1 6th of an inch in diameter. Or, after placing the oxide in a tube of this kind having thin walls, the tube may be carefully heated at a little distance above the point occupied by the oxide, in a small blow-pipe flame, and drawn out into a capillary neck; the oxide is then sublimed into the contracted portion of the tube. By this method the least visible quantity of the poison will yield a very satisfactory sublimate; at the same time, this method permits the application of the higher powers of the microscope for the examination" of the sublimate. Prof. Guy recommends [Cheni. News, i. 200) to heat the arsenious oxide in a perfectly dry tube of small diameter and about three- quarters of an inch in length and having its mouth covered with a warm slide or disk of glass. The crystals are deposited partly on the sides of the tube, but chiefly on the glass cover. This method oifers the advantage of having the deposit upon a flat surface for examination by the microscope; in point of delicacy, however, it is very far inferior to the preceding method. In applying this sublimation-test to a suspected substance, it must be borne in mind that there are other white powders besides arsenious oxide, as salts of ammonium, oxalic acid, and corrosive sublimate, which when heated in a reduction-tube may yield a crys- talline sublimate. But most, if not all, of these fallacious substances melt before volatilizing, and none of them condense in the form of octahedral crystals. 3. Reduction Test. a. If a small quantity of arsenious oxide be placed in the closed end of a narrow reduction-tube, or in the end of a tube drawn out in 17 258 ARSENIC. the form shown in Fig. 5, and a wedge of recently ignited char- coal, h, be placed in the tube a little distance above the arsenical fragment or powder, on heating the charcoal to redness by the flame of a spirit-lamp and then slowly erecting the outer end of the tube so that the flame may still heat the charcoal and at the same time volatilize the arsenious oxide, the latter will be deoxidized in its passage over the ignited charcoal and yield Fig. 5. a sublimate, c, of metallic arsenic. This ■^^--?— ■ -«S i^=ssi= ^^=(i i reduction may also be eifected by mixing O' o ... m V, ^ iv. J .• . ■ the arsenious oxide with a perfectly dry Tube for the reduction of arsenious ' j J oxide by charcoal. One-third nat- mixture of powdcrcd charcoal and sodium ""^^ ^^^^' carbonate, and heating the whole in a plain or bulbed reduction-tube. The sublimate thus obtained usually consists of two well-defined parts, the lower of which has a bright mirror appearance resembling polished steel; while the upper has a darker color, is destitute of lustre, and is gradually lost in a light-gray mist. The inner surface of the sublimate, especially of the lower ring, presents a bright crys- talline appearance. Sometimes the upper portion of the sublimate, wdien very thin, has a brownish color. So, also, sometimes its upper margin contains crystals of arsenious oxide. If the closed end of the tube be removed and the sublimate then heated, it is readily volatilized and oxidized into arsenious oxide, which condenses in octahedral crystals. The metallic, sublimate is soluble in a solution of either sodium or calcium hypochlorite. This confirmatory test may be applied by removing the lower end of the tube, and then immersing the latter in a small quantity of the sodium solution ; or, a few drops of the solution may be drawn into the tube, after the removal of its closed end, by suction with the mouth. The upper portion of the sublimate readily disappears when moistened with this liquid, but the lower part requires some little time for solution ; sometimes the deposit becomes detached and drops out of the tube in the form of a metallic ring. The arsenical nature of the sublimate may also be shown by dissolving it in a few drops of warm nitric acid, evaporating the solution to dryness by a moderate heat, and touching the residue with a drop or two of a strong solution of silver nitrate, when it will assume a brick-red color, due to the formation of silver arsenate. 6. One of the best methods yet proposed for the reduction of REDUCTION TEST. 259 solid urseiiious oxide, and one wliioli is equally applicable for arsenites and llio siil|)lii(les of arsenic, is hy means of a pcrfcdhj dry mixture of about ('(jnal j)arts of .-lodium carbonate and poldHHium ci/anlde. A small portion of the arsenical compound is introduced into tlu; bulb of a tube of the form shown in Fio;. 6, A, or of the form i> as iirst proposed by Berzelius, and covered with several times its volume of the above mixture. A gentle heat is then applied, first to the neck of the tube and afterward to the bulb; if in this opera- tion any moisture condenses within the tube, it should be carefully removed. On now strongly heating the mixture, the compounil under examination will be re- duced and yield a metallic sublimate at about the ]H)int 6. This reaction is ex- oc- 1 1 1*^ A„ ^^„^„:„11„ ,.A.^^ ■.^^,, Tubes for the reduction of araenious tremely delicate, especially wlien per- ^^.^^ formed in a Berzelius-tube. When only a very minute quantity of the arsenical compound is to be reduced, it may be placed in the closed end of an ordinary reduction-tube, covered by the reducing mixture, and the tube then heated at a little distance above the mixture in a blow-pipe flame, and drawn out into a contracted neck, as represented in Fig. 6, C. After the neck of the tube has cooled, the arsenical mixture is heated in the manner above described. A mixture containing only the 1-1 000th of a grain of arsenious oxide, when treated after this method in a tube having its neck contracted to about the 1— 20th of an inch in diameter, will yield a very satisfactory metallic subli- mate, which u})on resubliraation farther up the neck of the tube will furnish several hundred crystals of arsenious oxide, many of them measuring the 1-lOOOth of an inch in diameter. Compounds of antimonyyield no sublimate whatever when heated with the reducing mixture. c. As a reducing agent for arsenious oxide, arsenites, and the sulphides of arsenic, as well as for other metallic compounds. Dr. E. Davy, of Dublin, has recommended potassium ferrocyanide, or yellow prussiate of potash, previously dried at a temperature of i00° C. (212° F.). {Chemical News, iii. 288.) This salt has an advantage over potassium cyanide, in that it does not readily absorb moisture from the atmosphere. The arsenical compound is mixed 260 AESENIC. with about six or eight times its volume of the dried salt, and the mixture fused in one or other of the reduction-tubes already de- scribed. The mixture blackens before fusing. In point of delicacy the reaction of this reducing agent is quite equal to that of potas- sium cyanide. Fallacies. — \yhen, by either of the above methods of reduction, a metallic sublimate having the physical and chemical properties described is obtained, there is no doubt whatever of the presence of arsenic. Compounds of mereury, cadmium, tellurium, and selenium may under similar circumstances yield sublimates. These, however, may be readily distinguished from the arsenical sublimate, even by the naked eye ; under the microscope they would be found to con- sist of globules or drops. Moreover, neither of these sublimates when revolatilized will, like arsenic, furnish octahedral crystals; nor are tliey soluble in a solution of sodium hypochlorite. Xeither will they, when dissolved in hot nitric acid and the solution evaporated to dryness, leave a residue which assumes a brick-red color when moistened with a solution of silver nitrate. It has also been stated that a crust of charcoal or the employment of a reduction-tube containing lead might lead to error; but it is diffi- cult to conceive how either of these results could be mistaken for an arsenical sublimate by any one at all conversant with the physical appearances of the latter. Solutions of Aesexious Oxide. — xIrsexious Acid. Pure aqueous solutions of arsenious oxide have only a feeble acid reaction. This reaction is common to both varieties of the oxide, and is still manifest in a solution containing only the 1-lOOOth of its weight of the poison. On allowing a drop of a solution of this kind to evaporate spontaneously to dryness, for convenience on a glass slide, the oxide will be left chiefly in the form of white, oc- tahedral crystals, wdiich are readily dissipated by heat. The residue thus obtained from the 1— 100th of a grain of the acid will usually contain many crystals that measure the 1— 1000th of an inch in diameter. Equally satisfactory results may be obtained from the 1-lOOOth of a grain of the oxide, but the crystals are usually quite small. From the 1-10, 000th of a grain of the oxide the crystals are very minute, but under the higher powers of the microscope their true nature may be very satisfactorily determined. The production AMMONIO SILVER NITRATE TEST. 261 of these octaliedrul crystals, completely vaporizable by heat, is pe- culiar to arseiiious oxide. The dry residue thus obtained may, of <'uurse, be examined by any of the tests ah'cady mentioned for the poison in its solid state. In the followin*;- investitrations in regard to tiie behavior of solu- tions ot'arsenious oxide, solutions of the |)urc crystallized oxide were employed. The fractions indicate the amount of anhydrous oxide present in one grain of the solution. The results, unless otherwise stated, refer to the reactions of one grain of the solution. 1 . Ammonio Silver Nitrate. This reagent is prepared by cautiously adding a dilute solution of ammonia to a solution of silver nitrate, until the merest trace of the precipitate first produced remains undissolved. It is important that the proper quantity of ammonia be added : since if there is deficiency, the reagent will also produce yellow precipitates with solu- tions of the alkali phosphates and silicates; whilst, on the other hand, if there is excess, it occasions no preci])itate, or only a partial one, with arsenious acid. The reagent should always be freshly prej)ared. Nitrate of silver alone produces at most only a slight turbidity in solutions of free arsenious acid; but with neutral arsenites it behaves in the same manner as the ammonio-nitrate with the -free acid. This test was first proposed, in 1789, by Mr. Hume, of London. Ammonio silver nitrate throws down from aqueous solutions of arsenious acid a bright yellow precipitate of tribasic silver arsenite, AgjAsOj, the reaction being, j)erhaps, 2H3ASO3-I- GAgXHjNOg^^ 2Ag3As03-|- GNH^NOg. According to some observers, however, the reagent has the composition AgXH2,NH^X03, and the reaction is 2H3As03-f 6AgXH2,XH,X03= 2Ag3As03 + 6XH,X03 + 6XH3. The precipitate is readily soluble, to a colorless solution, in am- monia and in nitric and acetic acids, sparingly soluble in ammonium nitrate, and insoluble in the fixed caustic alkalies. After a little time the precipitate becomes more or less crystalline, and is then insoluble in ammonia and in acetic acid. Hydrochloric acid decomposes the precipitate with the formation of white insoluble silver chloride. 1. YoiF grain of arsenious oxide, in one grain of water, yields with the reagent a copious, bright yellow, amorphous precipitate, which after a little time becomes converted into yellowish-brown crys- tals, of the forms illustrated in Plate IV., fig. 6. The crystals 262 ARSENIC. closely adhere to the glass upon which they have formed, and are insoluble in large excess of ammonia and of acetic acid, 2. YFoo" gi'ai" yields a rather copious precipitate, which partly becomes crystalline. 3. 5-0V0" gi^aiii • a quite good deposit, which remains amorphous. 4. YF-ToT grain : an immediate yellowish turbidity, and in a little time small yellow flakes. 5. -g-g.-o-oo" gi'ain : after a little time the mixture becomes very dis- tinctly turbid, and when viewed over a white surface, as white paper, presents a slight yellow tint. Ten grains of the solution yield an immediate yellowish turbidity, and after a little time small flakes having a decided yellow color. When examined in large quantity, solutions even much more dilute than this will yield very distinct reactions. If the silver arsenite thrown down by this reagent be decomposed by slight excess of hydrochloric acid and the silver chloride separated by a filter, the clear acid filtrate will yield with sulphuretted hydro- gen gas a bright yellow precipitate of arsenious sulphide, having the properties to be pointed out hereafter. When the silver arsenite is washed, thoroughly dried, and heated in a reduction-tube, it under- goes decomposition with the production of a sublimate of octahedral crystals of arsenious oxide ; when heated in a similar manner with a reducing agent, such as potassium ferrocyanide, it yields a subli- mate of metallic arsenic. By either of these methods the arsenical nature of very minute quantities of the silver precipitate may be fully established. Fallacies. — Ammonio silver nitrate also produces in solutions of free phosphoric acid a yellow, amorphous precipitate, which is readily soluble in nitric acid and in ammonia ; this precipitate always remains amorphous. So, also, the reagent produces a somewhat similar pre- cipitate in solutions of free vanadic acid; but these solutions, unlike those of arsenious acid, have a yellow color. Both free phosphoric and vanadic acids, especially the latter, are extremely" rare, and there- fore not likely to be met with in medico-legal investigations. The properly prepared reagent fails to produce a precipitate in solutions of the salts of either of these acids. Again, solutions of the alkali iodides and bromides yield with the reagent yellowish precipitates ; but these precipitates are insoluble in dilute nitric acid, and only slightly soluble in caustic ammonia. AMMONIO (X)PPER SULPHATE TEST. 263 It need liiinlly Ix' rcmarketl that iicitlicr of" the al)ove precipi- tates, when dried and heated either ah)iie or with a ree introilueetl info an ordinary gas-evolution flask and covered with pure water; the mouth of the flask is then (;loscd by a cork having two perforations, one of which carries a Innnel-tnbe, and the other an cxit-lnbe bent twice at right angles. Sufficient sulphuric acid is then added to the contents of the flask, by means of the funnel-tube, to cause the evolution of a moderate stream of sulphuretted hydrogen ; this is conducted into the acidulated arsenical solution, contained in a test-tube or any convenient vessel. When the quantity of material to be examined is very small, the apparatus illustrated in Fig. 7 may be era- ployed. From very dilute solutions the precipi- tate does not separate until the excess of the reagent added is expelled by a gentle heat or by exposure to the air. In all cases a gentle heat hastens the complete separation of the precipitate. Arsenious sulphide is insoluble in cold hydro- chloric acid, and only very slightly soluble in Apparatus for detecting ,,.,. I'll •• -11 arsenic by sulpburet- tlie boiling concentrated acid; hot nitric acid de- ted hydrogen, composes and dissolves it to arsenic acid. It is readily soluble, to a colorless solution, in the caustic alkalies, and in the alkali sulphides and carbonates. When ten grains of a pure aqueous solution of arsenious oxide are placed in a small test-tube, acidulated with two drops of hydro- chloric acid, and treated with a slow stream of the washed sulphu- retted gas, the following results are obtained. 1. 1-lOOth solution (1-lOtli grain of arsenious oxide) yields a very copious, bright yellow precipitate, which remains amorphous. 2. 1-lOOOth solution : an immediate precipitate, which very soon becomes quite copious. 3. l-10,000th solution : an immediate yellow turbidity ; if the mixture, after being saturated with the gas, be allowed to stand at the ordinary temperature for several minutes, quite good yellow flakes appear, and these after a time fall to a very good deposit. If the mixture be heated, the precipitate separates almost immediately. 4. l-25,000th solution : very soon a yellow turbidity ; after stand- ing about ten minutes yellow flakes are just perceptible ; and after a few hours there is a quite satisfactory depasit. If after 266 ARSENIC. the introduction of the gas the mixture be heated, the deposit appears within a very few ruinutes. 5. 1— 50,000th solution: after a little time a perceptible yellowish turbidity; in about an hour distinct flakes appear suspended in the liquid, but their color is not satisfactory ; after a few hours they assume a distinct yellow hue, but still remain suspended in the fluid, from which, however, they almost immediately separate on the application of heat. 6. l-100,000th solution : after a few minutes the mixture presents a perceptible cloudiness ; after several minutes a distinct tur- bidity and a just perceptible yellow tint ; after a few hours distinct flakes appear, but their true color is not apparent; after thirty-six hours there is a quite distinct yellow deposit. One hundred grciins of the solution yield in a little time a very perceptible yellowish turbidity; after a few hours a decided yellow deposit ; in twenty-four hours the deposit is about the same as that from ten grains of a 1-1 0,000th solution which has stood the same length of time. When normal solutions of the acid are treated with the reagent, they also yield arsenious sulphide ; but under these conditions the arsenical sulphide, except when from concentrated solutions, entirely remains in solution, imparting a yellow color to the liquid. Ten grains of a 1-lOOth solution of this kind yield after a little time a quite good yellow precipitate ; but the same quantity of a 1— 1000th solution yields only an intensely yellow liquid; a 1-25, 000th solution yields a quite distinct yellow coloration ; and a 1-50, 000th solution, after a little time, acquires a perceptible yellow tint. Alkaline solutions of the acid, even when highly concentrated, altogether fail to yield a precipitate when treated with the reagent. The limit of the visible reaction of this test, when applied to acidulated solutions of the poison, has been variously stated by different observers. Thus, Lassaigne placed it, for solutions acid- ulated with hydrochloric acid, at one part of arsenious oxide in 80,000 parts of liquid ; Reiusch, at one part in 90,000 ; Brandes, one part in 160,000; Devergie, one part in 500,000; and Horsley, at one part in 1,120,000 parts of fluid. Dr. Taylor states that the l-400th of a grain of the poison in half an ounce of water pro- duced a scarcely perceptible yellow tint. In this case the acid was present in something less than 100,000 parts of liquid. SULPHURETTED HYDROGEN TEST. 267 As neither of tliese observei-s, except Dr. Taylor, states the quantify of sohition operated upon, these discrepancies are easily reconciled. The effect of quantity is well illustrated under experi- ment G, in which ten grains and one hundred f/j-ains respectively of the same solution were employed. Here it will be observe at intervals of" alxmt one .second, the redne- tion-tiibe is heated to redness at the point e by means of a spirit- hinip ; when e is red-hot, the flame of another hunp is applied to the mixtnre, proceed in i;- from b to e, until the whole of the arsenic is expelled. Tiie far ureater portion of the volatilized arsenic recon- denses at/* while a small j)ortion escapes through 7, imparting to the surrounding air a peculiar garlic-like odor. By slowly advancing the flame of the second lam]) up to /, the whole of the condensed arsenic collects in the narrow neck of the tube. The authors of this process state that it will yield a perfectly distinct metallic mirror from the l-300th of a grain of arsenious sulphide. Fallacies. — The only metal besides arsenic with which sulphu- retted hydrogen produces a bright yellow precipitate is cadmium. But, as the suljdiide of arsenic when precipitated from organic solu- tions may have only a dull yellow color, it is important to bear in mind that certain other metallic sulphides, either in their pure state or when mixed with organic matter, may also present a similar ap- pearance. The only substances that under any circumstance could thus be confounded Avith arsenic are cadmium, selenium, tin, and antimony. The sulphides of these substances pos.sess the following properties : 1. The sulphide of cadmium is thrown down by the reagent from moderately acid solutions of the salts of the metal, but strongly acidulated solutions fail to yield a precipitate. The precipitate is readily decomposed and dissolved by hydrochloric acid; so, also, unlike arsenious sulphide, it is insoluble in the alkalies and their sul- phides, and it is, therefore, produced in solutions containing a free alkali. When boiled with copper-foil in water acidulated with hydrochloric acid, it fails to produce a deposit upon the copper. Fused in a reduction-tube with a reducing agent, it yields a metallic sublimate, which, however, in its physical appearance is very unlike the arsenical deposit, and which when resublimed in the open tube fails to yield octahedral crystals. 2. Acidulated solutions of selenioiis acid yield with sulphuretted hydrogen a precipitate of selenium sulphide, which at first has a yellow color, but soon changes to reddish-yellow, and finally .to orange-red. In dilute solutions the precipitate may remain sus- pended for some time, and ])resent a yellow appearance, much like the arsenical compound ; but after a time it separates of its charac- 270 AESENIC. teristic color. The same precipitate separates from neutral and alka- line solutions. The precipitate, like the arsenical sulphide, is insolu- ble in hydrochloric acid, even on the application of heat. Unlike the arsenical compound, however, it is wholly insoluble in ammonia. It also fails to yield a metallic deposit when boiled with diluted hydrochloric acid and copper-foil. When fused with a reducing agent in a reduction-tube, it yields a sublimate which may resemble somewhat that produced by arsenic, but the deposit fails to yield octahedral crystals upon resublimation. 3. Per-combinations of tin, or stannie compounds, yield with the reagent from acidulated solutions a precipitate of stannic sulphide, SnSg, the color of which in the moist state somewhat resembles that of sulphide of arsenic, but when dried it has a very dull yellow color. The same precipitate separates from neutral, but not from alkaline, solutions. The precipitate is slowly soluble in cold hydro- chloric acid, but readily in the hot concentrated acid. It is very sparingly soluble in ammonia, but readily soluble in potassium hy- drate. When boiled with water containing hydrochloric acid and a slip of copper-foil, it may impart to the latter a slight stain, but when the stained metal is heated in a reduction-tube it fails to yield a crystalline sublimate. The precipitate also fails to yield a metallic sublimate when heated in a reduction-tube with a reducing agent. 4. The sulphides of antimony, as thrown down from pure acid- ulated solutions by sulphuretted hydrogen, have an orange-red color; the same precipitates are partially deposited in neutral and alkaline solutions of the metal. The precipitates, unlike the arsenious sul- phide, are soluble in cold concentrated hydrochloric acid, and nearly wholly insoluble in ammonia; they are readily soluble in potassium hydrate. When boiled with diluted hydrochloric acid and copper- foil, they impart to the latter a metallic coating, which usually has a violet color ; when the coated copper is heated in a reduction-tube, it generally fails to yield octahedral crystals. (See jpost, 275.) Nor will the precipitates when heated in a reduction-tube with a reducing agent yield a metallic sublimate. As a source of fallacy of the sulphur test, it has been claimed that if the iron sulphide contains metallic iron, as is frequently the case, and the iron salt or the acid employed for its decomposition is contaminated with arsenic, the nascent hydrogen evolved by the REINSCII'S TEST. 271 metallic ii'on will convert llu' arsenic, in part a( least, into arsenii- rettod liydroi^on, which may cjirry the metal over into the solution beinj>; tested ibr arsenic. This, liowcver, is an error. In repeated experiments with impure materials of this kind, we have failed to find the least trace of arsenic evolved from the mixture. Thus, when a mixture of 50 j^rammes each of iron sulphide and m(>tallic iron was treated in a flask with 100 c.c. of diluted sul- phui-ic' acid containing one gramme of arsenious oxide, added small portions at a time, and the washed evolved gas conducted into 100 c.c. of warmed nitric acid of sp. gr. 1.40, which readily decomposes both sulphuretted hydrogen and arsenuretted hydrogen, not a trace of arsenic was found in the nitric acid residue, when most carefully examined by Marsh's apparatus. Any arsenic present in the material employed for generating the sulphuretted hydrogen is immediately converted into arsenious sulphide, and remains as such in the gener- ating flask, the sulphide not being decomposed by nascent hydrogen. 4. Iteinsch's Test. When a solution of free arsenious acid or of an arsenite is strongly acidulated with hydrochloric acid, and the mixture boiled with bright metallic copper, the latter decomposes the arsenical com- pound and receives a coating of metallic arsenic. This fact was first observed, in 1843, by Reinsch ; but Dr. Taylor was the first to apply it as a test in medico-legal investigations. The proportion of hydro- chloric acid employed should form about one-eighth of the volume of the arsenical solution; without the addition of the acid the metal is not deposited. The copper may be employed in the form either of fine wire or of very thin foil ; the latter, however, is preferable. It is essential that the copper have a bright surface: this is readily effected by means of a fine file or of sand-paper. The color of the metallic deposit will depend much upon the thickness of the latter: when quite thin, it presents a bluish or violet appearance, but when comparatively thick, it has a steel-like or iron-gray color. When the metallic coating is very thick, continued boiling causes it to separate from the copper, in the form of grayish or black scales. This deposit is not, as was formerly supposed, pure metallic arsenic, but a combination of this metal and copper. M. Lippert maintains that it has a constant composition, being a definite alloy, consisting of 32 per cent, of arsenic and 68 per cent, of copper, its 272 ARSENIC. formula being CugAsa. The large proportion of copper contained by the deposit adds very much to the delicacy of the test. This reaction will serve to withdraw the whole of the arsenic from solu- tions of arsenious acid and of arsenites ; but when the metal exists in the form of arsenic acid, it is deposited only from somewhat strong solutions. The arsenical nature of the deposit may be shown in the following manner : the coated copper, after being carefully washed with pure water and dried in a water-bath, is heated by means of a spirit-lamp in a narrow, perfectly dry and clean reduction-tube, when the arsenic volatilizes, and, becoming oxidized, yields a sublimate of octahedral crystals of arsenious oxide. This sublimate usually forms within from a quarter to half an inch above the point at which the heat is applied. When the sublimate is not exceedingly minute, it presents a well-defined ring of sparkling crystals to the naked eye. Under the microscope, these crystals present the appearances illustrated in Plate lY., fig. 5. The absolute size of the crystals will depend somewhat upon the quantity of the metal present, as well as upon the diameter of the reduction-tube. The portion of the tube con- taining the sublimate may be separated with a file, boiled in a very small quantity of M'ater, and the solution examined by the ammonio silver nitrate or any of the other tests for arsenious acid. When one grain of a pure aqueous solution of arsenious oxide is acidulated with pure hydrochloric acid, and the mixture heated in a thin watch-glass with a small fragment of bright copper-foil, it yields the following results. 1. YoT g^^i" of arsenious oxide yields a copious, iron-gray deposit, which when heated in a narrow reduction-tube furnishes a very good sublimate, consisting of innumerable octahedral crystals. 2. YoVo g^^i'i yields a good, steel-like deposit, which when sublimed in a reduction -tube yields results similar to 1, only that the crys- tals are generally somewhat smaller. 3. Yo".ToT E^^^^ '• ^^ j.soon as the mixture is heated to the boiling temperature the copper shows a distinct deposit, which in a little time becomes quite satisfactory ; when this is volatilized in a very narrow reduction-tube, it yields a sublimate which is visible to the naked eye, and which under the microscope is very satisfactory. When deposits smaller than the one just mentioned are heated in reinsch's test. 27 "> a reduction-tiil)e of llic ordinary foi-in, even of very narrow bore, the results are not uniform, owing to the fact that the sublimate is (listributeil over a comparatively large space, and part of it seems entirely to escape condensation, at least in the lower portion of the tube. With such deposits, however, very uniform results may be obtained by the following method. A thin, j)erfectly clean and dry tube, of about the 1-lOth of an inch in diameter, is drawn out into a capillary neck having an internal bore of about the l-40th of an inch, as illustrated in Fig. 9, A. The coated copper is then intro- Fig. 9. duced through the wider por- j^ tion of the tube to the point ' mi'ii'^ c, and the neck of the tube at /m- B a little distance above the cop- c ,^^ ) per is moistened with water or 1^ wrapped with wet cotton. The Tubes for sublimation of arsenic. Natural size. wide end of the tube is then cautiously fused shut by a very small blow-pipe flame, and the fusion slowly advanced to the point occupied by the copper, as shown in B. The capillary end may now be fused shut. When wiped and exam- ined by the microscope, the arsenical sublimate will be found at about the point m, forming a very narrow ring of octahedral crystals. As these tubes may readily be formed with walls less than the 1-1 00th of an inch in thickness, they permit the application of the higher powers of the microscope. They may be reserved for future ex- amination ; after a time, however, the sublimate deteriorates some- what, and it may even, if the deposit is very small, wholly dis- appear. 4. yg-.^-jjij- grain : when a fragment of copper-foil measuring about 1-lOth by l-20th inch is employed, and the mixture kept at a boiling heat for some time, with renewal of the evaporated fluid by pure water, the copper acquires a decided steel-like coating; when this is sublimed in a tube of the form described above, it yields to the naked eye a visible mist, which under an ampli- fication of seventy-five diameters is found to consist of many hundreds of well-defined octahedral crystals. In a number of instances over one hundred crystals, varying in size from the l-2000th to the l-8000th of an inch in diameter, were counted in a single field of a two-thirds inch objective, \vithout change of 18 274 AESENIC. focus; most of the crystals measured about the l-4000th of an iuch in diameter, 5. -5-0,^-oT grain, when treated for some minutes as under 4, imparts to the copper a distinct steel-like tarnish, which when volatilized, in the manner described above, yields a very satisfactory micro- scopic sublimate. In many instances over fifty crystals, meas- uring from the l-3000th to the l-10,000th of an inch in diam- eter, were counted in a single field of the objective. So far as the evidence of the presence of octahedral crystals is concerned, this sublimate, under the microscope, is as satisfactory as that from the 1-lOOtli of a grain or larger quantity of arsenious oxide, the only difference being in the size and number of the crystals. 6. yoT/UTo" gi'ain : the copper receives a very slight tarnish, which when volatilized sometimes yields a satisfactory crystalline sub- limate; but frequently the crystals are so minute that their angular nature cannot be satisfactorily determined. For the examination of these sublimates a magnifying power of about seventy-five diameters is generally the most useful. Under this amplification, the angular nature of a crystal measuring the l-5000th of an inch in diameter is perfectly distinct and satisfactory : the weight of such a crystal would not exceed the 1 -200,000,000th of a grain. Under the same power, a crystal measuring the 1— 10,000th of an inch appears only as a distinct point ; but with a power of one hundred and fifty, its angular form may be distinctly recognized : its weight would be less than the 1-1, 000,000,000th of a grain. On account of the curvature of the glass tube, crystals but little less in size than the last mentioned are not easily determined, even with the higher powers of the microscope. It is not, of course, intended to imply that quantities of the poison in themselves as small as those just mentioned could be recovered from a solution and reproduced in the crystalline form ; but only that these crystals may thus be recognized and identified when they form separate portions of a sublimate. The least quantity of the poison that will furnish these crystals, even with the greatest care and under the most favorable circumstances, accord- ing to the above method, is about the l-50,000th of a grain. Various and very discordant limits have been assigned to this test by different observers. However, as these experimentalists only state the degree of dilution, without mentioning either the quantity FALLACIES OF REINSCIl's TEST. 276 of solution examined, tlie size of tlie copper, or the diameter of the reduction-tube employed, these discrepancies are readily explained. Fallacies. — The prodiirtion of ;i sublimate of octahedral crystiils by this test is quite characteristi(; of arsenic. \'ai'ious other metals, however, as antimony, mercury, silvei-, bismuth, platinum, palladium, and gold, are deposited upon cojipcr under the same conditions as arsenic. Tin may also impart a slight stxiin to the copper; so, also, organic matter, especially if it contain sulphur; and the prolonged action of boiling hydrochloric acid alone may produce a distinct tarnish. The antimonial deposit has usually a peculiar violet color, while the deposits from mercury, silver, and bismuth have generally a bright silvery appearance, and that from gold a yellow hue. Under certain circumstances, however, most of these deposits may closely resemble that from arsenic. The platinum and palladium deposits present an appearance very similar to that of the arsenical coating. Of these various metallic deposits, the only ones which, when heated in a reduction-tube, will, like arsenic, volatilize and yield a sublimate, are mercury and antimony. But the sublimate from mer- cury consists of opaque spherical globules, which, when viewed under incident light with the microscope, have a bright silvery appearance ; and that from antimony is usually either amorphous or at most gran- ular : both these sublimates, unlike that from arsenic, are insoluble in water. We have elsewhere shown [Amer. Jour. Med. Sci., Oct. 1877, 399) that the antimonial sublimate may contain octahedral crystals, at least when a comparatively large deposit is heated. But the antimony deposit requires a much higher temperature than arsenic for its vaporization, and, being less volatile, the sublimate is very near or only slightly in advance of the copper slip. Moreover, under the microscope, any crystals, if present, will be found in the lower margin of the deposit and mixed more or less with amorphous or granular matter. Sometimes, though rarely, the antimony subli- mate contains crystalline needles. In this connection it should be remembered that commercial tartar emetic sometimes contains suf- ficient arsenic, as an impurity, to yield in this manner a very distinct sublimate of octahedral crystals in advance of the antimonial deposit. A deposit of organic matter upon the copper may also give rise to a sublimate, but this is amorphous, and its true nature is at once revealed by the microscope. When very complex organic mixtures 276 AESENIC. strongly acidulated with hydrochloric acid are boiled for some time in contact with metallic copper, the metal may present a very dis- tinct stain, and yield an amorphous sublimate which sometimes contains small acicular crystals, consisting apparently of a compound of copper. This sublimate deposits very near the copper, and is not resublimed upon the further application of heat. If sulphur in certain states of combination, especially as sulphu- rous aeid or an alkaline sulphite, be present in the liquid, the copper will receive a deposit or coating very similar in appearance to that produced by arsenic in certain quantity. After a time the deposit may become detached in metal-like flakes, which have, as we have found, the composition CugS. When the coated copper is heated in a tube, a portion of the sulphur may be volatilized and yield a sublimate of minute globules which in certain respects may closely resemble an arsenical sublimate, but readily distinguished from it in not being crystalline. When, therefore, sulphurous acid is employed as a reducing agent in the preparation of a liquid for testing, it should be wholly expelled before the application of this test. Finally, if the copper-foil or the reduction-tube is not perfectly dry, the moisture may condense in the form of a mist-like deposit at about the point at which the arsenical sublimate usually forms; but the true nature of this deposit also is at once revealed by the microscope. From what has now been stated, it is obvious that the presence of arsenic is not fully established until the coated copper yields a sublimate of well-defined octahedral crystals. In applying this con- firmatory reaction, however, it should be borne in mind that when a comparatively large arsenical deposit is heated in a very small reduction-tube the sublimate may consist alone of granules, or a portion of the arsenic may even deposit in its metallic state. It rarely happens, however, that at least the upper margin of an arsen- ical sublimate does not contain the characteristic crystals. Should there be any doubt as to the nature of the sublimate, the lower end of the tube may be removed and the deposit resublimed, when, if consisting of arsenic, it will be converted into the crystalline form. In all cases the size of the reduction-tube should be in suitable proportion to the quantity of deposit to be examined. But even should this test, when applied to a suspected solution, vield an arsenical sublimate, it of course would not follow that the FALLACIES OF RKINSCH's TEST. 277 poison was really derived from tlio suspected li(|uid, unless the analyst was perfectly certain of the purity of the hydrochloric acid, and in some instances also of the cojjper, employed. As found in commerce, hydrochloric acid may contain very notable quantities of arsenic. In all cases a portion of the sample of the acid about to be employed should first be diluted with five or six volumes of water and boiled for about ten minutes with a slip of bright coi)per; if this fails to yield a deposit, the acid may be considered free from arsenic. In regard to the purity of copper, it is now known, chiefly through the researches of Dr. Taylor, that this metal, as usually employed in investigations of this kind, nearly always contains traces of arsenic. This impurity, however, could only lead to error when the copper is acted upon and dissolved by the liquid with which it is boiled; any arsenic thus dissolved might then deposit upon a fresh portion of the copper. This objection, therefore, has no practical force, except in cases in which a very notable quantity of the copper has dissolved and only a very minute trace of arsenic has been detected. When, in the application of the test to a sus- pected solution, the copper promptly receives an arsenical deposit, which after the addition of successive slips of the metal ceases to take place, it is quite certain that the poison is not-derived from the copjier. For the detection of traces of arsenic in copper we have found the following method, first advised by F. Field [Chem. Gaz., 1857, 313), exceedingly delicate. Ten grains of the copper are dissolved in slight excess of pure, hot nitric acid, the solution diluted to about three ounces of fluid, and ammonia added until the oxide of copper is precipitated, but not redissolved ; the precipitate is then redissolved by the addition of about twenty-five grains of ammonium oxalate, the copper oxalate thus produced precipitated by slight excess of hydrochloric acid, and the mixture allowed to stand some hours. The solution is then filtered, the filtrate saturated with sulphurous acid gas, concentrated to a small volume, and tested for arsenic, . either by sulphuretted hydrogen or by a fresh piece of copper. For this same pur])ose Dr. Odling recommends {Jour. Chem. Soe., July, 1863, 248) to distil a few grains of the copper, cut into small pieces, with an excess of pure hydrochloric acid and ferric chloride, the distillation being carried to dryness: the dry residue may be redistilled with a little fresh hydrochloric acid. By this *278 AESENIC. treatment the copper is quickly dissolved, and any arsenic present converted into chloride and thus carried over with the distillate. The distillate is tested for arsenic in the usual manner. Ferric chloride, Dr. Odling adds, may be purified from arsenic by evap- orating it once or twice to dryness with excess of hydrochloric acid. Interferences. — Should this test fail to yield a metallic deposit upon the copper, it would not follow from this fact alone that arsenic was entirely absent, even as arsenious acid, since the deposi- tion of the metal may be prevented by the presence of certain other substances. Thus, in even strong solutions of the poison containing only a small quantity of a chlorate, as potassium chlorate, the copper remains perfectly bright, but the liquid acquires a bluish or greenish- blue color, due to the formation of a soluble salt of copper. Should arsenic and a chlorate occur in the same mixture, the solution is cautiously evaporated to dryness, and the dry residue fused in a long, narrow glass tube until the evolution of oxygen ceases : by this operation the chlorate will be converted into a chloride, and the arsenic into arsenic oxide. The tube is then cut into small pieces and boiled with a small quantity of pure water until the saline mat- ter has entirely dissolved, and the solution thus obtained, after filtra- tion if necessary, is saturated with sulphurous acid gas, the excess of which is afterward expelled by a gentle heat. The solution, which now contains the arsenic as arsenious acid, together with the chloride resulting from the decomposition of the chlorate, may be acidulated with hydrochloric acid and examined in the usual manner. So, also, the presence of manganese dinoxide, and of other sub- stances that decompose hydrochloric acid with the elimination of free chlorine, may interfere with the reaction of the test. And the same is true of free nitric acid. This acid, however, has little action upon the test unless present in quite notable quantity or the solution be concentrated to a small volume, when it acts upon and dissolves the copper. In case of the presence of free nitric acid, the solution may be neutralized with potassium hydrate, then acidulated with hydrochloric acid, and tested as usual ; or the solution may be cau- tiously evaporated to dryness, the residue dissolved in water, this solution saturated with sulphurous acid gas, then gently heated to expel the excess of gas, and examined. The alkaline nitrates have little or no effect upon the test until the solution is evaporated to near dryness, when they cause the solu- marsh's tkst. 279 tion of" the copper. In a mixture coiitaiiiiiij;^ the l-5tli of" its weijrht of potassium nitrate and l-500tli of" arsenious oxide, the reaction takes place much the same as in a pure sohition of the oxide. In conclusion, it may be remarked that this method of Keinsch possesses several advantages which entitle it to more consideration than it has usually received at the hands of chemists. Thus, it is easily and quickly applied, requiring but little apparatus, and that of the most simple kind ; it usually requires the purity of only one substance, namely, the hydrochloric acid, to be known, and this is readily established by means of the test itself; it requires no dilution of the suspected liquid, but, on the contrary, permits its concentration to almost any extent while the test is being applied ; it may be applied directly to much more complex organic mixtures than either of the other tests for this poison ; and, finally, it serves to separate from complex mixtures and reproduce in an unequivocal form a less quantity of the poison than any other known test, except, perhaps, one of the methods of Marsh's process, with which, however, it is about equally delicate. 5. Marshes Test. "When metallic zinc is treated with diluted sulphuric acid, the hydrogen of the latter is displaced by the metal with the formation of zinc sulphate, the hydrogen displaced passing off in its free state : Zn + H2SO^=ZnS04 + H2, If, however, arsenious acid or arsenic acid or any of the soluble compounds of the metal be present, the nascent hydrogen decomposes the arsenical compound, and, uniting with the metal, forms arsenuretted hydrogen gas, ASH3, which is evolved in its free state. The reaction in the case of arsenious acid is as follows : 3Zn + SHgSO.H- H3As03=3ZnSO,-f 3H2O+ AsHg ; with arsenic acid: 4Zn-}-4H2SO^+H3AsOi=4ZnSO, + 4H20 + ASH3. When the arsenic is present as a chloride, it yields hydro- chloric acid and the arsenuretted gas. Xeither metallic arsenic nor the sulphides of the metal will yield a trace of the gas. The pro- duction of arsenuretted hydrogen, under these conditions, has long been known, but Mr. Marsh, of Woolwich, in 1836, was the first to employ it as a method for the detection of arsenic. Arsenuretted hydrogen is a colorless, extremely poisonous gas, having a peculiar alliaceous odor, and specific gravity of 2.695; it is neutral in its reaction, and but sparingly soluble in water. It burns 280 AESENIC. with a bluish flame, giving rise to arsenious oxide, and is readily- decomposed by heat into free hydrogen and metallic arsenic; it is also readily decomposed by solutions of the easily reducible metallic oxides. These properties serve, in the manner to be pointed out hereafter, for the detection of very minute traces of the gas. Various forms of apparatus have been proposed for the pro- duction of this gas in its application to the detection of arsenic, but the most efficient is that advised by Otto, as illustrated, in principle, by Fig. 10. The gas-flask A, which may be substituted by a sim- FiG. 10. Apparatus for the application of Marsh's test. pie wide-mouthed bottle or in delicate experiments by a long test- tube, is provided with a closely-fitting cork carrying the funnel-tube a and the exit-tube b ; this tube should be tolerably wide, and have its lower end cut obliquely, to facilitate the dropping back of any condensed liquid into the flask, c is a drying-tube containing frag- ments of potassium hydrate or of calcium chloride, kept in their place by loose cotton. Unless the experiment is to be continued for some time, it is^only necessary to fill the drying-tube loosely with asbestos marsh's test. 281 moistened with coticentratt'd sulplmric; acid. Tliis tube is connected with the tube h by means of a perforated cork, and with the reduc- tion-tube d by a short india-rubber tube. Tiie reduction-tube {d) should be of hard glass, free from lead, and have an internal diam- eter of about .'j-20ths of an inch, and walls not less than the l-20th of an inch in thickness; its outer portion should ha contracted in two or three places, as shown in the figure, and terminate in a turned-up, drawn-out j)oint, which is fused in a small flame of a spirit-lamp until tlic opening becomes quite small. By preparing the end of the tube in this manner there is no danger of its fusing shut when the jet of gas is afterward ignited. In very delicate experiments, the bore of the contracted portions of the tube should not exceed the l-20th of an inch in diameter. Several of these tubes should be prepared and at hand. About two ounces, or sixty grammes, of pure zinc, either granu- lated or cut into very small pieces, are placed in the flask A, and, the apparatus being adjusted, covered with a cooled mixture con- sisting of one measure of pure concentrated sulphuric acid and four measures of distilled water, added through the funnel-tube a, which should extend to near the bottom of the flask. The zinc will now decompose the acid, with the evolution of hydrogen, in the manner before described. If the zinc should act only very slowly upon the acid, as is frequently the case with the pure metal, the action may be hastened by the addition of a few drops of platinic chloride. For this purpose, it is sometimes advised to add a little cupric sulphate; but, according to M. Gautier [Ann, d'Hyg., Jan. 1876, 149), the addition of this salt is attended with the loss of arsenic. Should the zinc or the sulphuric acid be contaminated with ar- senic, this will give rise to arsenuretted hydrogen. Before, therefore, applying the test to a suspected solution, the purity of the materials employed must be fully established. For this purpose, after the apparatus has become completely filled with hydrogen and while the gas is still being evolved, the outer uncontracted portion of the re- duction-tube is heated to redness, as illustrated in the figure, for about fifteen minutes or longer. If this fails to produce a metallic deposit or stain in the contracted part of the tube, in advance of the part heated, the material may be considered free from arsenic. The purity of the materials having been thus established, it may be 282 ARSENIC. necessary to wash and renew the zinc, dry the tubes, and add a fresh portion of the diluted acid. Sulphuric acid in its concentrated state should not be added to the zinc mixture, since, as first shown by H. Kolbe [Ding. Poly. Jour., April, 1872, 160), and confirmed by our own experiments, if the undiluted acid be brought in contact with the metal in the pres- ence of nascent hydrogen, it may be reduced with the formation of sulphuretted hydrogen, which might in part or wholly retain any arsenic present by converting it into arsenious sulphide. When the acid is diluted with about twice its volume of water this reduction does not take place. The apparatus being adjusted and completely filled with evolved hydrogen, the jet of gas, as it issues from the drawn-out end of the reduction-tube, is ignited, care being taken not to apply a light until the whole of the atmospheric air is expelled from the apparatus, as otherwise an explosion might occur. A small quantity of the arsen- ical solution is then introduced into the funnel-tube, and washed into the flask by the subsequent addition of a few drops of the diluted sulphuric acid. The decomposition of the arsenical compound, with the evolution of arsenuretted hydrogen, will commence immediately. The presence of the arsenuretted gas may be established by three different methods, — namely : «■ By the properties of the ignited jet; /?. By decomposing it by heat applied to the reduction-tube ; and, y. By its action upon a solution of silver nitrate. a. The ignited jet. — As soon as the arsenical solution is intro- duced into the flask the evolution of gas increases ; this increase is quite perceptible even when the liquid within the flask contains only the 1-1 ,000,000th of its weight of arsenious oxide. The flame of the ignited jet will now increase in size, acquire a bluish tint, and, unless only a minute quantity of arsenic is present, evolve white fumes of arsenious oxide; so, also, sometimes, the flame emits a peculiar alli- aceous odor. If the white fumes thus evolved be received upon a cold surface, as an inverted watch-glass, they condense to a white powder, which sometimes contains octahedral crystals. The arsenical nature of this ])owder may be shown by any of the methods hereto- fore pointed out for the recognition of solid arsenious oxide. This, however, is by no means a delicate method for detecting the presence of the arsenuretted gas; and it should never be employed to the exclusion of that now to be mentioned. marsh's tf,st, 283 If tlie flame be allowed to strike aerlia|)s the first to resort to the decomposition of the arsenn- retted gas by heat, as a means of its detection. The :ipi)ani(iis being filled with hydrogen and the evolution of gas quite moderate, heat is aj)plied to the reduction-tube at a point about one-half or three- quarters of an inch on the inside of the outer contraction. When the part of the tube to which the flame is applied is quite red hot, a very small quantity of the arsenical solution is introduced, by means of the funnel-tube, into the flask. The arsenuretted hydrogen now' evolved, as it passes through the red-hot ])ortion of the reduction- tube, will be decomposed, with the production of a deposit of metallic arsenic in the contracted part, in advance of the flame. After a good deposit has thus formed, the heat of the lamp may be so changed that the metal may be deposited in the second contracted portion of the tube. The physical appearance of the deposits thus obtained depends somewhat upon the quantity of arsenic present, but they usually, especially when obtained from very dilute solutions, consist of three conjoined portions, the inner of which is transparent and of a brown color, while the central part has a brilliant metallic appearance, and this fades into a lighter-colored or gray portion, which is impercep- tibly lost. Very thick deposits may present much the same charac- ters as presented by the sublimed metal already described. When the quantity of arsenic present is comparatively large and the current of gas rapid, sometimes arsenical stains may be obtained from the ignited jet at the same time that a deposit is being formed in the heated tube. Delicacy of this method. — A much smaller quantity of the metal will yield deposits by this process than will serve for its detection from the ignited arsenuretted gas. This difference is due to the fact that by the method under consideration the metal eliminated from the decomposed gas may be collected at about the same point for several minutes, or longer if necessary; whereas from the gas when ignited it can be collected at the same place for only a few moments. Another advantage of this method over the preceding is, that it may 288 ARSENIC. be applied with a less quantity of liquid, since it requires only a feeble current of gas. In the following experiments, one hundred grain-measures of liquid, including the arsenical solution, were present in the apparatus, and the reduction-tube was contracted to a bore of about the 1— 20th of an inch in diameter. The arsenious oxide, as introduced in the apparatus, was in solution in ten grains of water. 1. 2W0" grain of arsenious oxide, in one hundred grains of liquid, or one part of the acid in the presence of 250,000 parts of fluid, yields in a very little time a very fine deposit, the inner portion of which has a brown color, while the outer part has a bright, metallic lustre. grain, under a dilution of 500,000 parts of liquid, yields 1 ■"• 5000 much the same results as 1. 3. x¥,Vro grain, under a dilution of 1,000,000, yields a quite good deposit. 4. "2 s-.VoT gi'3-in, under a dilution of 2,500,000, yields after some minutes a very satisfactory deposit. 5. -g-o^o- grain, in the presence of 5,000,000 parts of liquid, yields after several minutes a very distinct stain, the outer part of which has a dark, metallic appearance, and the inner, a brown- ish color. In regard to the delicacy of this method, it may be remarked that in the whole range of chemical tests there is perhaps no other that will indicate the presence of a substance under as great a degree of dilution. Fallacies. — Antimonuretted hydrogen also is decomposed under the above conditions, with the deposition of metallic antimony. Since, however, antimonuretted hydrogen is decomposed at a lower temperature than the arsenuretted gas, the antimony eliminated is always, in part at least and from dilute solutions wholly, deposited before reaching the part of the reduction-tube to which the flame is applied ; when it yields deposits on both sides of the flame, the outer one is quite near the flame. On the other hand, arsenic deposits about one-half or three-quarters of an inch in advance, or on the outer side of the flame, and never before reaching the part of the tube to which the heat is directly applied. This difference in itself is quite sufficient to distinguish between these metals, when only one of them is present. Again, the arsenical deposit has usually a bright, metal- lic lustre, whilst the antimonial has a dull and darker appearance. marsh's test. 289 Very thin deposits of the two raetiils, however, may present very siiuihir appearances. In regard to the action of heat and chemical reagents upon these metallic deposits, they differ in the following respects : a. If the tube, removed from the apparatus, be heated at a little distance from and on the inner side of the crust, and the heat then slowly advanced to it, the arsenical deposit readily volatilizes and recondenses a little farther on, in the form of brilliant, octahedral crystals of arsenious oxide. Under the same circumstances, the anii- monkil deposit requires a much higher temperature for its vaporiza- tion, and re-deposits quite near the point at which the heat is applied, and the sublimate produced is generally amorphous, or consists in part of minute granules and opaque granular masses; but it may contain well-defined octahedral crystals of antimonious oxide. The arsenical sublimate may be further identified by its ready solubility in a few drops of hot water, and by the resulting solution, when acidulated with hydrochloric acid and treated with sulphuretted hydrogen gas, yielding a yellow precipitate. These characters, how- ever, reveal themselves only in sublimates obtained from compara- tively tiiick crusts of the metal. b. The deposits of the two metals may also be distinguished by either a solution of ammonium sulphide, or of sodium hypochlorite, or by dissolving the crust in nitric acid, evaporating the solution to dryness, and treating the residue with silver nitrate, in the manner already described for the discrimination of stains obtained on por- celain from the ignited gas. c. If a slow stream of perfectly dry sulphuretted hydrogen gas be conducted through the tube containing the arsenical deposit, and the latter heated by a flame applied to the tube, beginning at the outer margin of the deposit, it in vaporizing is converted into arse- nious sulphide, which condenses at a little distance in advance of the heat to a yellow deposit, the inner margin of which, even after cool- ing, has sometimes an orange hue. The metallic deposit from the l-5000th of a grain of arsenious oxide will in this manner yield very distinct results. Under these same conditions, the antimonial crust also decomposes the sulphuretted gas, with the formation of antimonious sulphide, which, however, condenses to a reddish-brown or nearly black deposit. To effect this change requires a stronger heat than for the arsenical crust, and the sulphide formed deposits 19 290 ARSENIC. much nearer the flame of the lamp. In applying this method, it must be borne in mind that sulphuretted hydrogen alone, especially if moist, may be decomposed by the heat with the deposition of globules of sulphur, which while warm have a yellow color, but when cold they have only a very faint yellow tint. Arsenious sul- phide is readily distinguished from free sulphur in being soluble in ammonia. When exposed to a slow current of dry hydrochloric acid gas, antimonious sulphide readily disappears, whilst the sulphide of arsenic is unaffected by this gas. These methods of distinguishing between these deposits were first pointed out by Pettenkofer and Fresenius. There is no other metal, besides arsenic and antimony, that will, by this method of Marsh, yield a deposit in the heated reduction- tube. Sulphur may yield a yellowish -white, and selenium a reddish- brown, stain ; but these stains could not be confounded with the arsenical deposit. y. Decomposition by silver nitrate. — If the reduction-tube of the apparatus be substituted by a tube bent at a right angle (Fig. 10, e), and the arsenuretted hydrogen conducted into a solution of silver nitrate, both the gas and the silver salt undergo decomposition, with the production of arsenious acid, which remains in solution, and the elimination of metallic silver, which falls as a black precipi- tate. The reaction in this case is AsH3+6AgN03+3H20 = 6Ag -f-HgAsOg+GHNOg. The resulting solution, therefore, contains arsenious acid and free nitric acid, together with any excess of silver nitrate employed. In applying this test, which was first proposed by Lassaigne, the current of gas should not be rapid, and only a quite dilute solution of the silver salt should at first be employed ; more of the salt may afterward be added, if required. The presence of the arsenious acid thus produced may be shown by either of the following methods : 1. If the solution be filtered, and the filtrate exactly neutralized with ammonia, it will yield a yellow precipitate of silver arsenite, having the properties already described. Should the whole of the silver nitrate have been decomposed by the arsenuretted hydrogen, it will of course be necessary to add a little of this salt, after the neu- tralization by ammonia, before the precipitate will appear. Since in the application of this test the neutralization of the eliminated nitric acid will give rise to ammonium nitrate, in which the silver arsenite FALLACIES OF MARSIl's TEST. 291 is simringly soluble, the ,-™c,i„„ will not be c,uite a.s .lelleate as when the (est ,s a|,,>l,e,l lo u p„re ,sol„li„„ of arsenious aeid. h . u,l, an,l he h „,ue t.eute.l with sulphuretted hydrogen g^ it yields a br,ght yellow preeipitate of arseoious sulpbi.le Tife ar sen,e fr„.„ the l-l()„Oth of a grab, of arsenious oxide eun in tbi. .nanoer be reeovered without any appreciable loss. Instead of treat- ing the solution with sulphuretted hydrogen, after the removal of the KZeil t;:^ ""■"" "^ "^''■"'^'"-'" -'•"' ■■' -^ ^ --■-'> -y 3. If, after the removal of the excess of silver nitrate by the cautious addition of hydrochloric acid, the filtrate be cautiously evaporated to dryness, the arsenic will remain as a white deposit of ursenie a«rf, which, when moistened with a solution of silver nitrate assumes a brick-red color. "uiaie, micacy of thh readion-ln the following investigations the isenions oxide was dissolved in ten grains of pur^ water, the soint on placed ma small test-tube with a k.. fragments of ziLc, and then ^fficieiU diluted sulphuric acid added to evolve a slow'stream of gas. The gas thus evolved was conducted into five grains of a dilute solution of silver nitrate. 1. -rio grain of arsenious oxide yields a gas that produces a copious black precipitate in the silver-solution. 2- nr'rir g''ai" yields a good precipitate. 3- -nr.k^ grain ■ a black deposit soon appears in the immerse -P-ate Z detect arsenic in the presence of antimony, even, according to Dr 292 ARSENIC. Hofmann^ when the mixture consists of one part of the former and one hundred and ninety-nine parts of the latter metal, and only a minute quantity of the mixture is examined. So, also, will sulphuretted hydrogen and the hydride of phos- phorus produce black precipitates in a solution of silver nitrate. It is obvious, therefore, that the mere production of a black precipitate, in the silver-solution, is not in itself direct evidence of the presence of arsenic. When arsenuretted hydrogen is passed into a solution of corrosive sublimate it produces a yellow or brownish-yellow precipitate, which, according to H. Rose, consists of AsjSHggClg, — the reaction being, perhaps, 2AsH3-f 6HgCl2= 6HC1 + As23Hg2Cl,. Antimonuretted hydroo'en, under like circumstances, produces a white, flocculent pre- cipitate, which almost immediately turns gray, then dark gray or almost black. The reaction of the arsenuretted gas is extremely delicate. Thus, the gas evolved from the 1— 50,000th of a grain of arsenious oxide in ten grains of fluid will produce a quite distinct yellow deposit in the lower end of the delivery-tube. Since arsenuretted hydrogen is thus decomposed by salts of silver and of mercury, as well as by free chlorine, nitric acid, and certain other substances, if either of these be present in the flask in which the o-as is being generated, the latter may be entirely decomposed before leaving the apparatus. It is, therefore, obvious that if in the examination of a suspected mixture by the method of Marsh it should yield negative results, it would not follow, from this fact alone, that arsenic was entirely absent, even in a soluble form. M. Z. Roussin has recommended, for the evolution of the hydro- gen in the application of Marsh's test, to substitute for the zinc metallic magnesium, which may now be obtained in its pure state. If this metal be employed, before introducing the arsenical or sus- pected solution into the apparatus the evolved gas should be ex- amined by passing it through the red-hot reduction-tube for about ten minutes, for the purpose of testing its purity. This preliminary examination is necessary, since magnesium is sometimes contaminated with silicium, which might give rise to silicuretted hydrogen, with the deposition of a dark brown deposit in the heated tube. This deposit, however, differs from an arsenical crust in that it is un- bloxam's method. 293 affoc'ted by nitric acid and by a solution of :i liypochlorite, it being insoluble in tlu'so liquids. {Cheni. News, July, 1866, 27, 42.) Bloxam's Method. — When arsenious acid is present in a mix- tun* in wliioli watoi- is being deoomj)osed by a galvanic current instead of by zinc and sulphuric acid, the arsenical compound is also decomposed by the nascent hydrogen with the formation of ansenu- rettcd hydrogen gas. Prof. Bloxam has proposed this reaction as a ready means of detecting arsenic, and as free from some of the objections that may be urged against the method of Marsh. The form of apparatus he employs consists of a two-ounce narrow-mouthed bottle, the bottom of which has been cut off and replaced by a piece of vegetable parchment tightly stretched over it and secured by a thin platinum wire. The bottle is furnished with a cork, carrying a funnel-tube, and a small tube bent at a right angle and connected with the reduction-tube by a caoutchouc connection ; through the cork also passes a platinum wire bent into a hook, inside of the bottle, for suspending the negative plate. The bottle is placed in a glass vessel of such size as to leave a small interval between the two, and this arrangement placed in a large vessel of cold water; an ounce of diluted sulphuric acid -is then introduced into the apparatus, so as to fill the bottle and the outer space to about the same level, the positive plate being immersed in the acid contained in this outer space. The apparatus being thus adjusted, the terminal platinum plates, each measuring about two inches by tiiree-quarters of an inch, are connected by means of broad strips of platinum-foil with a Grove's battery of five cells ; the one within the bottle being connected with the zinc, and that in the outer vessel with the platinum extremity of the battery. When the bottle has become filled with hydrogen, the reduction-tube — which may be constricted at several places — is heated to redness for about fifteen minutes, to test the purity of the sulphuric acid employed. The liquid to be tested is then introduced into the bottle by means of the funnel-tube, and the gas evolved ex- amined in the same manner as in Marsh's method. If the mixture froths, from the presence of organic matter, a little alcohol may be added. The author of this method states that by it the 1-1 000th of a grain of arsenious oxide can be detected in an organic mixture with the greatest ease and certainty. 294 AESENIC. When the metal exists in the form of arsenic acid, no arsenu- retted hydrogen is evolved by this process. When in this form, however, the arsenic may be made to respond to the test by treating the solution, previous to its introduction into the apparatus, with sulphurous acid gas or a few drops of a solution of sodium disul- phite, and heating on a water-bath until the sulphurous odor has disappeared. The introduction of a few drops of a solution of sul- phuretted hydrogen gas into the apparatus also serves to reduce the arsenic acid, as the arsenic combines with the nascent hydrogen in preference to the sulphur; even when large excess of sulphuretted hydrogen is employed, it does not interfere with the evolution of the arsenuretted gas. But under these circumstances a deposit of sulphur may form in the reduction-tube outside of the arsenical deposit, and the latter may consist partly of arsenious sulphide ; the sulphide of arsenic may be distinguished from free sulphur by its deep yellow color, and its ready solubility in a warm solution of ammonium carbonate, in which the sulphur is insoluble. The addition of sulphuretted hydrogen to the arsenical solu- tion, under the above circumstances, would precipitate as a sulphide any antimony or mercury if present, in which form neither of these metals interferes with the detection of arsenic. Thus, Prof. Bloxam states that the 1-1 000th of a grain of arsenious oxide, converted into arsenic acid, by the action of hydrochloric acid and potassium chlo- rate, when mixed with one grain of tartar emetic and excess of sulphuretted hydrogen, and the mixture introduced into the decom- posing cell, furnished in the reduction-tube a distinct deposit of arsenic free from antimony. Similar experiments made with mix- tures of arsenious acid and corrosive sublimate furnished equally good results. Without the addition of the sulphuretted hydrogen, the antimony and mercury are deposited upon the negative plate; when, however, a comparatively large quantity of the former metal was present, it yielded a metallic mirror in the reduction-tube. [Quart. Jour. Chem. Society, xiii. 12, 338.) Various other modifications of Marsh's method have been pro- posed. Thus, Fleitmann has advised to generate the hydrogen by acting upon zinc with a warmed solution of potassium hydrate, in- stead of diluted sulphuric acid. Any arsenic now added, if in solu- tion, would be evolved as arsenuretted hydrogen, while if antimony bettendorff's test. 295 were present it would hi; retained in tlie metallic state by the al- kaline solution. Zinc, however, acts only very slowly upon the alkaline solution, and even if iron filinpearance, at least when rubbed. The coated copper is thoroughly washed in alcohol or ether, dried, then heated in a reduction-tube, and any sublimate thus obtained examined by the microscope. Another portion of the filtrate may be acidulated with hydro- chloric acid, and treated with excess of a solution of stannous chlo- ride, when, if it yields a dark gray precipitate, the mixture is gently heated until the precipitate has completely subsided ; the supernatant fluid is then decanted, the residue washed with hot water, then boiled with a little water strongly acidulated with pure hydrochloric acid, which will cause any finely divided mercury present to collect into comparatively large globules. It must be remembered that various organic solutions yield with the tin reagent a white precipitate, which may more or less conceal the color of the mercurial deposit. Under these circumstances, the precipitate is boiled for some time with a strong solution of caustic potash, which will dissolve the organic matter, leaving the mercury in the form of a grayish-black powder. This is then boiled with a little diluted hydrochloric acid, in the manner just described. If a portion of the filtrate be acidulated with hydrochloric acid and treated with sulphuretted hydrogen gas, any of the poison pres- ent will give rise to sulphide of mercury, which will be thrown down as a black precipitate, at least if excess of the reagent has been employed. After the precipitate has completely subsided, it may be collected on a filter, washed, and then dried. Its mercurial nature may be established l)y mixing it with several times its volume of recently ignited sodium carbonate and heating the mixture in a reduction-tube, when it will undergo decomposition with the produc- tion of a globular sublimate of metallic mercury, readily identified by means of the microscope. The positive reaction of either of the foregoing tests would, of course, simply indicate the presence of the mercury of the corrosive sublimate. For the purpose of showing the presence of the chlorine, 358 MERCUEY. it is best to agitate a portion of the filtrate with ether, in the manner already directed, then allow the ethereal solution to evaporate spon- taneously, dissolve the residue in a small quantity of warm water, and treat the solution with silver nitrate. As the alkaline chlorides are insoluble in ether, the detection of chlorine under these circum- stances would not be open to the objection that would hold if the silver reagent were applied directly to the original filtrate : especially will this objection be guarded against if the ethereal liquid, on evapo- ration, leave the poison in its crystalline state. Should the methods already given fail to reveal the presence of mercury in the filtrate, then the organic solids left upon the filter may be examined. For this purpose the mass is transferred to a porcelain dish, the solids cut into small pieces, and boiled for about twenty minutes with pure water, the mixture being frequently stirred by means of a glass rod. When the mixture has cooled, the liquid portion is separated by a filter, the filtrate concentrated to a small volume, and then examined in the manner before directed for the first filtrate. Instead of boiling the organic solids with pure water, they may be boiled with water containing hydrochloric acid until they are entirely disintegrated. If, however, this method be em- ployed, the presence of the chlorine of the corrosive sublimate can- not be established. Another method for the examination of the above organic solids is to boil the mass with a somewhat concentrated solution of potas- sium hydrate until the solids are entirely decomposed, and then treat the mixture with a solution of stannous chloride, the heat being con- tinued for some little time after the addition of the tin reagent. Any- dark gray precipitate thus obtained is carefully collected, washed, and examined in the manner already described. From the Tissues. — If there has been a failure to detect corrosive sublimate under one or other of the conditions now described, it will no longer be possible to show the presence of the poison as a whole ; but the presence of the absorbed mercury may be shown in some of the soft tissues of the body. For the recovery of the absorbed metal various methods have been advised. The finely divided tissue, as about ten ounces of the liver, may be made into a thin paste with water, containing about one-sixth of its volume of pure hydrochloric acid, and the whole heated at about the boiling tem- perature until the organic solids are completely disintegrated, which SEPARATION FIIOM THE TISSUES. 369 will usually require about two hours. The mass is theu allowed to cool, transfjerred to a linen strainer, the strained liquid filtered, and then conecntrated to a comparatively small volume. A portion of the liquid may now be heated to the boiling temperature, and ex- amined by the copper test, employing at first only a very minute slip of the metal. In applying this test, it should be remembered that the copper, after prolonged heating, may acquire a very distinct stain or tarnish, even in the absence of mercury or of any other metal. Before heating the copper in a reduction-tube it should be very thoroughly washed, first in water containing a little ammonia. Should the first portion of liquid examined fail to reveal the presence of mercury, then another and larger portion, or even the whole of the remaining liquid, should be examined in a similar manner. The. copper test will serve to recover very minute quantities of mercury from very complex organic liquids. A portion of a human liver, free from mercury, was boiled with diluted hydrochloric acid in the manner just described, and the liquid strained. To one hun- dred grain-measures of the strained fluid the 1-lOOOth of a grain of corrosive sublimate was added, — the poison then being under a dilution of 100,000 times its w^eight of the organic liquid, — and the mixture boiled with a very small slip of bright copper-foil. After a little time the copper received a very distinct metallic stain, and, when washed, dried, and heated in a small reduction-tube, yielded a sublimate which, under the microscope, was found to contain over one hundred characteristic globules of mercury. Should the examination of the first portion of the above liquid indicate the presence of mercury, and it be desired to pursue the in- vestigation, another portion may be treated wnth excess of stannous chloride, and gently warmed, until the precipitate has completely deposited. The precipitate is then collected, w^ashed, and boiled in a porcelain evaporating-dish with a solution of potassium hydrate until the organic matter is dissolved and the residue assumes a dark gray color. The clear supernatant liquid is then decanted, and the residue repeatedly washed with hot water, then boiled wuth hydro- chloi'ic acid, which will cause any finely divided mercury present, if entirely free from foreign matter, to coalesce into globules. Another, and in some cases preferable, method for breaking up the animal tissues is by means of hydrochloric acid and potassium chlorate, in the manner described for the recovery of absorbed arsenic. 360 MERCURY. The finely divided tissue is treated with about one-fourth of its weight of pure concentrated hydrochloric acid, and the whole made into a thin paste by the addition of water. The mixture is then heated to about the boiling temperature, and small quantities of powdered potas- sium chlorate occasionally added until the mass becomes perfectly homogeneous, after which it is kept at a gentle heat until the odor of chlorine has entirely disappeared. The mixture is now allowed to cool, the liquid filtered, and the solid matters on the filter well washed with hot water. The filtrate may now be partially neutral- ized with pure sodium carbonate, and concentrated until its volume is about three times that of the hydrochloric acid employed in the destruction of the organic matter. The liquid tluis obtained, after filtration if necessary, is exposed for several hours to a slow stream of sulphuretted hydrogen gas, then gently heated, and allowed to stand in a moderately warm place for about fifteen hours. Any mercury present will now be in the pre- cipitate, in the form of the black sulphide, together with more or less organic matter, the color of which may disguise that of the mercurial compound. The precipitate is collected upon a small filter, well washed, and then transferred to a porcelain dish, treated with a pro- portionate quantity of concentrated hydrochloric acid, and pure nitric acid added drop by drop until complete solution has taken place. By this treatment with the mixed acids the mercury of the mercurial sulphide will be dissolved to mercuric chloride, while the sulphur will be eliminated as a yellow adherent mass, which as it forms should be removed by means of a glass rod. On now cautiously evaporating the solution to dryness on a water-bath, the mercuric chloride will be left as a white crystalline mass; if the eliminated sulphur was not removed from the mixture, the residue may consist largely of mer- curic sulphate. A portion of the saline residue thus obtained may be tested for the poison in its solid state, and another portion dissolved in a small quantity of water, and the solution examined by the copper test. If the addition of water produces an insoluble yellow sulphate of mer- cury, its solution may be readily effected by the addition of a drop or two of hydrochloric acid. From the Urine. — About 300 c.c, or twelve fluid -ounces, of the urine are strongly acidulated with hydrochloric acid, evaporated to a small volume, filtered, the filtrate boiled with a small slip of bright FAILURE TO DETECT. 3G1 copper- foil, and the latter waslied, dried, and examined in the usual iiiaiuier. Another method for tiie examination of this fluid is to croncentrate it to near dryness, and then destroy the organic matter by means of hydrochloric acid and potassium chlorate, in the manner described for the recovery of the poison from the tissues. If the first of these methods be ad()j)ted and there is a failure to detect the metal, any solids separated by filtration should be examined. Dr. Thudichum remarks {Pathology of the Urine, 408) that in all cases where the urine contains mercury there is at the same time a peculiar albuminous substance present in it, which with nitric acid yields a faint reaction of albumen. A substance is also present having the reactions of sugar. In some cases of mercurial ism, he adds, the metal only appeared in the urine at intervals, even where the symptoms had undergone no remission. Failure to detect the Poisox. — It has not unfrequently happened in acute corrosive sublimate poisoning that there was a failure to detect the poison in any part of the dead body. In a case quoted by Dr. Beck [Med. Jur., ii. 638), in which a woman had poisoned herself with this substance, not a trace of the poison was found either in the matters vomited during life or in the contents of the stomach after death. So, also, in a case cited by Wharton and Stille (Med. Jur., 538), none of the poison was detected in the stomach and intestines of a young man who had taken three drachms of corrosive sublimate, and died from its effects on the sixth day. In another instance, recorded by Dr. Taylor (On Poisons, 471), in which two drachms were swallowed, and death occurred on the fourth day, a chemical examination of the stomach, blood, and tissues failed to reveal the presence of mercury. According to the observations of I. L. Orfila, absorbed mercury is eliminated from the system chiefly by means of the kidneys. In examining the urine of patients treated with mercurial preparations, he found the metal five days after it had ceased to be taken, but in eight days it was no longer discovered. In experiments upon dogs, he found the metal in the tissue of the stomach and liver of some of the animals as late as the eighteenth day, but in others, similarly treated, it had entirely disappeared. [Orfila'' s Toxicologie, 1852, i. 680.) When mercury remains in the body at the time of death, it, like 362 MERCURY. arsenic, may be recovered after very long periods. In a case of cor- rosive sublimate poisoning, which we examined some years since, and in which death occurred on the fourth day, the metal was readily detected in the stomach and liver of the body after it had been buried nine months: none of the other organs were chemically examined. It need hardly be remarked that, since mercurial preparations are so frequently taken medicinally, the detection of minute traces of the metal in the dead body would not in itself be any evidence that it was the cause of death. According to the researches of J. G. Smith, Ph.G. [Amer. Jour. Pharm., Aug. 1877, 397), commercial corrosive sublimate is fre- quently contaminated with minute quantities of arsenic, most likely derived from the sulphuric acid used in preparing the mercuric sul- phate, from which afterward tlie mercuric chloride is sublimed. In five samples of the salt in which the arsenic was determined quan- titatively, the proportion of this metal, expressed as arsenic oxide, varied from 0,033 to 0.096 per cent. Quantitative Analysis. — The quantity of corrosive sublimate present in a solution of the salt may be readily estimated by precipi- tating the metal as mercuric sulphide. For this purpose, the solution, acidulated with hydrochloric acid, is saturated with a slow stream of washed sulphuretted hydrogen gas, after which it is allowed to stand in a moderately warm place until the precipitate has completely sub- sided ; the precipitate is then collected on a small filter of known weight, washed with pure water until the washings no longer have an acid reaction, dried on a water-bath at 100° C. (212° F.), and weighed. One hundred parts by weight of the dried sulphide cor- respond to 116.81 parts of anhydrous corrosive sublimate, or 86.20 parts of metallic mercury. If in the application of the tin test a known quantity of the mercurial solution was employed, any globules of metallic mercury obtained may be carefully washed, dried, and weighed. One hundred parts by weight of the pure metal represent 135.5 parts of corrosive sublimate. LEAD. 363 CHAPTER TIL LEAD, COPPER, ZINC. Section 1. — Lead. History and Chemical Nature.— Lead is one of the elementary metals. Its symbol is Pb ; its atomic weight 207 ; and its density 11.44. It is fonnd in nature associated with several other elements, but it occurs principally as sulphide of lead, or galena. Lead has a bluish-gray color and a strong metallic lustre; it is quite soft, being easily scratched by the finger-nail, and leaves a well-known mark upon white paper. It is very malleable, and fuses at about 315.5° C. (600° F.). In its pure state lead is unacted upon by pure water. But if air be present in the liquid, or its surface be freely exposed to the action of the atmosphere, the metal rapidly becomes corroded, and gives rise to oxide of lead, which partly unites with water and partly with carbonic acid, forming a hydrated oxycarbonate of lead. This compound partly deposits upon the lead as silky scales or falls as a precipitate, while a portion remains mechanically suspended in the liquid ; at the same time some little of the compound becomes dis- solved. When, however, the water holds in solution certain salts, such as the carbonates, sulphates, or phosphates, an insoluble crust of lead salt slowly deposits upon the metal and protects it from further action, and thus none of the lead is dissolved. On the other hand, the presence of chlorides and of nitrates increases the corrosive action of water. Dr. Frankland found that water which acted on lead lost this power after passing through a filter of animal charcoal, owing to a minute quantity of calcium phosphate passing into the water from the charcoal. [Chem. News, Dec. 1868, 296.) Lead is readily soluble in diluted nitric acid, especially upon the application of heat, with the formation of lead nitrate, and the 364 LEAD. evolution of nitrous fumes. Cold diluted sulphuric acid fails to dissolve it, but the hot concentrated acid dissolves it to lead sulphate, with the evolution of sulphurous oxide gas. Hydrochloric acid, even under the application of heat, has but little action upon the metal. Heated on charcoal before the blow-pipe flame, it gives rise to a yellow or brownish incrustation of oxide of lead. Physiological Effects. — In its metallic state lead seems to be inert. But all the compounds of the metal that are soluble in water or in the animal juices are more or less poisonous. Acute poisoning by the preparations of lead has been of rare occurrence, and has chiefly been the result of accident. Of the salts of lead, the acetate, or sugar of lead, is one of the most active, and has more frequently been taken as a poison than any of the other compounds. This salt, however, is poisonous only when taken in large quantity. Van Swieten mentions an instance in which it was given to the amount of a drachm daily for ten days before it caused any material symptom. (Christison, On Poiscms, 430.) Cases are not wanting, however, in which it produced speedy and violent symptoms, and even death. Acetate of Lead. Symptoms. — AThen an overdose of acetate of lead is swallowed, the patient usually experiences at first a nauseous metallic taste in the mouth, with a sense of constriction or burning heat in the fauces and epigastrium. These effects are followed, sooner or later, by severe gastric and abdominal pains, which are generally relieved, but sometimes increased, by pressure ; sometimes the pain is constant, at other times intermittent. There is also nausea, and sometimes fre- quent vomiting of a yellowish or blackish liquid ; in some instances the vomiting has been very slight. The thirst is frequently very urgent ; the skin cold, but sometimes hot, and generally covered by a clammv perspiration ; the countenance anxious ; the strength greatly prostrated ; the pulse slow and feeble, but often accelerated. In some instances there has been severe and even bloody purging ; but gen- erally the bowels are obstinately constipated, there being either no discharge or the matters passed being hard, dry, and black and their discharge attended with pain. Sometimes the limbs become affected with spasms and a sense of constriction. The urine is usually diminished in quantity. The intellect generally remains clear. ClIliOMlC POISONING. 365 Dr. MascliUa relates the ca.se of* an a^ed man who liad been ill for some days, and when first seen by a physician was suffering from yellowness of the conjunctiva, loss of aj^petite, eructations, accumu- lation of phlejiin on the chest, and attacks of giddiness. The evac- uations were normal, the thirst not increased, pulse 80 to 90, the tongue coated, and the man felt weaU. On the following day the weakness and other symptoms had increased ; but under the ad- ministration of tonics the patient became better. On the evening of the fourth day, however, he became worse; his eyes were fixed, his breathing short and rattling, pulse weak, the extremities cold, and death shortly ensued. Lead in large quantity was found in the contents of the stomach. The quantity of sugar of lead taken just before the increased symptoms preceding death a])peared was said to have been 20.12 grammes. [Med.-Chir. Rev., 1872, 265.) A case is reported in which the death of an infant was caused by the use of a lotion of lead acetate applied for sore nipples. The mother omitted to wash the lotion off before putting the child to the breast. It was seized with violent colic, and died in a few days with the usual symptoms of lead poisoning. Dr. von Linstow reports {Viert.f. Gericht. Med., Jan. 1874) two cases of fatal poisoning by lead chromate, which occurred in children aged respectively one and three-quarters and three and a half years, caused by sucking some pastry colored by chrome yellow. Several hours after the poison had been taken, both children were taken with vomiting, which lasted several hours, the matters vomited having a yellow color. There was great prostration and extreme thirst, but no diarrhoea nor pain. On the second day both had a hot and red countenance, and were stupid. The younger, about twenty-four hours after the commencement of the symptoms, had a slight diarrhoea and convulsions, which continued until death, which took place in forty-eight hours. On the third day an erythema- tous eruption appeared on the chest and abdomen of the elder, and he was dull and stupid. On the fourth day the pulse and respira- tion became irregular, the breath extremely fetid, stupor and un- consciousness supervened ; and the patient died five days after the ingestion of the poison. The quantity taken in each case was be- lieved to be between the l-5th and the l-6th of a grain of the lead compound. Chronic Poisoning .—li is well known that the frequently re- 366 LEAD. peated introduction of even very minute quantities of any of the preparations of lead into the system may after a time induce serious symptoms. Under these circumstances, the patient experiences gen- eral depression, loss of appetite, a metallic taste in the mouth, and generally great thirst. The throat becomes dry, the breath fetid, the countenance dull and anxious, the skin dry and of a dull yellow color, the bowels constipated, and the urine generally diminished. At the same time a blue line forms along the margins of the gums ; and there is more or less uneasiness or pain in the abdomen. As the case advances, the pain in the abdomen becomes very severe, and more or less constant : the walls of this cavity are generally hard and depressed. These effects are frequently followed by sharp pains in the extremities, muscular emaciation, and paralysis. A remarkable series of cases of lead poisoning occurred a few years since from the use of flour from a mill in which the mill- stones had been repaired by filling the defective parts with lead. Of four hundred and twelve persons who suffered from the use of the flour, thirty died. {Med. Times and Gaz., May, 1878.) Other instances similar to this have been reported. Within recent years a number of cases of lead poisoning have occurred from the use of canned fruits preserved in tinned cans alloyed with lead. In a case of this kind reported by Dr. Magru- der {Med. News, Sept. 1883, 261), there were colic, arthralgia, and paralysis, involving first the extensors of the wrist, and then those of the lower extremities, and extending also to the flexors of both. The lead-cachexia was well marked, and the bluish line on the gums very distinct. In a case reported by Dr. G. A. Kunkler, the external appli- cation of white-lead to a scalded surface, as a dressing, produced unmistakable symptoms of lead colic, — acute abdominal pain, retrac- tion of the umbilicus, constipation, and slight discoloration of the gums. {Med.-Chir. Rev., Oct. 1857, 525.) And Dr. G. Johnson, of London, has reported (1875) a very severe case of chronic lead poisoning resulting from the use of flahe-white, composed chiefly of carbonate of lead, as a cosmetic. When Fatal. — In a case quoted by Dr. Beck, a soldier who swal- lowed an unknown quantity of acetate of lead in solution was soon seized with the most violent symptoms, indicative of gastric inflam- mation, and died in great agony at the end of three days. {Med. FATAL QUANTITY. 307 Jur. i. 690.) Dr. Tiiylor refers to two cases in \vlii<-li Goulard's extract— which is a solution of the subacetate of lead— was taken in unknown quantity by two children, aj^ed respectively four and six years, and tluy both died within thirty-six hours. The symptoms were at first violent vomiting and purging: in one case they re- sembled those of Asiatic cholera. {Op. cit., 482.) In a case men- tioned by Dr. Christison {On Poisons, 430) the same preparation of lead was taken in unknown quantity by a soldier. The first symp- toms could not be ascertained, but on the second day he was affected with loss of appetite, paleness, costiveness, and excessive debility ; on the third day he had severe colic, drawing in of the abdomen, loss of voice, cold sweats, locked jaw, and violent convulsions, and expired before the evening of the same day. Fatal Quantity.— In the few fatal cases of acute poisoning by lead acetate that have occurred, the quantity taken could not be accurately determined. Instances are reported in which doses of about an ounce were taken without producing any very serious re- sults. On the other hand, a case is quoted by Dr. Christison in which two doses of a drachm each taken by a man, with an interval of several hours between the doses, produced acute pain in the abdo- men, bilious vomiting, loss of speech, delirium, profuse sweating, and slow pulse: with the aid of treatment the patient recovered. Two cases have already been cited in each of which about the l-5th of a grain of the chro'mate of lead proved fatal to two very young children. Treatment. — In acute poisoning by the acetate of lead, the stomach should be immediately emptied by the administration of an emetic of zinc sulphate, and its action followed by large draughts of milk containing white of egg. Various chemical antidotes have been proposed. Among these the most useful is sulphuric acid in the form of a solution of magnesium or sodium sulphate. Either of these salts would decompose the lead compound, with the forma- tion of insoluble and inert lead sulphate. The alkaline sulphides have also been recommended. They would give rise to the insoluble sulphide of lead. These salts, however, are in themselves poisonous in large doses, and their use as antidotes has not been as successful as upon chemical grounds might have been expected. The hydrated sesquisulphide of iron has been strongly recommended by M. Bou- chardat; and its efficacy has been recently confirmed in a case 368 LEAD. reported by M. Lepage. As this compound is inert, it may be ad- ministered in large quantity. The alkaline carbonates are inadmis- sible, as they would give rise to lead carbonate, which is equally poisonous with the acetate of the metal. In chronic lead poison- ing, M. Rabuteau strongly advises sodium iodide as preferable to the potassium salt. Post-mortem Appearances. — In the case already cited from Dr. Beck, the mucous membrane of the stomach was found abraded in several places, particularly near the pylorus ; and the oesophagus, stomach, duodenum, mesentery, liver, and spleen were in a state of high inflammation. In the two cases mentioned by Dr. Taylor, the mucous membrane of the stomach was found of a gray color, but otherwise perfectly healthy ; and the intestines were much contracted. In the fatal case cited by Dr. Christison, the lower end of the oesoph- agus, the whole stomach and duodenum, part of the jejunum, and the ascending and transverse colon were found much inflamed ; and the villous coat of the stomach appeared as if macerated. It is necessary to bear in mind that acetate of lead has caused death without leaving any well-marked morbid appearance in the body. In the two cases in which the chromate of lead proved fatal, the raucous membrane of the stomach and duodenum was found swollen and loose, and in some places entirely destroyed, and at one spot per- foration had taken place, due to the corrosive action of the poison. There were also found hypereemia of the brain and its membranes, beginning fatty degeneration of the liver, commencing icterus, hyper- semia of the kidneys, suppurative pyelitis, and a softened condition of the spleen. Chemical Properties. General Chemical ISTature. — Acetate of lead, as usually found in the shops, is in the form of white crystalline masses, which have a density of about 2.6, a slight vinegar-like odor, and a sweet- ish, astringent taste. In its crystalline state this salt consists of one atom of lead, two molecules of acetic acid, with three of water, Pb2C2ll302 ; 3Aq ; it crystallizes in four-sided prisms. When the crystals are exposed to dry air they slightly effloresce, and after a time become partially converted into lead carbonate, from the absorp- tion of carbonic acid from the atmosphere. When moderately heated, SPECIAL CHEMICAL PROPERTIES. 369 they fuse and give oil" tlieir water of erystalHzation ; at higher tem- peratures the salt undergoes complete decomposition, leaving a black residue consisting of a mixture of charcoal and metallic lead. Solubility. 1. In Water. — When finely powdered crystallized acetate of load is agitated for a few minutes with its own weight of water, at a temperature of 15.5° C. (60° F.), and the liquid quickly filtered, crystals of the salt immediately begin to separate from the filtrate; if this mixture be allowed to evaporate spontaneously, it leaves a crystalline residue, indicating that the filtered fluid originally held in solution one part of the salt in 1.62 parts of the liquid. When the powdered salt is agitated for a few minutes with an equal weight of water at a temperature of 15.5° C. (60° F.), and the mixture allowed to stand at about the same temperature for forty-eight hours, and the liquid then filtered, the filtrate contains only one part of the salt in 2.67 parts of water. From these experiments it is obvious that the mere act of agita- tion very much increases the solubility of this salt in water. This circumstance may, in part at least, account for the discrepant state- ments of observers in regard to the solubility of the salt. 2. In Alcohol. — When large excess of the pulverized salt is agitated for a few minutes with pure alcohol of 97 per cent., and the solution quickly filtered, the filtrate contains one part of the salt in twenty parts of the liquid. But if, after agitating the mixture for a few minutes, it be allowed to stand quietly for twenty-four hours and the liquid then filtered, the filtrate contains only one part of the salt in about sixty-five parts of the menstruum. The more dilute the alcohol, other conditions being equal, the greater will be the quantity of the salt that it will dissolve. 3. In Ether. — Absolute ether, under any circumstance, fails to dissolve an appreciable trace of the salt. Special Chemical Properties. — When acetate of lead, in its solid state, is moistened with a solution of potassium iodide, it assumes a bright yellow color, due to the formation of iodide of lead. The least visible quantity of the salt will exhibit this reaction. Thus, a residue representing only 1-1 000th of a grain of lead oxide will yield a very satisfactory bright yellow coloration ; and even the l-10,000th of a grain, when deposited at one point, will assume a distinct yellow hue. The lead iodide thus produced is slowly soluble in large excess of the reagent. 24 370 LEAD. If a small portion of the salt be introduced into a drop of potas- sium chromate solution, it also assumes a bright yellow color, lead chromate being formed. Crushing the crystal facilitates the forma- tion of the yellow compound. When gradually heated on a piece of porcelain, acetate of lead fuses to a clear liquid, boils, and then becomes reduced to a white, anhydrous mass ; if the heat be continued, the mass again fuses, then becomes dry and charred, and slowly assumes a yellowish or reddish- brown color. This residue consists of a mixture, in variable propor- tions, of different oxides of lead. Almost the least visible crystal of the salt, when thus treated, leaves a brownish residue, apparently several times greater than the crystal employed. The carbonate of lead, when treated in this manner, does not fuse ; but it is slowly decomposed, with the production of a similar reddish-brown residue. Heated upon a piece of charcoal in the inner blow-pipe flame, acetate of lead fuses, then undergoes decomposition, with the produc- tion of bright, malleable globules of metallic lead, and the formation of a yellow incrustation of oxide of lead. The carbonate of lead, under these circumstances, yields at first a brownish mass, which soon furnishes bright, metallic globules. When acetate of lead is placed in a small quantity of ferric chloride solution, it slowly dissolves to a fine red solution of ferric acetate, FegGCaHgOg. If the salt be heated in a test-tube with concentrated sulphuric acid, it undergoes decomposition, with the evolution of pungent vapors of acetic acid. When heated with a mixture of equal volumes of alcohol and sulphuric acid, it evolves acetic ether, readily recognized by its peculiar aromatic odor. These reactions are simply due to the acetic acid of the lead salt, and are common to all acetates. Pure aqueous solutions of lead acetate are colorless, odorless, and have a sweetish, styptic taste, and, if not too dilute, a feebly acid reaction. When a solution of this kind is allowed to evapo- rate spontaneously, the salt is left in the form of white, crystalline needles. In the following examinations in regard to the behavior of re- agents with solutions of lead, the pure crystallized acetate was dis- solved in water very slightly acidulated with acetic acid. The fractions employed indicate the fractional part of a grain of lead oxide, PbO, or its equivalent, in solution in one grain of the liquid. SULPHURETTED HYDROGEN TEST. 371 Except wlioii otiierwise iiulicated, tlio results refer to the beliavior of one grain of the solution. One part of lead oxide represents 1.696 parts of crystallized acetate of lead. 1. Sulphuretted Hydrogen. This reagent, either in its gaseous state or in the form of an alkaline sulphide, throws down from neidral, acidulated, and alka- line solutions containing lead a black, amorphous precipitate of lead sulphide, PbS, which is insoluble in the caustic alkalies and in the diluted uiineral acids. Hot concentrated hydrochloric acid dissolves the precipitate, with the evolution of sulphuretted hydrogen and the formation of lead chloride, which, unless the quantity be very minute, separates, as the liquid cools, in the form of beautiful crys- talline plates. The precipitate is readily decomposed by hot nitric acid, with the formation of lead nitrate and the separation of free sulphur ; if the acid be concentrated and the heat continued, the separated sul- phur becomes oxidized into sulphuric acid, which, displacing the nitric acid, unites with the lead, forming lead sulphate. The sul- phate of lead thus formed generally separates . in the form of a white, granular powder, but sometimes in the form of small, bril- liant crystalline plates ; if, however, the quantity of the lead salt produced be only small, it may remain in solution in any excess of nitric acid present. In examining the limit of the reaction of this reagent, a slow stream of the washed sulphuretted gas was passed into ten grains of the lead solution, contained in a small test-tube. 1. 1-lOOth solution (= -j^Qth grain PbO) yields an immediate, copious, black deposit. When the precipitate is dissolved in the mixture, by excess of hydrochloric acid, it yields a white precipitate of crystalline needles of lead chloride. 2. 1-lOOOth solution yields an immediate precipitate. When a solution of this strength is exposed to the vapor of sulphu- retted hydrogen, its surface becomes covered with a black pellicle of lead sulphide. 3. l-10,000th solution : the first bubble of the reagent produces a deep brown coloration ; and a few bubbles produce a deep brown turbidity. After saturating the solution with the reagent, and 372 LEAD. allowing it to stand an hour, a very satisfactory black deposit separates. 4. l-50,000th solution : after a few moments the liquid assumes a distinct brown color, and very soon presents a brown turbidity ; after a few hours distinct brownish flakes separate. 5. l-100,000th solution : after some minutes the liquid assumes a distinct brownish tint, and soon afterward becomes turbid : after some few hours the brownish color deepens, but no deposit separates. 6. l-250,000th solution : after several minutes the liquid assumes a just perceptible cloudiness, with a faint brownish tint, which is only distinctly observed when compared with a clear solution, and best seen by looking through the liquid from the top. The formation of the precipitate from very dilute solutions is much facilitated by heating the mixture. The delicacy of the reac- tion of this test has been variously stated. Thus, Pfaff placed the limit of the brown coloration at one part of lead oxide, in the form of nitrate, in 100,000 parts of liquid ; Lassaigne, at 200,000 parts ; and Harting, at 350,000 parts. As, however, neither of these ob- servers states the amount of the solution operated upon, these dis- crepancies are readily explained. Fallacies. — The production of a black precipitate by this reagent is common to solutions of several other metals besides lead. The true nature of the lead precipitate may be established by dissolving it, by the aid of heat, in diluted nitric acid containing just suflScient of the acid to effect decomposition, and then testing the solution with either potassium iodide or potassium chromate, or with diluted sulphuric acid; or, after filtration, the nitric acid solution may be evaporated to dryness, and the residue examined by any of the tests already mentioned for salts of the metal when in the solid state. When strongly heated in a reduction-tube, lead sulphide is con- verted into a hard, brittle mass, but fails to yield a sublimate. 2. Sulphuric Acid. This acid and its soluble salts throw down from solutions of salts of lead a heavy, white precipitate of lead sulphate, PbSOi, which is soluble in large excess of the fixed alkalies, and in some of the salts of ammonium, but very sparingly soluble in diluted nitric and hy- drochloric acids. Strong nitric acid dissolves it in limited quantity UYDKOCIILOKIC ACID TKST. 373 to a clear solution. Concentrated hydrochloric acid dissolves it rather readily, especially upon the application of heat, yielding crystals of lead chloride as the mixture cools. From very dilute solutions of salts of lead the precipitated sul- phate does not separate until after some time: it then deposits in the form of small granules. Solutions of the alkaline carbonates, nor- mal and acid, convert lead sulphate, even at ordinary temperatures, into lead carbonate; solutions of normal alkaline carbonates, but not those of the acid carbonates, dissolve some of the lead compound in this process (H. Rose). From an alkaline solution of lead sulphate the metal is precipitated by sulphuretted hydrogen as lead sulphide. 1. -j-g-g- grain of lead oxide, or its equivalent, in one grain of liquid, yields with a drop of dilute sulphuric acid a copious precipi- tate, which partly consists of crystalline needles. If the drop of reagent be allowed to flow slowly into the lead solution, the precipitate generally consists of a mass of crystalline needles, Plate Y., fig. 3. 2. Yxroir grain yields a good precipitate, consisting principally of needles and granules. 3. 5-^0-j}- grain : an immediate granular precipitate, and in a little time a quite fair deposit. 4. ru",V(nr grain : after a few moments a cloudiness appears, and in a little time there is a very satisfactory granular deposit. 5. 2U.W(r grain yields after a few moments a slight cloudiness, and after a little time a satisfactory granular precipitate. If potassium sulphate be employed as the reagent, it produces the same results as the above. Free sulphuric acid, as well as soluble sulphates, also produces white precipitates in solutions of barium and strontium salts. The lead sulphate, however, is distinguished from that of either of these metals, in that when moistened with ammonium sulphide it is turned black, due to the formation of lead sulphide. When lead sulphate is intimately mixed with sodium carbonate and heated before the blow-pipe flame, on a charcoal support, it yields globules of metallic lead, 3. Hydrochloric Acid. Hydrochloric acid and its soluble salts occasion in somewhat strong solutions of lead salts a white precipitate of lead chloride, 374 LEAD. PbCl2, which is less soluble in diluted hydrochloric and nitric acids than in pure water. When excess of lead chloride is digested, at the ordinary temperature, with pure water for forty-eight hours, one part of the salt dissolves in 110 parts of the liquid : it is much more soluble in hot water. It is readily soluble in concentrated hydro- chloric acid. Chloride of lead bears a strong heat without decom- position ; but at higher temperatures, with a free supply of air, it is partially decomposed, with the evolution of chlorine, and leaves a residue consisting of a mixture of oxide and chloride of lead. 1. yl-Q- grain of lead oxide, in one grain of water, yields, with free hydrochloric acid, a copious, white crystalline precipitate, Plate v., fig. 4. 2. -g-^ grain : in a very little time a very fair deposit of granules and crystalline needles. 3. YWo^ grain yields after some minutes a quite satisfactory deposit of granules, needles, and prisms. The results under 2 and 3 are obtained only when excess of hydrochloric acid is employed. This reagent, as well as soluble chlorides, also produces white precipitates in solutions of silver and of mercurous salts. The chlorides of silver and mercury, however, are always thrown down in the amorphous form. The precipitated lead chloride is insolu- ble, and unchanged in color, by caustic ammonia ; whereas the silver precipitate is readily soluble in that alkali, whilst the mercury com- pound is turned black. The action of ammonia, therefore, readily serves to distinguish between the chlorides of these three metals. Moreover, the lead chloride is readily soluble, especially by the aid of heat, in large excess of water, whereas, on the other hand, the silver chloride and mercurous chloride are wholly insoluble in this liquid. 4. Potassium Iodide. This reagent produces in solutions of salts of lead a bright yellow precipitate of lead iodide, Pblg, which is readily soluble to a clear solution in potassium hydrate, but almost wholly insoluble even in very large excess of the precipitant; under the action of ammo- nia it slowly assumes a white color. It dissolves to a clear solution in strong hydrochloric acid ; nitric acid dissolves it to lead nitrate. Heated before the blow-pipe, on charcoal, it turns reddish-yellow, then becomes brownish, and finally volatilizes. POTASSIUM CH ROM ATE TEST. 375 Todido of lead is hut sparingly soluble in cold water, but at the boilini;- torn pcnit lire it dissolves more freely, and separates, as tlie liquid cools, in beautiful, six-sided laiuinfe. We have found that when excess of the well-washed salt is digested in pure water, with frequent agitation for twenty-four hours, at a temperature ranging from 15° to 21° C. (G0° to 70° F.), one part dissolves in 1528 parts of the fluid. It is, however, much less soluble in a dilute solution of potassium iodide. This reagent, therefore, produces a copious precipitate from a pure saturated aqueous solution of lead iodide ; even in the preseuce of slight excess of the reagent a precipitate will form when the lead iodide does not form more than the 1-1 0,000th part by weight of the solution. The precipitate from a 1-lOOOth solution of lead oxide does not usually entirely dissolve by heating the mixture to the boiling temperature. 1. y-J-jj grain of lead oxide yields a copious, bright yellow precipitate, which is usually partly granular and crystalline. 2. YU^ grain yields a very good deposit. 3. 2tW gr^in yields a quite good precipitate, which readily dissolves by heating tlie mixture to the boiling temperature, and again separates, as the liquid cools, in brilliant, golden-yellow, six- sided plates, Plate V., fig. 5. 4. 5-0V0 grain : a very fair deposit. 5. YcT.ToTr grain yields an immediate yellow precipitate, which soon becomes a fair deposit. 6. Y^.uim grain yields, with a very small quantity of the reagent, after a little time, a quite satisfactory deposit of granules and small plates. The production, by this reagent, of a yellow precipitate, which is soluble in boiling water, and separates as the mixture cools, in the form of six-sided plates, is characteristic of lead. 5. Potassium Chr ornate. Potassium chromate and the dichromate throw down from so- lutions of salts of lead a bright yellow, amorphous precipitate of lead chromate, PbCiO^, which is insoluble in acetic acid, and only sparingly soluble in diluted nitric acid, but readily soluble in potas- sium hydrate. Hydrochloric acid slowly changes it to white lead chloride; it is blackened by ammonium sulphide. 1. j^ grain of lead oxide yields a copious precipitate. 376 LEAD. 2. YWoT g'^aiii • ^ very good deposit. 3. Yo'.'UTo' g'^^iii yields a quite good, greenish-yellow precipitate. 4. -^^.-g-oo- grain yields an immediate cloudiness, and in a few minutes a very satisfactory greenish deposit. 5. YWohro gi"ain yields after a little time a greenish turbidity. The formation of the deposit from dilute solutions is facilitated by heating the mixture. Potassium chromate produces in dilute neutral solutions of salts of copper a yellowish precipitate, which after a time assumes a reddish-brown color, and which, unlike the lead chromate, is readily soluble in acetic acid. The precipitate from somewhat strong solu- tions of copper has at once a reddish-brown color. Potassium di- chromate produces no precipitate from even concentrated solutions of salts of copper. 6. Potassium Hydrate and Ammonia. The caustic alkalies produce in solutions of salts of lead a white precipitate, consisting chiefly of the hydrated oxide of lead, which is readily soluble in large excess of the fixed alkalies, insoluble in am- monia, and but sparingly soluble in ammonium nitrate. The precipi- tate is readily soluble in nitric acid, and is changed to lead chloride by hydrochloric acid. Upon the addition of sulphuretted hydrogen or ammonium sulphide, the precipitate is changed to black sulphide of lead. From solutions of acetate of lead ammonia causes only a partial precipitate, due to the formation of triplumbic acetate (tribasic acetate of lead), 2PbO ; Pb2C2H302, which remains in solution. 1. y-J-g- grain of lead oxide yields with either of the fixed alkalies a copious, white, amorphous deposit. 2. Y^^ grain : a very good precipitate, which is readily soluble in excess of the precipitant. 3. xo.Too" grain yields with a very small quantity of the reagent a very satisfactory deposit. These reagents also produce white precipitates with solutions of several other metals, which in some instances, as with bismuth and tin, are, like the lead deposit, blackened by ammonium sulphide. When, however, the dried lead precipitate is heated on charcoal before the reducing flame of the blow-pipe, it leaves malleable metallic globules, which are characteristic of this metal. REACTIONS WITH REAGENTS. 377 7. Alkaline Carbonates. The allcaline carbonates occasion in solutions of salts of lead a white amorphous precipitate of lead carbonate, together witli more or less hydrated oxide of the metal. The precipitate is almost wholly insoluble in excess of the precipitant, but readily soluble in nitric and acetic acids, and is changed to lead chloride by hydro- chloric acid ; it is also readily soluble in large excess of the fixed caustic alkalies. 1. Yffy- grain of lead oxide, in one grain of water, yields a copious precipitate. 2. YoVu" gi'ai^ • a very good deposit. 3. -j-jj.^-g-jj grain : a very satisfactory precipitate. 4. ■Bu-.-g-g-jr grain yields within a few minutes a quite distinct cloudi- ness. These reagents also produce white precipitates in solutions of many other metals. But from all these precipitates the lead com- pound is readily distinguished by its behavior before the blow-pipe flame. 8. Ammonium Oxalate. This reagent produces in neutral solutions of salts of lead a white precipitate of lead oxalate, which soon becomes crystalline. The precipitate is readily soluble in nitric acid, but insoluble in acetic acid, and blackened by ammonium sulphide. 1. Y^ grain of lead oxide yields a copious precipitate, which soon changes to a mass of long crystalline needles. 2. YoVo" gr^^n yields a very good deposit, which soon changes to granules and groups of needles. 3. T-o-Voir grain yields an immediate cloudiness, and after a little time a quite distinct deposit. 4. -g-g^.^-ij-g- grain yields after some minutes a quite satisfactory tur- bidity. When lead oxalate is heated before the blow-pipe on a charcoal support, it yields globules of metallic lead. 9. Zinc Test. When a drop of a solution of acetate of lead is placed in a watch-glass, and a fragment of bright zinc added, the lead com- 378 LEAD. pound is slowly decomposed, with the deposition of metallic lead upon the zinc, in the form of a brush-like, crystalline deposit. If the lead solution be placed upon a piece of bright copper and the metal touched through the drop with a needle of zinc, the lead deposits partly on the zinc and partly on the copper, as a strongly adhering, gray deposit, over the space occupied by the drop. 1. YoT graiii of lead oxide, when placed in a watch-glass and treated as just stated, yields a quite large, brush-like deposit. 2. YoTo grain : the zinc immediately darkens, and in a little time receives a quite satisfactory deposit. A solution of tin yields with a fragment of zinc a brush-like deposit of metallic tin, which sometimes very closely resembles that produced under similar conditions by lead. Potassium Jerroeyanide produces in solutions of salts of lead a white amorphous precipitate of ferrocyanide of lead, PbaFeCyg, which is slowly soluble in large excess of nitric acid, and changed to lead chloride by hydrochloric acid. One grain of a 1-1 000th solution of lead oxide yields with this reagent a quite good precipi- tate; and the same quantity of a l-10,000th solution gives after a little time a quite satisfactory deposit. Potassium ferricyanide throws down from solutions of acetate of lead a dirty-yellow precipitate, which is soluble in nitric acid, decomposed by hydrochloric acid, and blackened by ammonium sul- phide. With one grain of a 1-1 000th solution of lead oxide the reagent produces a quite good amorphous deposit; one grain of a 1— 10,000th solution yields after a few minutes a quite satisfactory granular precipitate. Both these reagents produce some^vhat similar precipitates in solutions of several other metals. Sepaeatiox from Orgaxic Mixtures. Suspected Solutioivs. — Various kinds of animal and vegetable substances more or less decompose and precipitate acetate of lead when in solution ; but most of these precipitates are readily soluble in diluted nitric acid. When a mixture of this kind is presented for examination, it should be acidulated with nitric acid and heated for some time, then allowed to cool, the liquid filtered, and the solids upon the filter washed, the washings being collected with the SEPARATION FUoNf OIUiANK' NflXTIIHI-X. P>7^ orifriiml filtrato, and tlu; solids reservotl. TIk- filtrate, after coiux'n- tration it" ncocssarv, is tiion saturated willi siilpliiirctted liylaee for some time; any |)reeipitate tlms pioduced is colieeted on a small filter, washed, and, while still moist, washed from the filter into a test-tnhe or any convenient vessel, by means of a jet of water from a wash-bottle. When the j)recii)itate lias completely subsided, most of the super- natant fluid is decanted, and the solid residue dissolved, by the aid of a gentle heat, in the least possible quantity of nitric acid, added drop by drop. By this means any lead sulphide present will be converted into lead nitrate, while the sulphur set free will remain unoxidized. The mixture is now diluted somewhat with pure water, the liquid filtered, and a portion of the filtrate tested with a solu- tion of potassium chromate. Other portions of the filtrate may be examined by any of the other tests already pointed out. The sulphide of lead precipitated from the 1-lOOOth of a grain of lead oxide, when diffused in ten grains of water and heated with one drop of nitric acid, yields a clear solution, which gives with reagents about the same reactions as a 1-1 0,000th solution of lead oxide. If large excess of nitric acid has been used for dissolving the lead sulphide, the filtered liquid should be carefully neutralized by pure potassium hydrate before the application of any of the tests. It would rarely, if ever, happen with organic mixtures of this kind containing lead that the metal would entirely escape solution in diluted nitric acid. If, however, there has been a failure to detect the metal by the above method, the solids obtained by filtration from the original mixture may be boiled for some time with water containing about one-sixth of its volume of nitric acid, the solution filtered, the filtrate evaporated to dryness, and the residue inciner- ated. This residue is treated with a little nitric acid, the solution diluted with a small quantity of water, then filtered, and the filtrate neutralized and tested in the ordinary manner. Contents of the Stomach. — These, after the addition of water if necessary, may be acidulated with nitric acid, and examined in the manner just described for suspected solutions. If an alkali sulphate had been administered as an antidote, the poison may be in the form of insoluble lead sulphate. Under these circumstances, the contents of the stomach should be carefully exam- 380 LEAD. ined, and any white powder found collected and washed, then boiled with a strong solution of pure caustic potash, and the lead precipi- tated by sulphuretted hydrogen. Or, any lead sulphate obtained may be placed in a wide test-tube and agitated occasionally for sev- eral hours with a strong solution of acid sodium carbonate, the clear liquid decanted, and the operation repeated with a fresh portion of the sodium solution. By this means the lead sulphate will be con- verted into insoluble lead carbonate. This is washed, then dissolved in a little acetic acid or in very dilute nitric acid, and the solution tested. According to the observations of Orfila, in acute poisoning by the salts of lead, the villous coat of the stomach frequently presents numerous white points which contain lead, and which are blackened by sulphuretted hydrogen. From the Tissues. — The solid organ, such as a portion of the liver, is cut into small pieces and boiled in a porcelain dish with nitric acid, diluted with about four parts of water, until the mixture becomes homogeneous. AYhen the mixture has cooled, the liquid is filtered, the filtrate evaporated to dryness, the residue moistened with nitric acid, again evaporated to dryness, and the heat continued until all vapors cease to be evolved and the residue becomes a car- bonaceous mass. The mass thus obtained is pulverized and boiled with a small quantity of strong nitric acid, the mixture diluted with water, the solution filtered, the filtrate evaporated to dryness, and the residue dissolved in a small quantity of water slightly acidulated with nitric acid. This solution, after filtration if necessary, is satu- rated with sulphuretted hydrogen gas, and allowed to stand until the precipitate has completely subsided. Any lead sulphide thus deposited is collected on a small filter, washed, then suspended in a small quantity of water and dissolved, by the aid of heat, in the least possible quantity of nitric acid, and the solution tested in the usual manner. If the quantity of lead sulphide precipitated by the sulphuretted gas is too minute to be separated from the filter, the filter, or that portion of it containing the deposit, may be heated with sufficient dilute nitric acid to dissolve the precipitate ; the solution is then filtered, neutralized, and tested. From the observations of several experimentalists, it appears that absorbed lead is very slowly eliminated from the system. Orfila QUANTITATIVE ANALYSIS. 381 States {Toxicohgie, i. 858) that wlien dogs were given alwut oight grains of acetate of lead daily for one month, the metal was found in the liver and brain of the animals when killed ono hundred and four davs after thoy had ceased to take the poison. According to this observer, tiie metal is eliminated from the body principally with the urine. From the C/rmf?.— Fifteen or twenty ounces of the urine, acidu- lated with nitric acid, may be evaporated to dryness, the residue carbonized by nitric acid, and the carbonaceous mass treated in the manner just described for the separation of the metal from the tissues. By Ibllowing this method we detected the metal in notable quantity in the urine almost daily for about two weeks, in two instances of severe chronic lead poisoning resulting from the use of water col- lected in a leaden cistern. Of eight persons who used this water, only two were affected by it, and these the elder members of the family. Kletzinsky proposes, after rendering the urine alkaline by potas- sium hydrate, to add about two per cent, of its weight of potassium nitrate and evaporate to dryness. The residue is then exposed to a dull red heat, whereby the whole of the organic matter is destroyed. The cooled mass is powdered and boiled for some time with a half- saturated solution of neutral ammonium tartrate, to which some caustic ammonia has been added, the solution filtered, the filtrate acidulated with hydrochloric acid, and then precipitated by sulphu- retted hydrogen. The precipitate is allowed twenty-four hours to subside, then washed, redissolved in warm dilute nitric acid, and the solution filtered, neutralized, and tested in the usual manner. (Thudichum, On the Urine, 406.) Quantitative Analysis.— Lead may be very accurately esti- mated in the form of sulphide of the metal. The solution, very slightly acidulated with nitric acid, is treated with a slow stream of washed sulphuretted hydrogen gas as long as a precipitate is pro- duced, and the mixture then allowed to stand in a moderately warm place until the precipitate has completely deposited. The precipitate is collected on a filter of known weight, washed, thoroughly dried on a water-bath, and weighed. One hundred parts by weight of the dried sulphide correspond to 86.19 parts of metallic lead, or 93.33 of lead oxide, or 158.37 of pure crystallized acetate of lead. 382 COPPER. When the lead exists in the form of sulphate, this may be washed with water containing a little alcohol, dried at 100° C. (212° F.), and weighed. One hundred parts by weight of the dried sulphate cor- respond to one hundred and twenty-five parts of crystallized acetate of lead. Section II. — Copper. History and Chemical Nature. — Copper is represented by the sym- bol Cu; its atomic weight is 63.4, and its specific gravity 8.95. This metal is frequently found in its uncombined state in nature ; its most common ore is copper pyrites, which consists of a mixture of the sulphides of copper and iron. According to VValchner, copper is as widely distributed in nature as iron. In some mineral waters it is said to exist to the extent of half a grain to the gallon of water. It is also found in sea-water and in sea-weeds. Sarzeau states that he found it in minute quantity in various vegetable substances, such as coflTee, sugar, wheat, and flour ; and minute traces of it have been found in the blood and various organs of the healthy human body. In fourteen human bodies examined by Dr. G. Bergeron, the metal was found in the liver in each case, but in no instance did the amount exceed about one milligramme (l-65th grain) in the entire liver. [Jour, de Chim. Med., Nov. 1874, 503.) In the ash obtained from a million parts of grain and of flour. Dr. Van den Berghe found from eight to eleven parts of copper. (Chem. Zeit., March, 1882, 223.) Copper, in its uncombined state, is a rather hard, quite tough, ductile metal, of a peculiar red color, and a somewhat granular frac- ture ; its fusing point, according to Daniell, is about 1091° C. (2000° F.). When exposed to moist air, it slowly absorbs oxygen and car- bonic acid, with the formation of a green coating of hydrated oxy- carbonate of copper, CuOjCuCOgjHaO, known also as natural verdi- gris. Immersed in pure water, copper undergoes little or no change ; but in water containing common salt it slowly becomes covered with a layer of oxychloride of the metal. In water containing an organic acid, as vinegar, or when certain kinds of fatty matters are present, the metal is more readily acted upon. Nitric acid rapidly dissolves it, with the evolution of nitrogen dioxide and the formation of copper nitrate. Cold sulphuric acid has no direct action upon the metal ; but the hot acid readily dissolves it, with the evolution of sulphu- PHYSIOLOGICAL EFFECTS. 383 I'oiis oxide gas (SOj), to coj)j)er sulphate. Hydrochloric acid, even at the boiliniij toiu|)C'ratiire, lulls to act upon the metal. C'ombinationa, — C<)j)per readily unites with most of the n<»n- metallic elements. With oxygen it unites in two proportion.s, form- ing the monoxide (C'uO) and the suboxide (CuoO), the former of which has a black, and the latter a red, color. In its hydrated state the monoxide has a blue color; the color of the hydrated suboxide is yellow. The monoxide of copper readily unites with acids, form- ing salts known as the cupric salts, which in their hydrated state have either a blue or a green color, and several of which are freely soluble in water. The suboxide forms but few salts, and these are quite unstable. The most important compounds of copper, in regard to their medico-legal relations, are the sulphate and the subacetate, or verdigris. Sulphate of coppe)', or blue vitriol, in its crystallized state, has the composition CuS0j;,5Aq, its molecular weight being 249.4. In this state it forms large blue crystals, which have a nauseous metallic taste, and a density of 2.27. It is soluble in between two and three times its weight of water at the ordinary temperature, and in less than its own weight of boiling water : the solution has a blue color, and a distinctly acid reaction. At a temperature £»f about 204° C. (400° F.) the salt becomes anhydrous and crumbles to a nearly white powder ; at a strong red heat it undergoes decomposition, evolving free oxygen and sulphurous oxide, and leaving a residue of copper monoxide. Verdigris, as found in the shops, is a mixture in variable propor- tions of the lower acetates of copper, having either a blue or a green color, and a disagreeable acetous odor. It is usually met with in the form of hard, irregular masses, but sometimes as a fine powder. Under the action of water verdigris is only partly dissolved, a green- ish residue of tribasic oxyacetate of copper (2CuO ; CU2C0II3O2) being left. It is completely soluble in water containing a little free hvdro- chloric or nitric acid. Sulphuric acid readily decomposes it, with the formation of copper sulphate and the elimination of acetic acid. Physiological Effects. — When swallowed in its metallic state, copper seems to be entirely inert, at least so long as it retains its metallic form ; should, however, the metal become oxidized within the alimentary canal, it may give rise to severe symptoms. In a case quoted by Dr. Beck, in w^iich six copper penny-pieces were swallowed 384 COPPER. and retained in the body for five years^ no inconvenience was expe- rienced except the eifects of mechanical obstruction. On the other hand, a case is related by Dr. Jackson, of Boston, in which a copper half-cent gwallowed by a child produced nausea and vomiting, with other symptoms of copper poisoning. The compounds of copper, when taken in large doses or in fre- quently repeated small doses, are all more or less poisonous. Even some of the compounds that are insoluble in water are capable of pro- ducing very active effects. The preparations of this metal have been rarely administered for criminal purposes; but numerous instances are recorded of accidental poisoning by some of them, resulting from the use of food prepared in copper vessels. Symptoms. — The usual effects produced by the preparations of copper when swallowed in poisonous quantity are a coppery taste in the mouth, nausea, a sense of burning heat in the mouth and throat, eructations, severe headache, violent vomiting, with more or less purging, and acute pain throughout the stomach and bowels. The pulse becomes small, frequent, and irregular ; and there may be great dizziness, difficulty of breathing, great anxiety, cold sweats, extreme thirst, cramps in the extremities, scantiness or entire suppression of urine, and death is sometimes preceded by convulsions and insensi- bility. Among the symptoms occasionally present is jaundice. Dr. Maschka observed this symptom in a case in which death ensued on the third day, and he attributes it to fatty degeneration of the liver, as in arsenic and phosphorus poisoning. When taken in frequently repeated small doses, the preparations of copper produce much the same symptoms as those just described. There is loss of appetite ; a coppery taste in the mouth ; nausea, with frequent efforts to vomit ; violent headache ; irregular and frequent . pulse ; hot skin ; impaired respiration ; great thirst ; extreme debility ; sharp, shooting pains in the stomach, with tension and tenderness of the abdomen ; frequent purging, the discharges being usually dark- colored and their passage attended with pain ; and there is more or less alteration of the color of the skin. A not unfrequent cause of slow poisoning by copper, as already intimated, is the use of utensils of the metal for the preparation of food. The risk of contamination in these cases is always much in- creased by the free action of the atmosphere, and by allowing the food to cool and remain in contact with the vessel. By employing bright PERIOD WHK.N FATA I.. 385 Vessels, and rcmovinjj; the food as soon as prepared, there is little danjjer in tlie use of the metal for such purposes. An instance is related in which ten persons partook of sou|) pre- pared in a copper vessel that had not been properly cleaned. They all speedily sullbrcd most violent symptoms, and five of the j)ersons died IVom its ciVects within several hours after the souj) had been taken. {Jour, de Cliim. Mhl, July, 1870, 334.) Period ichcn Fatal. — The time at which death has taken j)lnce, in acute poisoning by copper, has been subject to considerable variation. In the case of a young lady, mentioned by Dr. Percival, death oc- curred on the ninth day. In this case tiie poisoning resulted from the eating of pickles contaminated with copper. The symptoms were sharp pains in the stomach, an eruption over the breast, general shooting pains, thirst, a small, frequent pulse, vomiting, iiiccough, and purging : there were neither convulsions nor stupor. In a case related by Pyl, two ounces of verdigris proved fatal in three days to a woman. In another instance, quoted by Dr. Christison, a lady and her daughter were poisoned by sour-krout which had been kept in a copper vessel. They were soon seized with pain in the stomach, then nausea and vomiting, followed by purging, convulsions, and in- sensibility. The daughter died in twelve hours, and the mother an hour later. [On Poisons, 362.) A child, aged sixteen months, swal- lowed an unknown quantity of solid sulphate of copper, and died from its effects four hours afterward. This is perhaps the most rapidly fatal case yet recorded. Fatal Quantity. — In a case quoted by Dr. Beck, one ounce of sulphate of copper, taken with suicidal intent by a man aged forty years, proved fatal within twelve hours. {Med. Jur., ii. 667.) In another instance, seven drachms of the same salt, with three drachms of sulphate of iron, caused the death of an adult in three days. Dr. Percival states that the most violent convulsions he ever wit- nessed were produced in a young woman by two drachms of blue vitriol : under appropriate treatment she recovered. In a case cited by Dr. Taylor, half an ounce of verdigris destroyed the life of a woman in sixty hours; and in another, about twenty grains of the subchloride of copper caused the death of a child. {On Poisons, 524.) On the other hand, Dr. Vergely reports a case {Jour, de Chim. Med., April, 1873, 152) in which a w'oman, aged thirty-two years, 26 386 cx)PPER. drank a solution of fifteen grammes (about two hundred and thirty- two grains) of copper sulphate, and speedily experienced violent symptoms of copper poisoning; but under active treatment she entirely recovered within a few days. And in a case quoted by Dr. A. Stills {3fat. Med., i. 325), in which an ounce of blue vitriol had been swallowed with suicidal intent, complete recovery took place, although the patient refused to take an emetic. Treatment. — In acute poisoning by any of the preparations of copper, the vomiting should be encouraged by the free administration of demulcent liquids ; or the stomach may be emptied by means of the stomach-pump. As a chemical antidote, albumen in large excess was strongly advised by Orfila. The white of egg should be freely given, and its exhibition followed by large draughts of tepid water. An excess of albumen readily decomposes the soluble salts of copper, with the formation of albuminate of copper, which is said to be but sparingly soluble in the juices of the stomach. According to the experiments of Dr. Schrader, of Gottingen, milk is equally efficient witli albumen as an antidote. The case- ate of copper thus produced should be speedily removed from the stomach by vomiting. [Amer. Jour. Med. Sci., Oct. 1855, 540.) M. Duval strongly advised the use of sugar ; but it is very ques- tionable whether this substance can be regarded as an antidote : it might, however, be administered in connection with albumen or milk. Among the other substances that have been proposed as anti- dotes may be mentioned potassium ferrocyauide, iron filings, calcined magnesia, and hydrated sulphide of iron. The employment of the alkaline sulphides, and also of vinegar, would be inadmissible. Post-mortem Appeaeaxces. — The morbid appearances in poi- soning by the preparations of copper are usually confined to the alimentary canal. In acute cases, the inside of the stomach and of the intestines not unfrequently presents a bluish or greenish appear- ance, due to the presence of the poisonous compound. It should be remembered, however, as first pointed out by Orfila, that a some- what similar appearance may result from the presence of altered bile. The lining membrane of the stomach is usually inflamed and softened ; and in some few instances it presented an ulcerated, and even gangrenous, appearance. Similar aj)pearances have been found in the intestines ; in some few cases the intestines were found per- CHEMICAL PROPERTIES. 387 forated, ami (ln'ir contents had partially escaped into the cavity of the abdomen. In the fatal case cited by l^r. Bc(!k, the itant, forming a greenish liquid, from which, by continued boiling, the whole of the chromium is reprecipitated as green, hydrated sesquioxide of the metal. These are the only two metals which yield with these reagents precipitates the color of which might be confounded with that of the copper precipitate. Potassium and sodium carbonate occasion in aqueous solutions of cupreous salts a greenish-blue, amorphous precipitate of hydrated oxycarbouate of copper, CuO,CuC03,H20, which is sparingly solu- ble, to a bluish liquid, in excess of the precipitant. If an excess of the reagent be added and the mixture boiled, the precipitate 392 COPPER. becomes converted into black anhydrous cupric oxide. The b'mit of the reaction of these reagents is the same as that of the fixed; caustic alkalies. 4. Potassium Feri^ocyanide. This reagent throws down from somewhat strong solutions of salts of copper a reddish-brown, amorphous precipitate of ferro- cyanide of copper^ CugFeCyg, which is insoluble in excess of the precipitant, and in acetic and hydrochloric acids, but sparingly soluble in ammonia to a bluish-green liquid, from which it is re- precipitated by excess of acetic acid. From more dilute solutions the reagent produces a purple precipitate; while from still more dilute solutions it fails to produce a precipitate, but the mixture assumes a reddish color. 1. Y^ grain of copper oxide yields a copious, reddish-brown, gelat- inous precipitate. 2. xoVq- grain : an immediate purple precipitate, which soon becomes a quite good, reddish-brown deposit. 3. x¥,'on' grain : a reddish, flocciilent turbidity. 4. -js-.TDT grain yields a slight cloudiness; when viewed over white paper, the mixture exhibits a distinct reddish color. When jive grains of a 1-1 00,000th solution are treated with a small quantity of the reagent, the mixture presents a quite distinct reddish color. This color is readily observed even in more dilute solutions, when larger quantities are examined. Potassium ferrocyanide also produces in solutions of uranic salts a precipitate very similar in color to that of the ferrocyanide of copper. But the uranium precipitate is changed to a yellow com- pound upon the addition of excess of ammonia ; whereas, as before stated, the copper ferrocyanide is soluble to a limited extent in ex- cess of this alkali, yielding a bluish-green liquid. Moreover, solu- tions of copper are readily distinguished from those of uranium by their behavior with sulphuretted hydrogen and ammonia, as already pointed out. Copper and uranium are the only metals that yield reddish-brown precipitates with potassium ferrocyanide. The reaction of this reagent with solutions of salts of copper is much modified by the presence of even minute quantities of iron, with which it produces a blue precipitate. IRON TEST. ;i93 6. Iron Test. When a piece of bright iron or steel is immersed in a solution of a salt of copper, it sooner or later decomposes the salt and receives a conting of metallic copper, having tlu? characteristic color of the metal ; at the same time, a salt of iron, containing the acid previously combined with the copper, is formed. This reaction, especially from dilute solutions, is mucli facilitatcil by the presence of a little free sul])huric or hydrochloric acid. In examining the limit of this test, a single grain of the copper solution, placed in a watch-glass, was acidulated with sulphuric acid, and a small portion of a bright sewing-needle introduced into the mixture; in the very dilute solutions the length of the needle did not exceed -^ of an inch. It is obvious that the thickness of the deposit from a given quantity of copper, and consequently the deli- cacy of the test, will depend very much upon the extent of surface over which the metal is distributed. 1. Yuir grain of copper oxide yields a very fine coating. 2. YUou grain : in a little time the needle acquires a very satisfactory deposit. 3. xTj.-l-oiT grain : in a few minutes the needle presents a reddish tint, and in fifteen minutes receives a satisfactory coating. 4. ^ovoiTd grain : after several minutes the neeille exhibits a just j)er- ceptible reddish hue, which improves, and after an hour becomes perfectly satisfactory. By allowing the needle to remain in the acidulated liquid for several hours, satisfactory deposits may be obtained from solutions much more dilute than the last-mentioned. The true color of very thin deposits is best determined by the aid of a hand-lens. It need hardly be remarked that this reaction is peculiar to copper. The cupreous nature of the deposit may be shown by dis- solving out the iron from the coated needle with diluted sulphuric acid, and then dissolving the washed coating in a little nitric acid, evaporating the solution to dryness, redissolving the residue in a few drops of water, and testing the liquid with potassium ferrocyanide. 6. Platinum arid Zinc Test. When a solution of a salt of copper is acidulated with hydro- chloric or sulphuric acid, and placed in a platinum dish, and then a 394 COPPER. fragment of bright zinc placed in the liquid, the cupreous compound quickly undergoes decomposition, with the deposition of a coating of metallic copper, of its peculiar color, upon the platinum covered by the liquid. 1. YF¥ grain of copper oxide in one grain of fluid, when treated after this method, yields a very fine deposit. 2. YoVo" E^^^^ • after a few minutes the platinum exhibits a very satisfactory coating. 3. gQ^QQ grain : after several minutes there is a quite distinct deposit. This method will not serve for the detection of as minute quan- tities of copper as the iron test, since in its application the metal is distributed over a larger surface than when the iron-method is em- ployed. If the washed deposit be moistened with a few drops of caustic ammonia, the liquid slowly acquires a blue color, due to the formation of a soluble compound of the metal. 7. Potassium Ar senile. This reagent throws down from neutral solutions of salts of copper, when not too dilute, a bright green precipitate of cupric arsenite, CuHAsOg, known also as Scheele's green. This precipitate is readily soluble in ammonia and in free acids. 1. Yw gi^ain of copper oxide, in one grain of water, yields a copious precipitate. 2. YcToo" grain : a quite good, yellowish-green deposit. 3. YF.Wo gi'a-hi : after a little time the mixture becomes decidedly turbid ; but the green color is not perceptible. With larger quantities of the solution the reagent produces satisfactory results, even in much more dilute solutions. The production of a bright green precipitate by this reagent is quite characteristic of copper. However, solutions of salts of nickel yield with the reagent a pale green deposit, which, like the copper precipitate, is readily soluble in ammonia and in acetic acid. 8. Potassium Chr ornate. Monochromate of potassium, when added in excess to somewhat strong solutions of salts of copper, produces a reddish-brown pre- cipitate of cupric chromate, which is readily soluble in ammonia, forming a beautiful green liquid ; the precipitate is also soluble in acetic acid, and in excess of the copper solution. From more dilute POTASSIUM lODIDK TEST. 396 solutions the roagciit throws down a yoUow or greenish-yellow laced on the tongue of a cat. In ten seconds the animal fell on the right side perfectly prostrated, then had con- vulsive movements of the legs, voided urine, and died in two min- utes and a half, (c) A third cat, to which a similar quantity had been administered, fell in about twelve seconds, had violent convul- sions of the extremities, and was dead in seventy-Jive seconds after taking the poison. Period when Fated. — In fatal poisoning by tobacco, death does not usually occur until after some hours, but it may take place within a very much shorter period. In a case in which about an ounce of crude tobacco had been swallowed, death took place in about seven hours ; while in another, an unknown quantity of snuff administered in whiskey proved fatal in about one hour. 438 NICOTINE. Most of the reported cases of death from tobacco have been occasioned by its use in the form of clyster. M. Tavignot relates a case in which an injection prepared by mistake with nearly two ounces of tobacco (sixty grammes), instead of nine grains and a quarter (sixty centigrammes), was administered to a stout man, aged fifty-five years. In seven or eight minutes afterward he was seized with stupor, headache, paleness of the face, pain in the abdomen, indistinct articulation, and convulsive tremors, at first of the arms, then of the whole body. These symptoms were soon followed by extreme prostration and slow laborious breathing, and then coma, which terminated fatally in about eighteen minutes after the injection had been administered. {Gazette Med. de Paris, Nov. 1840, 763.) In a case quoted by Dr. Beck {Med. Jur., ii. 878), a female affected with worms used an enema of tobacco, and was soon seized with violent convulsions, and died from its effects fifteen minutes after- ward. Fatal Quantity. — In most of the fatal cases of poisoning from the swallowing of tobacco, the quantity taken could not be accurately determined. In a case reported by Mr. Skae, a man who had swal- lowed a large mouthful of crude tobacco became suddenly insensible, motionless, and relaxed, with contracted pupils, and a scarcely per- ceptible pulse. These symptoms were followed by convulsions, loud cries, dilated pupils, active vomiting and purging, and death by syncope. {8tille's Mat. Med., ii. 298.) Administered in the form of enema, tobacco has proved fatal in comparatively small quantity. Thus, several instances are re- ported in which a decoction of a drachm exhibited in this manner caused death. In one of these, quoted by Dr. Christison, death took place in thirty-five minutes. In a case cited by Dr. Pereira {Mat. Med., ii. 494), an injection containing only half a drachm was followed by fatal results. Treatment. — This consists in the speedy removal of the poison, in case it has been swallowed, from the stomach; and the subse- quent exhibition of stimulants. Animal charcoal, tannic acid, and an aqueous solution of iodine in potassium iodide have been advised as chemical antidotes. Opium may sometimes be found useful to allay the excessive vomiting. Post-mortem Appearances. — These are subject to great varia- tion. In a case quoted by Dr. Taylor {On Poisons, 747), in which GENERAL CHEMICAL NATURE. 439 something less tlian an ounce of" crude tobacco had been swallowed and death occurred in about seven hours, the following appearances were observed forty Jiours after death. The sul)stance of the brain and the upper part of the sjiiiiai marrow were somewhat congested ; the heart was empty, small, and contracted ; and the liver and kid- neys were much congested. The mucous membrane of the stomach presented several red patches. The intestines were contracted through- out, and contained only a mucous fluid tinged with blood ; the mucous membrane was of a red color, partially abraded, and full. The bladder was contracted and empty. The blood throughout the body was dark-colored and liquid. In a case in which an enema prepared with about an ounce of tobacco proved fatal in three-quarters of an hour, the only abnormal appearances observed two days after death were a gorged condition and redness of the inner and outer coats of the large and small intes- tines, and patches of extravasation in some parts of the mucous membrane, together with an empty state of the heart and of the blood-vessels of the abdomen. The stomach and brain were natural. CHEMiCAii Properties. General Chemical Nature. — Nicotine, when perfectly pure, is a transparent, colorless, oily liquid, having a strong alkaline reac- tion, and a density of about 1.048. Its odor is usually described as acrid, unpleasant, and resembling somewhat that of tobacco : this is true of most samples as met with in the shops, but when perfectly pure it has, as remarked by Otto, a rather pleasant ethereal odor. The odor may be perceived, but is not characteristic, in a few drops of a pure l-50,000th aqueous solution of the alkaloid. Nicotine has a pungent, acrid taste, even when highly diluted, producing a peculiar sensation in the throat and air-passages. It slowly distils at about 146° C. (295° F.), and boils at about 243.5° C. (470° F.), recondensing for the most part unchanged ; in an atmos- phere of hydrogen gas it may be distilled without any decomposition. It imparts a transient greasy stain to white paper, and burns with a white, smoky flarae. On exposure to the air, nicotine slowly be- comes yellow, then brownish and thick, being finally converted into a resinous mass. Solubility. — Nicotine is freely soluble in all proportions in water ; it is also soluble in alcohol, ether, chloroform, the fixed oils, and in 440 NICOTINE. oil of turpentine. By the use of some of these latter solvents the alkaloid may be extracted to a greater or less extent from its solu- tion in water. For this purpose ether has usually been employed^ but this liquid is inferior in this respect to chloroform, as may be seen from the following experiments. 1. Extraction by Ether. — When one volume of a 1-lOOth aqueous solution of nicotine is agitated with jive volumes of absolute ether ^ and the latter liquid, after repose, decanted, the aqueous solution yields with reagents somewhat better reactions of the presence of nicotine than a pure l-500th solution of the alkaloid ; thus showing that the ether extracted less than four-fifths of the vegetable base. When a 1-lOOth solution is agitated with twenty-five volumes of ether, the aqueous liquid is reduced to about a l-1200th solution. Experiments made with aqueous solutions of the hydrochloride of nicotine, by decomposing the salt with potassium hydrate and then extracting with absolute ether, gave results similar to those just mentioned ; as did also experiments in which concentrated com- mercial ether was employed as the extracting liquid. ' 2. By Chloroform. — When a 1-1 00th aqueous solution of pure nicotine is agitated with five volumes of pure chloroform, and the latter carefully decanted, the former liquid is reduced to about a l-4000th solution of the alkaloid. So, also, under like circum- stances, a 1-lOOOth aqueous solution is reduced to about a l-40,000th solution. These experiments show that under these conditions chlo- roform separates about 39-40ths of the alkaloid. Special Chemical Properties. — If a drop of nicotine be placed in a watch-glass, and this covered by a similar, inverted glass containing a small drop of either hydrochloric or nitric acid, the glasses become filled with white fumes. These fumes are not so dense as those obtained from conine under similar circumstances ; nor are they, as in the case of conine, attended with the formation of crystals. When the pure alkaloid is treated directly with concen- trated hydrochloric acid, it yields a syrupy liquid, without the forma- tion of crystals; with nitric acid it yields a reddish syrupy fluid. When the alkaloid is touched with concentrated sulphuric acid, it undergoes little or no change until the mixture is heated, when it acquires a brownish color. It need hardly be added that these reactions in themselves are not characteristic of this alkaloid. A pure aqueous solution of nicotine is colorless, has the peculiar PI.ATINIC CHLOIUDK TKST. Ill odor and taste t)t' tlic alkaloid, and an alkaline reaction, Wli(;n snch a solution is distilled, the alkaloid passes over with the vapor of water. Nicotine readily unites with acids, forming salts, some of which are readily crystallizable. The salts of nicotine have the peculiar taste of -the alkaloid, hut are destitute of odor. They arc mostly soluble in water and in alco- hol, but insoluble in ether. Their aqueous solutions lose part of the alkaloid upon evaporation, and are decomposed by the mineral alka- lies, evolving the odor of nicotine. When such an alkaline mixture is agitated with chloroform, this liquid, after decantation and evapo- ration, leaves the extracted alkaloid in the form of oily drops or streaks. On distilling a solution of a salt of nicotine which has been treated with excess of potassium or sodium hydrate, the free alkaloid will be found in the distillate, together with any ammonia that may have been present in the mixture. If the distillate thus obtained be neutralized with oxalic acid, then gently evaporated to dryness, and the residue treated with alcohol, this liquid will dissolve the oxalate of nicotine produced by the neutralization, while any ammo- nium oxalate present will remain, it being insoluble in this men- struum. On now evaporating the alcoholic solution to dryness, the oxalate of nicotine may be obtained in its pure state. In the following examinations of the limit of different tests for nicotine when in solution, the pure, colorless alkaloid was dissolved in distilled water. The fractions indicate the fractional part of a grain of the alkaloid in solution in one grain of water. The results, except when otherwise stated, refer to the behavior of one grain of the solution. 1. Platinic Chloride. This reagent throws down from somewhat strong aqueous solu- tions of nicotine and of its salts a yellow precipitate of the double chloride of platinum and nicotine, having, according to Ortigosa, the composition CioHi^N2,2HCl; PtCl^. The precipitate produced from aqueous solutions of the free alkaloid by the pure reagent is at first amorphous, but after a little time it becomes, in part at least, crystal- line. But when from solutions of the hydrochloride of nicotine, or if the reagent contains free hydrochloric acid, the precipitate immedi- ately assumes the crystalline form. From more dilute solutions of the alkaloid or of its salts the precipitate separates only after a time, and then in the crystalline state; its separation is much facilitated 442 . NICOTINE. by stirring the mixture. The precipitate, in its crystalline form, dis- solves but slowly in large excess of hydrochloric acid ; in its amor- phous condition, however, it is much more readily soluble. It is insoluble in acetic acid, in alcohol, and in ether, but soluble in excess of free nicotine. The crystals are permanent in the air. 1. y^ grain of nicotine, in one grain of water, yields with the re- agent a quite good deposit of orange-yellow crystals, Plate VI., 2. -^^ grain : after a little time the mixture becomes turbid, and ultimately yields small crystals of the double salt. If the mix- ture be stirred with a glass rod, it very soon yields granular streaks on the dish or glass-slide over the path of the rod, and in a little time a quite satisfactory crystalline deposit. Platinic chloride also produces yellow crystalline precipitates in solutions of potassium hydrate and of ammonia ; but the forms of the crystals thus produced are wholly different from those of the double nicotine salt. (Compare Plate I., fig. 1.) The application of some of the tests, such as the iodine reagent, which produce precipi- tates with nicotine but none with the inorganic alkalies, would also readily distinguish the former from the latter. If the solution under examination has been prepared by extraction from a suspected mix- ture by chloroform or ether, then a mineral alkali could not be present, since they are insoluble in these liquids. This reagent also throws down yellow precipitates from solutions of most of the other alkaloids, some of which, like the nicotine deposit, are crystalline ; but in no instance have the crystals the same microscopic forms as those obtained from somewhat strong solutions of nicotine. The production of this crystalline precipitate, together with the odor and physical state of nicotine, readily serves to distinguish this alkaloid from all other substances. 2. Mercuric Chloride. Mercuric chloride, or corrosive sublimate, produces in strong solutions of nicotine a copious, white, curdy precipitate, which soon acquires a yellow color and deposits beautiful groups of colorless crystals, which are permanent in the air. The precipitate produced from somewhat dilute solutions of the alkaloid remains white, and after a time yields the same crystals as from strong solutions. These precipitates are readily soluble in hydrochloric and acetic acids. The MERCURIC CHLORIDE TEST. 443 white precipitate is soluble in ammonium chloride, from which, after a time, it is redej)ositc(l ; the yellow precipitate is immediately de- colorized by ammonium chloride and, in part at least, dissolved, but after a time it separates in the form of a white powder. The pre- cipitates are to a greater or less extent dissolved upon the application of heat, but again rejiroduced as the solution cools. 1. y^J-jj grain of nicotine, in one grain of water, yields a copious, white precipitate, which in a little time becomes yellow and yields a mass of large groups of crystals, Plate VI., fig. 2. These crystals are especially beautiful under polarized light. 2. 3^ grain yields a rather copious, dirty-white precipitate, which soon deposits colorless crystals. 3. Y^jVij" grain J in a few seconds the mixture becomes turbid, and soon there is a quite good, white, flocculent precipitate, which after a time yields crystals having the same forms as illustrated above. If upon the addition of the reagent the mixture be stirred with a glass rod, it immediately yields streaks on the bottom of the watch-glass over the path of the rod, and soon in- numerable opaque granules and granular masses appear, which after a little time present the appearances illustrated in the lower portion of the above figure. 4. YT^i) gi'aiii : if the mixture be stirred and allowed to stand, it yields after some time quite a number of large crystalline groups. Although corrosive sublimate also produces white precipitates with ammonia and various inorganic substances, as well as with most of the alkaloids and many other kinds of organic matter, yet all these deposits, unlike that from nicotine, remain amorphous, except the precipitate from strychnine, and in this case the crystals, which are usually obtained with difficulty, are always of a wholly different form from those produced by the nicotine deposit. (Compare Plate XI., fig. 2.) It may be added thd,t the nicotine precipitate is very readily soluble in excess of acetic acid, whereas the strychnine com- pound is soluble with difficulty in this acid. We have found, in repeated experiments, that the precipitate produced by this reagent from quite impure solutions of nicotine will after a time yield characteristic crystals, even in the midst of a dense deposit of foreign matter. Nevertheless, it must be borne in mind that under these circumstances the precipitate may fail to crystallize. In applying this test to somewhat complex organic 444 NICOTINE. liquids, the precipitate should be stirred and allowed to stand for at least an hour, with the occasional addition of very small quantities of pure water to prevent the deposit becoming dry, before it is fully concluded that crystals will not form. This is the most valuable test yet known for the detection of nicotine when in solution. 3. Picric Acid. An alcoholic solution of picric, or carbazotic, acid, throws down from aqueous solutions of nicotine a yellow, amorphous precipitate, which soon becomes a mass of crystalline tufts. It is necessary to use large excess of the reagent, otherwise either no deposit will form, or if produced it will soon disappear. 1. YFo" grain of nicotine yields an immediate yellow or greenish- yellow precipitate, which soon becomes a mass of groups of yellow, crystalline tufts, Plate YI., fig. 3. 2. iQQQ grain : a rather copious precipitate, which soon crystal- lizes. 3. xo.Wo grain yields a very good crystalline precipitate. 4. 4^,Vfo gi'ain yields a just perceptible precipitate. This reagent also throws down from sohitions of the inorganic alkalies, and of several of the other alkaloids, besides nicotine, yel- low precipitates which become crystalline. But by the aid of the microscope the crystallized nicotine compound may generally be readily distinguished from all of these deposits except that produced from very strong solutions of sodium hydrate (Plate I., fig. 6), which 'has frequently much the same crystalline form as that assumed by the nicotine salt. Any doubt as to the true nature of the deposit may, of course, be readily removed by the application of other reagents. This reagent will often produce crystals with only the l-10,000th of a grain of nicotine, in one grain of water, in the presence of for- eign organic matter. But in mixtures of this kind the formation of crystals is more readily interfered with than in the application of the preceding reagent. 4. Iodine in Potassium Iodide. This reagent may be prepared by dissolving five parts of potas- sium iodide in one hundred parts of water, and then adding two AURIC <'[ir,()Rii)F, rKs'i'. 445 |)arts (tf pure iodine. A dro]) or (wo of lliis niixtiirc (lirows down from solutions of nirotiiu' luul of its salts a rcddisli-hrown, hrouiiisli- yellow, or yellowish, amorphous precipitate, its exact color depending somewhat upon the strength of the alkaloidal solution, and also upon the quantity of reagent added. After a little time the precipitate may entirely disajipear; hut it is immediately reproduced upon fur- ther addition of the reagent. The precipitate is readily soluble in potassium hydrate and in alcohol. 1. ^1^ grain of nicotine, in one grain of water, yields a very coi)ious deposit. 2. YxiVir grJ^'" : ^ copious, reddish-brown precipitate. 3. Yir.VuT gi'^i" yields a good reddish-yellow deposit. 4. -^--^^jj-jj-jj- grain : a quite distinct greenish-yellow precipitate. 6. -Bij-.Viro" gi'ain : a quite good turbidity. 6. "nJT.xnnr gi"^iii- ^ very obvious turbidity. 7, Y^V.innr g^'^i^ yields a perceptible cloudiness. As a solution of iodine in potassium iodide causes no precipitate in solutions of the inorganic alkalies and has its color immediately discharged by them, it readily serves to distinguish nicotine from these substances. But, as the reagent produces with most of the alkaloids and many other substances precipitates similar to that from nicotine, it has no positive value, for the detection of this alkaloid, further than to confirm the reactions of other tests. From the fact that the limit of the reaction of this reagent exceeds that of either of the other tests for nicotine, it is obvious that should this test fail to produce a precipitate, in a solution sus- pected to contain nicotine, it would be fruitless to apply any of the other tests to the same solution, unless possibly there should be some substance present that interfered with the reaction of this reagent. 5. Aiwio Chloride. Trichloride of gold produces in aqueous solutions of nicotine a yellow, amorphous precipitate, which is nearly insoluble in acetic and hydrochloric acids, but soluble, to a clear solution, in excess of the caustic alkalies. 1. y^ grain of nicotine yields an immediate, copious, yellow pre- cipitate, which remains amorphous J the deposit is not entirely soluble in several drops of strong acetic acid. If several grains or more of the nicotine solution be precipitated by the reagent 446 NICOTINE. and the mixture then heated, the precipitate dissolves to a beautiful purple solution. 2. YWoo grain yields a good, yellow deposit, which is slowly soluble in a few drops of a strong solution of potassium hydrate. If the precipitate produced from several grains of the solution be heated in the mixture, it dissolves, and is reproduced unchanged as the mixture cools. 3. gQ - QQ grain : an immediate greenish-yellow precipitate, which soon increases to a quite good, dirty-yellow deposit ; the precip- itate is readily soluble in a drop of potassium hydrate solution. 4. YO-Qo" grain yields a good, yellowish precipitate, which imme- diately disappears upon the addition of an alkali. 5. YF.Voir grain : in a few moments a distinct turbidity, and in a little time a quite satisfactory precipitate. 6. -g-o.Vcro" gi'ain : in a little time the mixture becomes turbid, and soon there is a quite distinct deposit. Trichloride of gold also produces yellow, amorphous precipitates with most of the alkaloids and various other substances. 6. Bromine in Bromohydrio Acid. Aqueous solutions of nicotine yield with a strong aqueous solu- tion of bromohydric acid saturated with bromine a yellow, amor- phous precipitate, which in a little time disappears. 1. yi-g- grain of nicotine yields a copious, bright yellow precipitate, which soon disappears, but is reproduced upon further addition of the reagent. 2. YFoo" gi^ain : a rather copious precipitate. 3. 5-^00" gi^ain yields a very good, greenish-yellov/ deposit, which soon dissolves, and is not reproduced upon further addition of the reagent. 4. i-o.^-Q^ grain yields a slight turbidity. The reaction of this reagent is common to most of the alkaloids and many other organic compounds. The reagent produces no pre- cipitate and has its color discharged when added to solutions of the caustic alkalies. 7. Tannic Acid. Tannic acid produces in aqueous solutions of nicotine a white, amorphous precipitate, which readily dissolves to a clear solution on SEPARATION FROM ORGANIC MIXTURES. 447 the additioii of a small (i.iantity of hydrochloric acid, but is repro- duced upon further addition of the acid, and is then insoluble in larantity of water, and the liquid filtered. On now treating the filtrate with lead acetate, any meconic acid present will be precipitated as meconate of lead : it should be borne in mind that under these circumstances the lead re- agent not unfrequently produces a yellowish-white precipitate, even in the absence of meconic acid. Any precipitate thus obtained is separated by a filter and examined in the usual manner for the or- ganic acid, while the filtrate is tested for morphine. The repeated digestions with alcohol, in the above process, are rendered necessary on account of the extreme tenacity with which these opium principles, especially the meconic acid, adhere to the al- buminous matter of the blood. In fact, this organic acid forms with albumen a precipitate, which is very sparingly soluble in water, and only slowly yields the acid to alcohol. In operating on a fluid-ounce of blood, according to this method, the smallest quantities of meconic acid and morphine from which we succeeded in recovering crystals of both substances were the one- twentieth of a grain of each. In one of these instances, the final mor- phine solution being concentrated to three drops, two of the drops 512 MECONIC ACID AND MORPHINE. gave respectively witli nitric acid and ferric chloride very satisfac- tory evidence of the presence of the alkaloid, while the third, when exposed to the vapor of ammonia, and then to the air for several hours, deposited four comparatively large groups of crystals of the pure alkaloid. In the same case, the evidence of the presence of the meconic acid was about equally satisfactory. With mixtures containing smaller quantities of the opium prin- ciples, the final solutions, even when only the 1-lOOth of a grain of each substance had been added, gave results that no doubt were due to the presence of these principles ; yet the reactions were by no means conclusive. On examining for only one of these substances, crystals may be obtained from a somewhat smaller quantity of either than before stated. On applying the foregoing method to the examination of the blood of eight different dogs and cats poisoned by opium, the final solutions in some instances gave results which there is little doubt were due to the presence of meconic acid and morphine; while in others they failed to reveal the presence of a trace of either of these substances. In no instance, however, were crystals obtained or were the results, with perhaps a single exception, such as would have been satisfactory in an unknown case. In the exception just mentioned, two grains of morphine in solu- tion had been given to a large cat; an hour afterward an ounce of laudanum was administered, and in another hour one ounce more. In an hour after the last dose the animal was killed by a blow on the head, and four ounces of blood were carefully taken from the body. On treating the whole of the fluid after the manner before described, and concentrating the final solution, supposed to contain meconic acid, to two drops, and testing one of these directly with ferric chloride, and evaporating the other to dryness and testing the resi- due in the same manner, both gave results identical with those occa- sioned by minute traces of the organic acid. So, also, the morphine solution, when reduced to two drops and these tested separately by nitric acid and a ferric salt, gave equally distinct evidence of the presence of the alkaloid. Bearing in mind that at most only a minute quantity of the organic poisons enters the blood, and the great loss attending the separation of the opium ])rincii)les from this fluid, we were not much disappointed in the results of the foregoing experiments. FAIUTIIK TO DETKCr. 513 The Urine. — Accordino; to M. liouohardat, morphine, when taken either in its free state or under the form of opium, si)eediiy appears in the urine, and may be detected by the liquid yielding a reddish-brown precipitate with a solution of iodine in potassium iodide. Since, however, as we have already seen, this reagent also produces similar precipitates with most of the other alkaloids and with certain other organic substances, this reaction in itself could by no means be regarded as direct proof of the presence of this alka- loid. Moreover, we find that the reagent not unfrequently throws down a precipitate from what may be regarded as normal urine; while, on the other hand, it sometimes fails to produce a precipitate, even when comparatively large quantities of the alkaloid have been purposely added to this liquid. Failure to detect the Poison. — It has not unfrequently happened that there was a failure to detect a trace of either meconic acid or morphine in any part of the alimentary canal, even when large quantities of the poison had been taken and the conditions for its detection were apparently very favorable. Thus, in a case re- lated by Dr. Christison, he failed to obtain any direct evidence of the presence of the poison in the contents of the stomach of a young woman who died in five hours after taking not less than two ounces of laudanum. In another case, the contents of the stomach, evac- uated two hours after seven drachms of laudanum were swallowed, had no odor of opium, nor did they reveal the presence even of meconic acid. Prof. L. A. Buchner relates an instance in which he failed to find any morphine in the stomach of a boy, five years old, who was killed by three doses, of two grains each, of the acetate of morphine. {Amer. Jour. Pharm., Sept. 1867, 415.) And Dr. Ebertz reports a case {Ann. d'Hyg., 1875, 220) in which a woman took in mistake for quinine about four grains (.25 gramme) of the hydrochloride, and died from its effects in from forty to fifty minutes. On examination of the contents of the stomach, the upper portion of the small intes- tines, the liver, spleen, kidneys, and the blood of the right ventricle, no trace of morphine was found. So, also. Dr. Ogston mentions a case {Med. Jur., 1878, 567) in which a woman had taken not less than from nine to ten grains of the hydrochloride, and died within a few hours, and, although there had been no vomiting and no remedy applied, a most careful examination by himself and the late Prof. 33 514 MECONIC ACID AND MOEPHINE. Gregory failed to detect any trace of morphine in the alimentary tube or elsewhere. Since the tests and methods for separating meconic acid from foreign substances are somewhat more satisfactory than those for morphine, in poisoning by opium, the acid has sometimes been de- tected when there was a failure to detect the alkaloid. On the other hand, the poison has been detected even when taken in only comparatively small quantity and death was delayed for several hours. In a case related by Dr. Skae, in which not more than half an ounce of laudanum had been taken, and death did not occur until thirteen hours afterward, the contents of the stomach furnished evident indications of the presence- of morphine, and faint evidence of meconic acid. It need hardly be remarked that, since opium or its active alkaloid is so frequently administered medici- nally, the detection of mere traces of the poison in the dead body would not in itself be positive proof that it was the cause of death. Quantitative Analysis. — For the purpose of estimating the quantity of morphine present in an aqueous solution of any of its salts, the somewhat concentrated solution may be slightly supersatu- rated with pure aqua ammonise, and allowed to stand quietly in a cool place for about twenty-four hours. The alkaloid, with the ex- ception of the merest trace, will now be precipitated in its crystalline form. The crystals are then carefully separated from the liquid, washed with absolute ether, dried at the ordinary temperature, and weighed. One hundred parts by weight of the pure crystallized alkaloid represent 123.8 parts of crystallized hydrochloride of mor- phine, Ci7Hi9N03,HCl,3Aq ; 125 parts of the crystallized sulphate, 2C„Hi9N03: H2S04,5Aq;or 131.6 parts of the acetate of morphine, C,,H,9N03,C2HA,3Aq. The quantity of opium or morphine found in the stomach, in poisoning by one or other of these substances, is usually too minute to admit of a direct quantitative analysis. Under these circum- stances, the quantity may sometimes be estimated with considerable accuracy by observing the intensities of the reactions of the reagents applied, and comparing these with the reactions of known quantities of the poison. NARCOTINE. 515 IV. Narcotine. History. — The existence of narcotine was iirst pointed out, in 1803, by Derosne; but Robiquet, in 1817, was the first to indicate its chomical nature. Blyth, in 1844, assigned to it the fornnula C23II05NO7. The more recent investigations of Messrs. Matthiessen and Foster led them to adopt the formula C22H23NO7. {Jour. Chem. Soc, 1863, 342.) Wertheim has described three homologous forms of narcotine in opium, having the formulae 022^23^^7? ^^23ll25^^7> and C.^HgyNOy, which he named, respectively, methylo-, ethylo-, and propvlo-narcotine, from the fact that when passed over soda-lime they yield methylamine, ethylamiue, and propylamine. The investi- gations of Matthiessen and Foster, as well as those of Dr. Anderson, however, render the existence of these varieties very doubtful. Narcotine usually constitutes from six to eight per cent, of good Smyrna opium ; but in some varieties of the drug it forms only about one per cent. As this substance may be extracted from the drug by ether, without the addition of either an alkali or an acid, it would appear that it exists principally in its free state. It has only feebly basic properties. Preparation. — This substance may be obtained either by adding ammonia to the mother-liquor from which hydrochloride of morphine has been prepared, or by digesting the insoluble part of opium in acetic acid, and precipitating by ammonia. The impure narcotine is purified by digesting its hot alcoholic solution with animal charcoal and recrystallizing (Gregory). Physiological Effects. — Much discrepancy has existed among ex- perimentalists in regard to the action of narcotine upon the animal system, some observers considering it as almost inert, whilst others attribute to it narcotic properties. These narcotic eflPects, however, may have been due to the presence of morphine in the preparation employed. Dr. O'Shaughnessy, of Calcutta, attributed to it powerful antiperiodic properties, and used it, he states, with great success in the treatment of intermittent fever. He prescribed it in doses of three grains, three times a day. Dr. S. Weir Mitchell, in experiments upon himself, found narco- tine to produce little or no effect, even when taken in doses of thirty grains. It seemed to be equally inert when given by the mouth to 516 NARCOTINE. pigeons ; but when administered hypodermically in two-grain doses, it caused feebleness, unsteady gait, and early convulsions, without in any instance stupor. [Amer. Jour. Med. Sei., Jan. 1870, 23.) This observer also found that pigeons possessed an entire immunity to the action of opium and morphine, even when administered in enor- mous doses. Chemical Peoperties. — In its pure state, narcotine crystallizes in the form of transparent, colorless, rhombic prisms ; sometimes, how- ever, it appears in the form of oblong plates, and at other times as a granular powder. In its solid state, it is nearly destitute of taste, but when in solution, it has an intensely bitter taste, even exceeding that of morphine. When moderately heated, it fuses to a colorless liquid ; at higher temperatures it takes fire, burning with a smoky flame. According to Prof. Guy, narcotine fuses at 115.5° C. (240° F.), and volatilizes at 154.4° C. (310° F.). Under the action of oxidizing agents narcotine is readily decom- posed, giving rise to a variety of new compounds, among which is opianyl, one of the other opium principles. The pure alkaloid, when in solution, has little or no action upon reddened litmus-paper, in which respect it differs from morphine ; so also, unlike morphine, it fails to strike a blue color either with a ferric salt or with a mixture of iodic acid and starch. Narcotine fails to neutralize diluted acids, but it readily unites with them, forming salts, which, for the most part, are uncrystal- lizable. Concentrated sulphu7nG acid slowly dissolves the alkaloid to a yellow solution, which, when stirred with a crystal of j)otassium nitrate, acquires a deep blood-red color. When the simple acid so- lution is moderately heated, it acquires a purplish color, even when only a very minute quantity of the alkaloid is present. When the acid solution is stirred with a crystal of potassium dichromate, the results depend much upon the relative quantity of the salt employed (see post). Concentrated nitrie acid also dissolves the alkaloid to a more or less yellow solution ; hydrochloric acid dissolves it without change of color. It is slowly soluble in large excess of concentrated acetic acid, but insoluble in the diluted acid. When large excess of powdered narcotine is digested for twenty- four hours, at the ordinary temperature, with pure water, this liquid fails to dissolve even the 1— 20,000th of its weight of the alkaloid. Absolute ether, under similar circumstances, takes up one part of BEHAVIOi: WITH 11 IK ALKALIES. 617 the alkaloid in 20.S luirts of the liquid, iSarcoliiio is Holuhle in all proportions in chloroform, and dissolves readily in alcohol, but is insoluble in the caustic alkalies. The salts of the alkaloid are, for the most part, readily soluble in water and in alcohol. Narcotine and morphine may be separated from each other by agitating the mixture with chloroform or ether, which will dissolve the former but not the latter ; so, also, these substances may be sepa- rated bv a solution of either of the fixed caustic alkalies or by diluted acetic acid, which will take up the morphine but not the narcotine. Narcotine may be readily separated from aqueous solutions of its salts by treating the solution with slight excess of a free alkali, and agitating the mixture with chloroform or ether. Upon spontaneous evaporation, the extracting liquid will usually leave the alkaloid in the form of beautiful groups of brilliant crystals, similar to those of the crystallized acetate (Plate VIII., fig. 3). In the following examination of the reactions of narcotine when in solution, the pure alkaloid was dissolved in water by the aid of the least possible quantity of hydrochloric acid. The fractions employed indicate the amount of pure alkaloid in solution in one grain of water; and, unless otherwise intimated, the results refer to the be- havior of one grain of the solution. 1. The Alkalies and their Carbonates. The fixed caustic alkalies, and ammonia, as also their carbonates, produce in aqueous solutions of salts of narcotine a white precipitate of the free alkaloid, which is insoluble in even large excess of the precipitant and in diluted acetic acid, but readily soluble in hydro- chloric and nitric acids. After a little time the precipitate becomes crystalline. 1. YTo gi'E^i" of narcotine, in one grain of water, yields a very copious, amorphous deposit, and very soon the mixture becomes a nearly solid crystalline mass. 2. Yruu grain yields an immediate precipitate, which in a little time becomes converted into beautiful, and somewhat characteristic, crystalline tufts, Plate YIII., fig. 2. 3. Yo'.TOir grain : an immediate cloudiness, and in a few moments crystals appear; after a little time there is a quite good crystal- line precipitate, the crystals having the forms just illustrated. 4. 4-(5-,^-c-(r gi'ain : if only a very minute trace of the reagent be em- 618 NAECOTINE. ployed, the mixture soon becomes opalescent, and after a little time, especially when examined by the microscope, yields a very satisfactory deposit of crystalline needles. This precipi- tate fails to appear in the presence of even very slight excess of the reagent. If a drop of an aqueous solution of a salt of narcotine be ex- posed to the vapor of ammonia, it soon becomes covered with a white crystalline film, even when it contains only the l-5000th of its weight of the alkaloid. 2. Sulphuric Acid and Potassium Nitrate. If a solution of narcotine or of any of its salts be evaporated to dryness, the residue dissolved in a small quantity of concentrated sulphuric acid, and then a small crystal of potassium nitrate or a trace of free nitric acid be stirred in the mixture, the latter quickly acquires a deep blood-red color, even if only a minute quantity of the alkaloid be present. This color is discharged by large excess of free nitric acid. 1. Y0T g^^iii of narcotine, when dissolved in a single drop of the concentrated acid, and a small crystal of nitre added, yields a deep red coloration. If the nitre be first dissolved in the acid and the mixture then allowed to flow over the narcotine deposit, the latter immediately assumes a deep red color, and slowly dissolves to a solution of the same hue. 2. YWo" gr^i^^ '• if the acid mixture be flowed over the deposit, the latter becomes blood-red, and soon dissolves to a yellow solution. 3. Yo".Wo gi'^ij^ • the deposit acquires a red color, and very soon dissolves to a faintly yellow solution. This is one of the most characteristic tests yet known for the detection of narcotine. Under its action the true nature of the precipitate produced by the caustic alkalies or their carbonates may be fully established. For this purpose the precipitate is washed, dried, then dissolved in a drop of sulphuric acid, and a small crystal of nitre stirred in the solution. When a solution of narcotine in concentrated sulphuric acid is stirred with a very small crystal of potassium dichromate, the fluid acquires a beautiful wine color, which remains unchanged for many days. If, however, an excess of the potassium salt be used, the liquid passes through several colors, and ultimately becomes either POTASSIUM ACETATE TEST. 519 green or blue, tlie liiuvl color depending upon the relative amount of the salt employed. The permanent color is readily obtained by stirrinj^ the potassium salt in the acid solution until it imparts the desired tint, and then removing the crystal from the mixture. The color may thus be obtained from even a very minute quantity of the alkaloid. 3. Potassium Acetate. A solution of potassium acetate produces in aqueous solutions of salts of narcotine a white precipitate of the acetate of narcotine, which is insoluble in large excess of the precipitant, but readily soluble in most free acids, and in excess of the narcotine solution. If, therefore, the solution contain a free acid, or if the reagent be not added in excess, the mixture may fail to yield a precipitate. The formation of the precipitate from dilute solutions is much facilitated by stirring the mixture. 1. __L_ grain of narcotine, in one grain of water, yields a very copious, amorphous deposit, which after a time becomes converted into beautiful groups of crystals, Plate YIII., fig. 3. 2. —l^ grain : an immediate cloudiness, and soon a quite good crystalline deposit. 3. ^i_ grain yields after a little time a good deposit of crystalline needles. 4. ^-^1^5-5- grain : after a few minutes crystals appear. 5. ^\^^ grain: after several minutes crystalline needles appear along the edge of the drop, and after a time there is a very satisfactory deposit. The same precipitate is thrown dow^n from solutions of salts of narcotine by other acetates, such as the acetate of barium, of zinc, and of lead ; but the reactions of these, especially the last-mentioned, are not quite so delicate as that of the potassium salt. The production of a precipitate by the neutral alkali acetates is rather characteristic of narcotine, since it is the only substance, except solutions of salts of silver and mercurous compounds, with which they produce a precipitate, at least in the form of an acetate. In solutions containing silver or mercury, however, the reagent fails to produce a precipitate unless the solution be quite concentrated and a corresponding solution of the reagent be employed. As the acetates thus serve for the detection of narcotine, so, on the other hand, solutions of salts of the alkaloid serve for the pre- 620 NAECOTINE. cipitation of combined acetic acid, for which heretofore we had no ready precipitant. However, as the acetate of narcotine is readily soluble in excess of a soluble salt of the alkaloid, the latter is not so delicate a test for the acetates as these are for narcotine. 4. Potassium Chr ornate. This reagent throws down from aqueous solutions of salts of narco- tine a yellow, amorphous precipitate, which after a time becomes crys- talline. The precipitate is readily soluble in acids, even acetic acid. 1. Y^ grain of narcotine, in one grain of water, yields a very copious deposit, which slowly assumes the crystalline form. 2. xru'o" grain : a quite good precipitate, which soon yields crystal- line tufts of the same form as produced by the caustic alkalies (Plate VIII., fig. 2). 3. 5-^5-0 grain : much the same as 2. The formation of the crystals is much facilitated by stirring the mixture. 4. Yo.Vro E^^^^'^ yields in a very little time, especially by stirring, a good crystalline deposit. 5. ■25-,Vfo grahi : after a few minutes a very satisfactory deposit of crystalline needles and tufts. The forms of the crystals produced by this reagent are somewhat peculiar to solutions of narcotine. Potassium dichromate produces in somewhat strong solutions of salts of the alkaloid a yellow, amorphous precipitate, which after a time becomes granular. One grain of a 1-1 00th solution of the alkaloid yields a copious deposit; and a similar quantity of a 1— 500th solution a quite fair, light yellow precipitate; but a 1-lOOOth solu- tion fails to yield any visible change. 5. Potassium Sulphocyanide. This reagent occasions in solutions of salts of narcotine a white precipitate, which is insoluble in the alkalies, but readily soluble in acids, even acetic acid. 1. Y^ grain of narcotine yields a very copious deposit, which soon becomes a mass of crystals of the same form as those produced by the caustic alkalies. 2. y-^g-g- grain : an immediate precipitate, which soon becomes crys- talline. BROMINE IN BROMOIIYDRIC ACID TEST. 521 3. -j-y;^ grain: after a little time, especially if the mixture be stirred with a gla&s rod, it yields a very satisfactory crystalline deposit. 4, -^-^ grain: after a time a (luite satisfactory deposit of crystal- line needles. This reagent produces no precipitate in solutions of salts of morphine. 6. Auric Chloi'ide. Trichloride of gold produces in solutions of salts of narcotine a bright yellow, amorphous precipitate, the color of which is per- manent, even upon the addition of caustic potash: in this respect narcotine differs from morphine. Upon heating the mixture the precipitate dissolves, but it is reproduced as the solution cools. The precipitate is but very sparingly soluble in large excess of acetic acid. 1. _^ grain of narcotine, in one grain of \\-ater, yields a very copious precipitate. 2. ^-^ grain : a very good deposit, which is insoluble in several drops of a strong solution of potassium hydrate. 3. j-g-Ljj-y grain yields a very satisfactory precipitate. 4. ^-—^ grain : after a little time a quite perceptible deposit. 5. ^y^j^ grain yields a perceptible turbidity. 7. Iodine in Potassium Iodide. A solution of iodine in potassium iodide throws down from solutions of salts of narcotine a reddish-brown, amorphous precipi- tate, which is nearly insoluble in the caustic alkalies, and only very sparingly soluble in acetic acid. 1. _i_j. grain of narcotine yields a very copious deposit. 2. Ywro g^^'" • ^ copious precipitate. 3. -^-L^ grain yields a quite good precipitate, which is readily soluble to a clear solution in potassium hydrate. 4. -g-g-i-g^ grain : a brownish-yellow deposit. 5. ^-,5-j5-ijj^5^ grain yields a very perceptible turbidity. 8. Bromine in Bromohydric Acid. A solution of bromohydric acid saturated with bromine produces in solutions of salts of narcotine a bright yellow, amorphous precipi- tate, which is insoluble in large excess of the precipitant, and only sparingly soluble in acetic acid. Upon the addition of potassium 622 NAECOTINE. hydrate, the precipitate acquires a white color, except when produced from very dilute solutions, when it dissolves to a clear liquid. 1. Ywo gJ'S'iii of narcotine yields a very copious precipitate, which after a time dissolves, but it is reproduced upon further addition of the reagent. 2. iQ-QQ grain : a copious precipitate, which is soluble in potassium hydrate, but is almost immediately replaced by a white deposit. 3. xo.^-o-o grain : a quite good deposit, which, when dissolved in potassium hydrate, yields a slight, white precipitate. 4. -g-Q-.Too" grain yields a quite distinct, yellowish precipitate. 5. i-Q o'iWo' gJ^ain : a quite distinct cloudiness. 9. Potassium Ferrocyanide. This reagent produces in aqueous solutions of salts of narcotine a dirty- white, amorphous precipitate, which is very readily soluble in acetic acid, but insoluble in large excess of the precipitant. 1. Y^ grain of narcotine, in one grain of water, yields a quite copious deposit. 2. YToo" gi^ain : a very good precipitate. 3. i-o,Wo grain yields a quite strong turbidity. Potassium ferricyanide throws down from quite strong solutions of narcotine a yellow, amorphous precipitate, which is readily soluble in excess of the precipitant and in acetic acid. 10. Picric Acid. An alcoholic solution of picric acid throws down from solutions of salts of narcotine a bright yellow, amorphous precipitate, which is slowly soluble in large excess of the precipitant, and also in large excess of acetic acid. 1. YTo grain of narcotine yields a very copious precipitate, which remains amorphous. 2. YoVo grain : a very good deposit. 3. yo.Vfo grain yields a quite obvious precipitate. Platinie chloride produces in somewhat strong solutions of salts of narcotine a light yellow, amorphous precipitate, which is sparingly soluble in acetic acid. One grain of a 1-lOOth solution of the alka- loid yields a very copious precipitate, and the same quantity of a 1-lOOOth solution, a quite fair deposit; but a l-2500th solution CODEINE. 523 yields no iiulications. Palladium chlojnde produces similar results. Tannic acid and corrosive sublimate throw down from concentrated solutions of the alkaloid white, amorphous precipitates. When somewhat strong solutions of salts of narcotine are treated with a stream of chlorine gas, the liquid quickly assumes a yellow color, which soon changes to reddish-brown ; on now adding a solu- tion of ammonia, the mixture acquires a deep brown color. Ten grains of a 1-1 00th solution of the alkaloid will yield these results. A similar quantity of a 1-lOOOth solution, when treated with the gas, acquires a distinct yellow tint, which is changed to reddish- brown by ammonia. In these reactions narcotine closely resembles morphine. V. Codeine. History. — Codeine, or codeia, as it is frequently called, was first discovered, in 1832, by M. Robiquet. It exists in opium in combina- tion with meconic acid, and usually forms considerably less than one per cent, of the crude drug. The formula for codeine, in its anhy- drous state, according to Gerhardt, is CisHgiNOg; in its crystalline form, it usually contains one molecule of water of crystallization. It has a bitter taste and strong alkaline properties, q\iickly restoring the blue color of reddened litmus-paper. Preparation. — Codeine may be obtained, according to Dr. Greg- ory, by concentrating the mother-liquor from which morphine has been precipitated, when, after a time, a mixture of the hydrochlo- rides of codeine and morphine will be deposited. This deposit is dissolved in a little hot water, and the solution treated with excess of potassium hydrate, which precipitates the codeine, partly in the form of crystals and partly as a viscid mass, which soon becomes solid and crystalline ; at the same time, most of the morphine prasent remains in solution in the alkaline liquid. The precipitate is then treated with ether or with water, either of which will dissolve the codeine, while any morphine present will remain undissolved. The ethereal solution, upon spontaneous evaporation, leaves the alkaloid in the form of beautiful anhydrous prisms ; while the aqueous solu- tion deposits it in the form of octahedral crystals, containing one molecule of water of crystallization. Physiological Effects. — The statements in regard to the effects of codeine when taken into the stomach have been quite contradictory. 524 CODEINE. According to the results of some observers, it has strong narcotic properties, similar to those of morphine, only that it has to be given in larger quantity, and never induces the unpleasant after-effects so frequently witnessed in the administration of that alkaloid. Dr. Gregory observed that in some instances it excited a sense of intense itching of the entire skin, and states that probably the itching caused in some persons by opium and some of the salts of morphine may be due to the action of codeine, this substance being not unfrequently present in some of the preparations of morphine. On the other hand, other observers were led to conclude that codeine was nearly or entirely destitute of narcotic properties. Five grains of codeine, taken by Dr. S. Weir Mitchell, caused slight giddiness and nausea, with some cerebral heaviness. Dr. Wood states that he has given it in doses of eight grains per day without any marked effect. Chemical Peopeeties. — Codeine is a white, crystallizable, and strongly basic substance, precipitating the oxides of many of the metals from solutions of their salts, but in its turn being precipitated by the caustic alkalies. It is readily distinguished from morphine by not striking a blue color with a ferric salt. When heated, it first parts with its water of crystallization, and at about 120° C. (248° F.) fuses to a colorless liquid, which at higher temperatures takes fire, burning with the evolution of dense fumes. Codeine completely neutralizes diluted acids, combining with .them to form salts, most of which are readily crystallizable. Con- centrated sulphuric acid slowly dissolves the pure alkaloid without change of color; if a solution of this kind be heated on a water- bath, it acquires a beautiful purple color, even when only a minute quantity of the alkaloid is present : this result, however, is some- v/hat influenced by the amount of acid and heat employed. A small crystal of potassium nitrate stirred in the cold acid solution yields a faint greenish, then reddish, coloration; while a crystal of potas- sium dichroraate yields a green color, due to the formation of ses- quioxide of chromium. Concentrated nitric acid, it is said, produces no change of color with codeine ; but the few samples we have examined became more or less orange-yellow, and dissolved to a yellow solution, when treated with this acid, especially when a not inconsiderable quantity of the alkaloid was employed. Similar results have also been obtained by various other observers. Stannous chloride added to the nitric acid solution causes it to undergo little CHEMICAL i»ropp:rtie8. 525 or no change. Ilydrocliloric acid readily dissolves the alkaloid to a colorless solution, which rcnuiins unchanged upon the applicration of heat. When excess of Hnely-powdered codeine is digested with pure water at tiie ordinary temperature, with frequent agitation, for twenty-four hours, the solution then filtered, and the fdtrate evap- orated to dryness, it leaves a crystalline residue indicating that one part of the alkaloid had dissolved in 128 parts of the fluid. It is much more freely soluble in hot water, from which, however, much of the excess separates as the solution cools. Absolute ethei-, under the foregoing conditions, dissolves one part of the alkaloid in 55 parts of the liquid. Chlorofoiin, under similar conditions, takes up one part in 21.5 parts of fluid. The alkaloid is also freely soluble in alcohol, and somewhat soluble in solutions of the caustic alkalies, but less so than in pure water. The salts of codeine are, for the most part, readily soluble in water, and in alcohol ; but they are nearly or altogether insoluble in ether, and in chloroform. Aqueous solutions of codeine, when not too dilute, have a strongly alkaline reaction and a very bitter taste. The alkaloid may be extracted from its aqueous solution by agitation with ethe^' ; but, as codeine is not very much less soluble in water than in ether, repeated agitations with the latter are required for the complete separation of the alkaloid. It is much more readily extracted by chloroform. By either of these liquids it may be separated from morphine. The alkaloid may, of course, be extracted in a similar manner from aqueous solutions of its salts, by first treating them wnth slight excess of a free mineral alkali. The codeine employed in the following investigations was pre- pared by E. iSIerck, of Darmstadt : it was in the form of large, colorless crystals, and apparently perfectly pure. Its solutions were prepared in the form of the acetate. The fractions indicate the fractional part of a o^rain of the pure alkaloid in solution in one grain of water ; and, unless otherwise stated, the results refer to the behavior of one grain of the solution. 1. The Caustic Alkalies. The fixed caustic alkalies and ammonia throw down from con- centrated aqueous solutions of salts of codeine a white, amorphous precipitate of the pure alkaloid, which is readily soluble in free acids. 526 CODEINE. One grain of a 1-lOOth solution of the alkaloid yields a quite good deposit, which remains amorphous. On account of the solu- bility of codeine in water, solutions but little more dilute than that just mentioned fail to yield a precipitate with either of these reagents. Since the alkaloid is less soluble in alkaline solutions than in pure water, it is partly precipitated from its pure aqueous solutions, when not too dilute, by the caustic alkalies. 2. Iodine in Potassium Iodide. A solution of iodine in potassium iodide produces in solutions of salts of codeine a reddish-brown precipitate, which is readily soluble to a colorless solution in potassium hydrate; it is also soluble in acetic acid. 1. ^-1^ grain of codeine, in one grain of water, yields a very copious precipitate, which after a time becomes more or less crystalline, Plate VIII., fig. 4. The precipitate is readily soluble in alco- hol, from which after a time it separates in the form of crystal- line plates, Plate VIII., fig. 5, which are especially beautiful under polarized light. Solutions but little more dilute than this fail to yield crystals. 2. YWWo grain yields a copious deposit. 3. Yo^.^-QT gi'aiii : a very good, reddish-yellow precipitate, 4. -3^,^-0-0 grain : a yellowish deposit. 5/_^-g-^L__ grain : a quite perceptible precipitate. 6. 5-ot3oTo" grain yields a distinct turbidity. This reagent also produces crystalline precipitates with some of the other opium principles; but the deposits produced by the reagent from most other substances remain amorphous. 3. Bromine in Bromohydric Aeid. A solution of bromohydric acid saturated with bromine throws down from solutions of salts of codeine a yellow, amorphous pre- cipitate, which after a time dissolves, but it is reproduced upon further addition of the reagent. 1. -L grain of codeine yields a very copious, bright yellow deposit. 2. xoW grain : a copious precipitate. 3. xo.Too" grain ; a fair, yellow deposit. 4. 2-5,^-0^ grain yields a quite perceptible cloudiness. AURIC OIir.ORIDE TEST. 527 The reaction of this reagent is common to solutions of most of the alkaloids, and also to other organic principles. 4. Potassium Sulphoeyanide. This reagent occasions in somewhat strong solutions of salts of codeine a white crystalline precipitate of the sulphocyanide of codeine, which, according to Anderson, has the composition Ci8H2iN03,HCNS. The precipitate is readily soluble in acetic acid. 1. yIto gi'^i'i o^ codeine : after some minutes crystalline needles begin to separate, and after a little time there is a copious crys- talline deposit, Plate VIII., fig. 6. If the mixture be stirred, it immediately yields crystals, and very soon the drop becomes a mass of crystalline groups. 2. Tj-J-_ grain : on stirring the mixture, crystals soon appear, and after a time there is a very satisfactory deposit. This reagent also produces crystalline precipitates with solutions of several other alkaloids. 5. Potassium Dichromate. Potassium dichromate produces in quite strong solutions of salts of codeine a yellow crystalline precipitate, which is readily soluble in acetic acid. Very concentrated solutions of the alkaloid yield beautiful groups of bold, red crystals. One grain of a 1-1 00th solution yields no immediate precipi- tate, but, after standing some time, crystalline tufts separate, and the mixture ultimately becomes a nearly solid mass of crystals, Plate IX., fig. 1. The formation of the precipitate is much facilitated by stirring the mixture. Potassium chromate produces with very strong solutions of the alkaloid a yellow precipitate of crystalline plates and prisms. 6. Auric Chloride. This reagent throws down from solutions of salts of codeine a reddish-brown amorphous precipitate, which when treated with caus- tic potash yields a dark-bluish mixture. 1. Y^ grain of codeine yields a very copious precipitate: after standing some time, the supernatant fluid acquires a bluish color. 528 OODEINE. 2. YoTo g^^^i° yields a very good, yellow deposit. 3. g-^g-g- grain yields a very distinct cloudiness. 7. Platinic Chloride. This reagent precipitates from strong solutions of salts of codeine a yellow, amorphous deposit, which is readily soluble in acetic acid, but unchanged by caustic potash. 1. ylg- grain of codeine yields a copious deposit, which after a time becomes more or less granular. 2. -5-^0- grain yields after several minutes a partly granular precipi- tate. 8. Piei'ic Acid. An alcoholic solution of picric acid produces in solutions of salts of codeine a bright yellow, amorphous precipitate. 1. yly- grain of codeine yields a very copious deposit. 2. Y^oT g^^ain : a quite good precipitate. 3. 2W0 gi'^^^^ yields after a little time a quite distinct cloudiness. 9. Nitric Acid and Potassium Hydrate. When a small quantity of codeine, in its solid state, is added to a drop of concentrated nitric acid, it dissolves with the evolution of nitrous fumes, yielding an orange-yellow solution, which, when evaporated to dryness on a water-bath, leaves a yellow residue. If this residue be treated with a drop of caustic potash, it acquires a beautiful orange color, and partially dissolves to a solution of the same hue, which is permanent. 1_ ^_L_ grain of codeine yields the results just described. 2. YFoT gJ^aiii • the nitric acid solution leaves a slightly yellow residue, which with caustic potash yields a good orange-colored mixture. 3. Yi),-woT g^^^" '■ the slightly yellow residue left by the acid is but little changed by the potassium compound ; but if this mixture be evaporated, it leaves a yellowish-orange deposit, mixed with crystals of potassium nitrate : a drop of water readily dissolves these crystals, and yields a yellow-orange mixture, the color of which is permanent. Potassium iodide produces in concentrated solutions of salts of NARCEINE. 529 codeine, especially u{)oii stirring- the mixture, a crystalline precipitate of tiif'ts of needles, Plate IX., fig. 2. Corrosive sublimate, potassium ferro- and ferri-cyanide, copper sulj)hate, and silver nitrate produce no precipitate, at least imme- diately, in a 1-lOOth solution of salts of codeine. VI. Narceine. HiMory. — Narceine, which is said to form from six to twelve per cent, of Smyrna opium, was discovered, in 1832, by Pelletier. Its formula, according to Dr. Anderson, is 023^29^^)9. ^^ seems to be a neutral substance, yet it will unite with acids to form salts, all of which have an acid reaction. The statements of observers in re- gard to the constitution and properties of narceine have been very conHicting, and it is probable that two or perhaps three different substances have been described under this name. Preparation. — This substance may be obtained, according to Dr. Anderson [Quart. Jour. Chem. Soc, v. 257), from the mother-liquor of hydrochloride of morphine by diluting it with water, filtering, and then adding ammonia as long as a precipitate is produced. Nar- ceine and meconin remain in solution, while narcotine, resin, and small quantities of papaverine and thebaine are deposited. The filtered liquid is treated with excess of lead acetate, the dirty-brown precipitate produced removed by a filter, the excess of lead separated from the filtrate by sulphuric acid, and the liquid saturated with ammonia, then evaporated at a moderate temperature to a syrup, when it is allowed to stand some days. The precipitate then formed is collected on a cloth and washed with water, then boiled with a large quantity of water and the hot solution filtered. On cooling, the liquid becomes filled with fine silky crystals of narceine, which are separated from traces of calcium sulphate by solution in alcohol, and further purified by boiling with animal charcoal and reerystal- lization from water. Physiological Effects. — Experiments upon inferior animals indi- cate narceine to be an inert substance. Chemical Properties. — Narceine crystallizes in beautiful, colorless, delicate needles, which when dry form an exceedingly light, spongy mass. It is unchanged by persalts of iron. At a moderate heat it fuses to a clear liquid, and at higher temperatures burns like a resin. 34 530 NAECEINE. The narceine used in the present investigations was prepared by E. Merck : it was in the form of very delicate, colorless, silky needles. Concentrated sulphuric add causes the alkaloid to assume a reddish-brown color, and dissolves it to a reddish or yellowish-red solutioD, which upon the application of a moderate heat acquires an intense red color, and at higher temperatures darkens. These results, however, are much influenced by the amount of acid and heat employed. In no instance, with the single specimen examined, did we obtain the green color described by Anderson {Quart. Jour. Chem. Soc, v. 259), nor, with the diluted acid, the blue color ob- tained by other observers. A crystal of potassium nitrate stirred in the cold acid solution yields a reddish-brown, violet, or purple coloration, according to the relative quantities of the different sub- stances present : the color is discharged by heat. Potassium dichro- mate produces with the acid solution a dirty-red color, which on the application of heat is changed to green, due to the production of sesquioxide of chromium. When treated with concentrated nitrie acid, narceine assumes an orange-red color and dissolves to a more or less yellow solution, which suffers little or no change by a moderate heat. The solution is unaffected by stannous chloride, even upon the application of heat. The sample under consideration, when dropped into concentrated hydrochloric acid, became blue, and dissolved to a perfectly color- less solution. Pelletier described this reaction as characteristic of narceine, while Anderson failed to obtain a blue color from samples which he considered pure. When excess of narceine is digested, with frequent agitation, for twenty-four hours in water at the ordinary temperature, it requires 1660 parts of the liquid for solution. It is much more soluble in hot water, from which the excess slowly separates as the solution cools. One part of the alkaloid dissolves in five hundred parts of water as soon as the mixture is brought to the boiling temperature ; this solution may then be exposed for half an hour or longer to a temperature of 15.5° C. (60° F.) before crystals begin to separate. A concentrated aqueous solution of narceine has no action upon red- dened litmus. Absolute ether, under the foregoing conditions, dis- solved one part of narceine in 4066 parts of the liquid. Chloroform, under similar circumstances, dissolved one part in 7950 parts of BROMINE IN BROMOHYDRIC ACID TEST. 531 liquid. It is luticli nioro soluble in iilcoliol than in water, and is also somewhat soluble in dilute solutions of the caustic alkalies. In the followinti; investi^jations, the 1-lOOtli solutions were ob- tained by the aid of hydrochloric acid and a gentle heat; the more dihite solutions were prepared l)y dissolvinjjj the narceine, when necessary by the aid of heat, directly in distilled water, A 1-lOOth solution of narceine in the form of hydrochloride, unless main- tiiiued at a gentle temperature, soon becomes filled with a net-work of long, delicate, crystalline needles. 1. Iodine in Potassium Iodide. A solution of iodine in potassium iodide produces in solution of narceine a reddish-yellow precipitate, which almost immediately be- comes crystalline. The precipitate is slowly soluble in large excess of acetic acid. 1. YoT grain of narceine, in one grain of water, yields a very copious deposit, which very soon becomes a mass of crystalline needles and tufts; at the same time the mixture acquires a blue color. The precipitate is readily soluble in alcohol, from which it soon again separates in the crystalline form. 2. yuVu" grain yields a coj)ious precipitate, which soon changes to exceedingly delicate crystalline tufts, Plate IX., fig. 3. After a time the mixture acquires a more or less blue color. 3. 5",^ grain after a time yields some few crystalline tufts, of the forms just illustrated. The production of these crystalline tufts is quite peculiar to solutions of narceine. 2. Bromine in Bromohydrio Acid. A solution of bromine in bromohydric acid throws down from solutions of narceine a bright yellow, amorphous precipitate, which after a time dissolves, but is reproduced upon further addition of the reagent. The precipitate is soluble in acetic acid and in alcohol. 1. Yo y grain of narceine, in one grain of water, yields a very copious precipitate. 2. jtjVo grain : a copious deposit. 3. y^.Voir grain yields after a very little time a quite fair, yellow precipitate. 532 NAECEINE. 3. Auric Chloride. This reagent occasions in solutions of narceine a yellow, floccu- lent precipitate, which remains unchanged in color. The precipitate is soluble in the mixture upon the application of heat, and is repro- duced unchanged as the solution cools. It is readily soluble to a clear solution in potassium hydrate. 1_ _i_^ grain of narceine yields a very copious deposit. 2. x^Vo gi'ain : a very good precipitate. 3. yp-L-g-^ grain yields after a little time a perceptible turbidity, which soon becomes quite well marked. . 4. PlatiniG Chloride. This reagent precipitates from solutions of narceine a yellow, flocculent deposit, which is readily soluble in acids. After a time the precipitate yields granules and crystalline needles. 1 . _i_^ grain of narceine yields a very good deposit. 2. -g i-g- grain : a very fair precipitate. 3 YoW grain : no indication. 5. Picric Acid. An alcoholic solution of picric acid causes in solutions of nar- ceine a yellow, amorphous precipitate, which is readily soluble in acetic acid. 1_ 1^- 2;rain of narceine yields a copious deposit. 2. YWWo gi'ain : a good precipitate. 3. _^ grain yields after a little time a quite satisfactory deposit. 6. Potassium Bichromate. This reagent produces in strong solutions of narceine a yellow, amorphous precipitate, which soon becomes crystalline. 1. 1^ grain of narceine yields a very copious precipitate, which almost immediately becomes a mass of crystals. 2. -g-i-g- grain yields a very good crystalline deposit, Plate IX., fig. 4. Potassium chromate produces in solutions of the alkaloid much the same results as the dichromate. Potassium iodide, potassium sulphocyanide, corrosive sublimate, OPIANYL. 533 potassiinn ferro- and ferri-cyanide, produce no precipitate in even saturated aqueous solutions of narceine. VII. Opianyl. Hidovij. — Opianyl, or Meconine, n.s it was fornierly named, was discovered, in 1826, by M. Dublanc, but first descrilx;d by M. Couerbe, in 1832. It is a neutral crystal lizable substance, and forms less than one per cent, of opium. Its formula, as first determined by Couerbe, and afterward confirmed botii by Regnault and by An- derson, is CioHi„0^. It therefore differs from the alkaloids in not coiitainin*; nitrogen. Preparation. — Opianyl may be obtained from the mother-liquor from which narceine has been prepared by agitating it with suc- cessive portions of ether, as long as this liquid becomes colored. The united ethereal solutions are then evaporatedy and the brown syrup treated with dilute hydrochloric acid, which dissolves the papa- verine, while the opianyl, together with some resin, remains. The opianvl is then crystallized several times from boiling water, with the addition of animal charcoal, when it finally separates in color- less needles. It may also be obtained by acting upon narcotine with nitric acid. Physiological Effects. — From the few experiments made with this substance, it would seem to be inert. Chemical Properties. — Opianyl readily crystallizes in the form of long, colorless, six-sided prisms, or as delicate needles; it has a somewhat bitter taste. At a moderate heat, it fuses to a color- less liquid, which upon cooling solidifies to a radiated crystalline mass ; at higher temperatures, it is dissipated in the form of white fumes. When cautiously heated in a glass tube, it sublimes in beau- tiful crystals (Anderson). According to Dr. Guy, opianyl fuses at 48.8° C. (120° F.), and vaporizes at 82.2° C. (180° F.). Although a perfectly neutral body, opianyl is soluble in acids. The following observations are based upon the examination of a single specimen of opianyl, prepared by E. Merck. It was in the form of delicate, snow-white crystals. Concentrated sulphuric acid dissolves it to a colorless solution, w^hich when heated acquires either a beautiful blue or purple color, the hue depending upon the relative quantity of acid employed (see 534 OPIANYL. post) ; the cooled mixture, upon the addition of water, becomes reddish-brown and yields a brownish precipitate. Nitric acid also dissolves it to a colorless solution, which on being heated acquires a more or less yellow color, and on evaporation leaves a colorless crys- talline residue. It is also soluble in concentrated hydrochloric acid without change of color, even upon the application of heat. When excess of opianyl is digested in water for several hours, with frequent agitation, at a temperature of about 15.5° C (60° F.), one part dissolves in 515 parts of the liquid. According to Couerbe, it dissolves in 265 parts of cold water ; while Anderson states that at 15.5° C. (60° F.) it requires 700 parts of this liquid for solution. It is much more freely soluble in hot water, but much of the excess separates in its crystalline state as soon as the solution begins to cool. When excess of opianyl is boiled with water, it melts under the liquid ; yet, according to Anderson, when in its dry state, it requires a temperature of 110° C. (230° F.) for its fusion. Absolute ether, when in contact with excess of opianyl for several hours at the ordi- nary temperature, dissolves one part in 136 parts of the liquid. Chloroform dissolves it in all proportions. It is also readily solu- ble in alcohol; but it is not more soluble in solutions of the caustic alkalies than in pure water. In the following investigations, the opianyl was dissolved, when necessary by the aid of a very gentle heat, in pure water. 1. Iodine in Potassium Iodide. A solution of iodine in potassium iodide produces in aqueous solutions of opianyl a yellowish-brown, amorphous precipitate, which quickly becomes quite dark brown, and then changes to a mass of yellow crystals, which in their dry state resemble spangles of gold- dust. The precipitate is readily soluble in alcohol. 1. -g-l^ grain of opianyl, in one grain of water, yields a very copious precipitate, which very soon becomes converted into yellow crys- tals, Plate IX., fig. 5. 2. YWo" S^^^^ • ^ good, yellowish-brown deposit, which soon darkens. 3. -aFoT grain yields after a little time a slight cloudiness, followed by the precipitation of dark-colored granules. The reaction of this reagent is quite peculiar to solutions of opianyl. .SULPHURIC ACID TEST. 535 2. Bromine in Bromohydric Add. This reagent precipitates from solutions of opianyl a deposit of short needles, and groups of hair-like crystals. The precipitiite is insoluble in acetic acid, and hut slowly soluble in large excess of alcohol. 1. -j-J^y grain : after a few nionients crystals begin to form, and soon there is a quite copious deposit, Plate IX., fig. 6 ; after a time the mixture becomes a colorless mass of crystals. 2. -Yy}\)\) gi'ain : in a very little while a quite good crystalline deposit. 3. yTTUir g^^i" yields after a little time a very satisfactory crystal- line precipitate. The production of this crystalline precipitate is quite character- istic of opianyl. 3. Sulphuric Acid and Heed. When a small quantity of opianyl in its solid state is heated "with a very minute portion of concentrated sulphuric acid, it yields an intense blue color, which, as the heat is increased, changes to purple ; when a larger quantity of acid is employed, the heated mixture acquires a transient blue color, which passes to purple; while with a still larger quantity the mixture, when heated, assumes at once a beautiful purple color. This experiment may be performed in a thin, annealed watch-glass. 1. ^Jpy grain of opianyl, when moistened with a very small quantity of the acid, and heated, yields an intense blue coloration. 2. ydVo- grain : much the same as 1. For the success of this reac- tion it is essential that the least possible quantity of acid be employed. This is best attained by touching the deposit with a glass rod moistened with the acid; the mixture is then heated over the flame of a spirit-lamp, until it begins to assume a blue color, — which does not usually occur until vapors of the acid are evolved, — when the heat is withdrawn. 3. xir.Vro grain, when treated as just described, yields very satisfac- tory results. 4. Yohwo gi'ain : if the deposit be not distributed over a large space, it yields a very distinct blue coloration. With a very small quantity of the acid, a blue color may be 536 OPIANYL. obtained from a much less quantity of opianyl than will yield a purple color with a larger quantity of the acid. The production of this blue coloration is quite characteristic of opianyl. Narcotine when heated with a small quantity of sulphuric acid yields a purple mixture, which darkens as the heat is increased. So, also, a sul- phuric acid solution of codeine, when heated, acquires a purple color. A sulphuric acid solution of opianyl, when stirred with a few crystals of potassium nitrate, yields a yellow mixture, soon changing to a beautiful scarlet-orange color, which but slowly fades. Almost the least visible quantity of the substance, when treated in this man- ner with a very small quantity of the acid and nitre, yields very satisfactory results. On heating the mixture, the orange color is changed to yellow. In these reactions opianyl somewhat resembles narcotine. As opianyl forms no definite combinations with acids or with the metals, it is not precipitated by the ordinary reagents. Accord- ing to Couerbe, it yields a crystalline precipitate with basic lead acetate ; but, like Anderson, we failed to obtain a precipitate by this reagent. NUX VOMICA. 537 CHAPTEE III. NUX VOMICA, STRYCHNINE, BJiUCINE. I. Nux Vomica. Histcrry and Composition. — Nux vomica is the seed of the Strychnos nux vomica, a tree found native in the East Indies and the ishind of Ceylon. The seeds are flat, nearly round, and some- thing less than an inch in diameter, being slightly concave on one side, and convex on the other, and covered with short, silky, grayish or vellowish hairs, which are attached to an investing membrane and incline towards the circumference of the seed. The seeds are very hard, diflScult to pulverize, and when chewed have an intensely bitter taste, but they are destitute of any well-marked odor. In its powdered state nux vomica has a yellowish-gray color, and a peculiar odor, not very unlike that of liquorice. Nux vomica possesses powerful poisonous properties, due to the presence of the alkaloids strychnine and bnicine, which exist in the seed in combination with a peculiar organic acid, known as strychnic, or igasuric, acid. The seeds also contain, according to the analysis of Pelletier and Caventou, yellow coloring matter, gum, a waxy substance, starch, a concrete oil, woody fibre, and earthy, salts. A third alkaloid, under the name of igasurine, was described by M. Desnoix. But, according to W. A. Shenstone {Jou7\ Chem. Soc, Sept. 1881, 453), the substance thus described is nothing more than impure bnicine. The powdered seeds yield their active properties to water, but much more freely to alcohol. Poisoning by this sub- stance has been of quite frequent occurrence. Symptoms. — The symptoms produced by poisonous doses of nux vomica, or either of its active alkaloids, are very uniform in their nature, and quite peculiar. There is at first a sense of numbness in 538 NUX VOMICA. the extremities, with more or less trembling of the muscles, and a feeling of great anxiety. These effects are soon succeeded by violent muscular contractions, in which the limbs are extended and perfectly rigid, the head thrown back, the jaws fixed, the face livid, and the respiration apparently suspended. After a little time, varying from a few moments to some minutes, the convulsive paroxysm subsides, and the patient then feels much exhausted, and is usually extremely sensitive to external impressions. This condition, however, is usually of short duration, the convulsions being succeeded by others, which increase in violence, and speedily run to a fatal termination. In some instances death takes place during a paroxysm, but more gen- erally from extreme exhaustion. The intellectual faculties usually remain unaffected, even up to the time of death. The time within which the symptoms first manifest themselves is subject to con- siderable variation, they occurring in some instances almost imme- diately, and in others being delayed for even more than an hour. The following case, reported by Mr. Oilier, well illustrates the usual effects of uux vomica. A young woman purposely swallowed, in suspension in water, about three drachms of the powder. When seen about half an hour afterward, she was calm and quite well. But in about ten minutes more she was seized with a convulsive fit, and in a few minutes afterward had another, which was soon suc- ceeded by a third : the duration of these paroxysms was about two minutes each. During the attacks the whole body was extended and rigid, the legs widely separated, the face and hands livid, and the muscles of the former violently convulsed : no pulse or breathing could be perceived. In the intervals she was quite sensible ; com- plained of being sick, and made many attempts to vomit; had in- cessant thirst, a very quick and feeble pulse, and perspired freely. A fourth attack soon followed, in which the whole body was ex- tended to the utmost and rigidly stiff. She now fell into a state of asphyxia, relaxed her grasp, white foam issued from her mouth, the expression of the countenance became most frightful, and death ensued in about an hour after the poison had been taken. (London Med. Repository, xix. 448.) In a non-fatal case related by Dr. Basedow, of Merseburg, the following symptoms were observed. A young lady took by mistake a tablespoonful of the powdered drug. She was almost instantly deprived of the power of walking, and fell down, but still retained PERIOD WHEN FATAL. 539 her consciousness. When first seen by Dr. Basedow, almost imme- diately afterward, her connteiiaiu'C was pale, and exhibited alternately an expression of indiilcrence and anxiety ; the eyes were wide open, and the pupils contracted. The respiration was irregular and short; the pulse irregular and small, and the skin cool. The forearms were coustantlv in a half-bent position, and the hands and lingers affected with convulsive twitches; but the legs were motionless and rigid, all the muscles being hard and tetanically contracted. The patient had not the slightest jniin or sickness; but her breathing became every moment more difficult, and she complained of impending suffoca- tion. An emetic was now administered, and its action followed by the exhibition of small doses of a mixture of oil of turpentine and sulphuric ether. The dyspnoea gradually subsided, and in about six hours after the poison had been taken the tetanic spasms of the mus- cles of the legs, as well as the convulsive movements of the hands, had ceased, and the respiration was free; but the patient complained of a sense of bruising over the whole body, and pain in the limbs, for some days afterward. {New York Med. and Phys. Journal, xxx. 448.) In some few of the recorded cases of poisoning by this sub- stance, the first symptoms observed were nausea and vomiting; while in others the tetanic symptoms were followed by purging, and inflammation of the stomach and bowels. Period when Fatal. — In fatal poisoning by nux vomica, death usually takes place within a very few hours after the poison has been taken ; but life has been prolonged for some days. In a case cited by Dr. Christisou, in which a man swallowed an unknown quantity of the powder mixed with beer, death occurred in fifteen minutes after the poison had been taken. [On Poisons, 686.) Several in- stances are related in which death took place in from one to two hours. On the other hand, in a case cited by Orfila {Toxicologie, ii. 605), a man swallowed a considerable quantity of the powder, and almost immediately was seized with violent convulsions ; yet death did not occur until the fourth day. Fatal Quantity. — In a case quoted by Dr. Christison, an old woman who was using an alcoholic extract of nux vomica for palsy took an overdose of three grains, which soon produced violent tetanic spasms, followed by an attack of inflammation of the stomach and intestines, and death on the third day. The quantity of the crude 540 NUX VOMICA. powder represented by the extract taken in this case is quite uncer- tain. In another case,/oitr gi^ains of the extract taken by a lady, through the mistake of a druggist, caused her death within a few hours. [Amer. Jour. Pharm., July, 1867, 379.) In an instance re- lated by Hoffmann, thirty grains of the crude powder, taken in two equally divided doses, caused death. Dr. Taylor mentions two cases, in each of which fifty grains of the powder proved fatal : in one of these, death took place in an hour. {On Poisons, 767.) In another instance, two drachms caused death in about two hours. A boy, aged twelve years, took into his mouth about eight grains of the extract, thinking it was liquorice. Finding it very bitter, he spat out as much as he could. About an hour later, there were some slight twitchings of the muscles, and soon after, well-marked opis- thotonos, with an increase of the spasms, and the face was flushed and anxious. The patient was aware of the approach of the spasms, saying, "It's coming;" and there was a sense of impending death, he saying, " Good-by ; I'm dying." Under treatment, the boy re- covered within a few days. {Guy's Hosp. Rep., xiv. 266.) Recovery has not unfrequently taken place after comparatively large quantities of nux vomica had been swallowed. Teeatment. — The stomach should be emptied as speedily as pos- sible, either by means of the stomach-pump or by the administration of an emetic. Since the poison, when taken in the form of powder, sometimes adheres tenaciously to the walls of the stomach, the use of the pump, or the action of the emetic, should be continued for some time. Various chemical antidotes have been advised, but none of these are reliable. After the contents of the stomach have been evacuated, vegetable astringents, or a solution of iodine in potas- sium iodide, might be found useful for the purpose of neutralizing any remaining portions of the poison. Other methods of treatment will be referred to hereafter, when considering the antidotes for poisoning by strychnine. PoST-MOETEM ApPEAEANCES. — Nux vomica may occasion death without leaving any well-marked morbid change in any part of the body. In Mr. Ollier's case, before cited, in which death took place in an hour, five hours after death the body was as straight and stiff as a statue, so that if one of the hands was moved the whole body moved with it. On dissection, the stomach was found nearly natural, the blood-vessels of the brain congested, and the heart of a pale color, CHEMKAL PIIOPERTIES, 641 t-mply, and ilaccid. In another case, in wliidi ahont an ounce (tf the poison had been taken and proved rapidly fatal, large (piantities of a sangninok'nt fluid were found in the cavities of the brain and be- tween its membranes ; and the lungs, as well as the heart, were highly gorged with black lluid blood. The stomach was healthy, except a j)atch of the nuicous membrane in the larger curvature of the organ, which was evidently inflamed, and of a deep red color, the intensity diminishing from the circumference to the centre. In the case cited from Orfila, in whidi death did not take place until the fourth day, tlie following appearances were observed forty- eight hours after death. The body was considerably rigid, and of a violet hue. The lateral ventricles of the brain, and the cavity of the arachnoid membrane, contained large quantities of serum; but no a})preciable alteration was detected in either the meninges or the cere- bral substance. The internal surface of the stomach presented at different points a color which varied from red to deep black ; and the duodenum and upper portious of the small intestines were manifestly inflamed. The lungs were gorged with blood ; the heart was natural. Chemicai- Properties. The physical properties of nux vomica, when 'in its solid state, readily distinguish it from all other substances. If a small portion of the powdered seed be moistened with a drop of water, and exam- ined under a low power of the microscope, the broken fibrous hairs may be readily distinguished, they apparently forming a large por- tion of the powder. The hairs acquire a yellow color upon the addition of a solution of iodine in potassium iodide; when the crude powder is thus treated, it assumes a deep brown color. When touched with a drop of concentrated nitric acid, the powder acquires a deep orange-red color, which is slowly discharged by a solution of stannous chloride. Concentrated sulphuric acid causes it, like most vegetable powders, to assume a brownish, then black color. Hydro- chloric acid produces little or no change. When moderately heated, the powder evolves dense, white fumes having a peculiar odor ; at higher temperatures it becomes ignited. When powdered nux vomica is macerated in water or diluted alcohol, the liquid takes up the strychnine and brucine, as salts of their peculiar acid, and more or less coloring matter: this extraction is much facilitated by a moderate heat. The solution thus obtained 542 STRYCHNINE. has an intensely bitter taste, strikes a red color with nitric acid, and yields a copious reddish-brown precipitate with a solution of iodine in potassium iodide. It acquires a greenish hue when treated with a solution of a ferric salt; ammonio-copper sulphate produces a somewhat similar coloration, and, after a time, a greenish-white precipitate. Tannic acid throws down from the solution a copious, dirty-white precipitate. It is obvious that there can be no chemical test by which the presence of nux vomica as a whole, when in a complex organic mix- ture, can be directly shown ; but this may be inferred by proving the presence of one or more of its peculiar principles. Of these principles, strychnine is usually much the most easy of detection. Since, however, this alkaloid is so frequently met with in its pure state, or that of some of its salts, its mere detection would not, independent of other circumstances, prove the presence of nux vom- ica. The methods for the separation of strychnine and brucine from organic mixtures of the crude drug are the same as those for their recovery from organic mixtures in general, as will be pointed out hereafter under the special consideration of these alkaloids. II. Stryehniiie. History. — Strychnine, or strychnia, was discovered, in 1818, by Pelletier and Caventou, both in the seed of Strychnos nux vomica and the St. Ignatius' bean, which latter is the seed of the Strychnos Ignatii. Thus far it has been found only in five species of the Strychnos genus of plants, and in most of these it is accompanied by brucine. Several of the species of this genus of plants con- tain neither strychnine nor brucine. The composition of strychnine, in its anhydrous state, according to Regnault, and since confirmed by Nicholson and Abel, is C21H22N2O2 ; molecular weight 334. Ac- cording to most analysts, strychnine forms something less than one-half per cent, by weight of nux vomica ; Mr. Horsley, however, states that he obtained about one per cent, of the alkaloid from that substance. From the St. Ignatius' bean Pelletier and Caventou obtained from one to two per cent, of the alkaloid. Preparation. — Strychnine may be obtained from nux vomica by the following process. The rasped seeds are digested for twenty- four hours in water acidulated with hydrochloric acid, the decoction then strained through linen, the strained liquid concentrated to a PHYSIOLOGICAL EFFECTS. 543 small voluiMc, ami tlicn j)recipi(at('(l with milk of" liruo; the pre- cipitate tliiis produced is collected on a cloth, washed with cold water, tlien dried, and the pulverized nia.ss exhausted witli suc- cessive portions of alcohol until dej>rived of its bitterness. The mixed alcoholic liquids are concentrated on a water-i>ath, and then treated with water containino; a little sulphuric acid, by which the strvchnine will be dissolved in the form of sulphate. This solution is boiled with animal charcoal, filtered, concentrated to a small volume, and the alkaloidal sulphate allowed to sejiarate by crystal- lization. The crystals may now be dissolved in pure water, and the alkaloid precipitated by slight excess of ammonia, then collected on a filter, Avashed with cold water, and allowed to dry. As thus ob- tained, strychnine usually contains more or less brucine. Mr. Horsley's method for preparing the alkaloid consists in first exhausting powdered nux vomica by repeated extractions with water strongly acidulated with acetic acid. The united acid liquids are then filtered, and the filtrate evaporated to a syrupy consistency. The cooled residue is diluted with water, slight exce&s of ammonia added, and the mixture allowed to re])Ose for one or two days. Any crystals thus obtained are washed, dried, then redissolved in water containing acetic acid, and the solution filtered. The liquid is now treated with a solution of potassium chromate, by which the alkaloid is precipitated as strychnine chromate. This is collected, washed, then digested in a solution of ammonia, when, the chromic acid uniting with the ammonia, the strychnine separates in its pure state. Strychnine is one of the most virulent poisons known. It is found in the shops both in its free state and in the form of some of its salts ; its principal salts are the sulphate, the hydrochloride, or muriate, and the acetate. The ordinary medicinal dose of strych- nine, or of any of its saline combinations, is about one-sixteenth of a grain. Symptoms. — These are the same in kind as those produced by nux vomica, but they usually manifest themselves even more promptly. The first symptoms are usually a sense of oppression and great anxiety, with quivering and spasmodic movements of the muscles of the extremities. These effects are sooner or later suc- ceeded by violent muscular convulsions, in which the head is thrown back, and the whole body is rigidly stiff, the extremities being ex- tended, the hands firmly clinched, and the feet arched. In this 544 STEYCHNIiSrE. state, the jaws are usually firmly closed, the eyes prominent, the pupils dilated, the face livid, the expression anxious, and often foam issues from the mouth ; the muscles of the chest and dia- phragm are also strongly contracted, and the respiration is appar- ently arrested ; the pulse is either very rapid or altogether imper- ceptible. In a little time, varying from less than a minute to several minutes, this tetanic condition usually entirely disappears, and there is a state of calm. During this state the patient feels extremely weak, usually experiences great thirst, and is sometimes inclined to sleep. After a little time, however, the system again becomes excited, the special senses being exceedingly acute, and frequently there is a sense and declaration of impending death. A second paroxysm may now be induced by very slight causes, or it may appear wnthout any apparent cause. Not unfrequently the patient is perfectly conscious of the approach of the attack, and desires to be held or rubbed. After a succession of attacks, varying from two to several, death takes place either during a paroxysm from asphyxia, or, more frequently, soon after from complete ex- haustion. The interval between the paroxysms has varied from a few minutes to more than half an hour. The intellect usually remains clear up to the time of death. In a case reported by Dr. Blumhardt, in which a young man, for the purpose of self-destruction, swallowed forty grains of strychnine, the following symptoms were observed. The patient soon experienced great anxiety and agitation, and after the lapse of fifteen minutes, an emetic having been administered, but with the effect of producing only slight vomiting, he lay stiff upon his back, with the head some- what bent backwards ; the lower extremities were perfectly stiff, but the upper still free ; the countenance was pale and haggard ; the pulse quick and contracted. He still spoke with a firm voice and in a col- lected manner, but trismus was evidently commencing. The attacks soon became more violent, and the spasms extended to the muscles of the chest ; the thorax appeared compressed, and the respiration was impeded. The paroxysms were now repeated at intervals of about a minute, for a short time, when the whole body became affected and as stiff as a board. The suffocation was now extreme ; the jaws firmly locked together ; the upper extremities firmly flexed at the elbow-joints and applied across the chest ; the lower extremities extended and stiff, and the soles of the feet concave. By degrees the resj^iration became PHYSIOLOGICAL EFFECTS. 545 more une(|iial, and liiially ccasod ; the pulse hecaiiui imperceptible; the skin of a dusky hlue coh)r ; the face deep purple ; the eyes promi- nent, and the pupils dilated and insensible. All signs of conscious- ness soon disappeared, and the patient lay for a few minutes without motion, in a state of universal tetanus. A remission of the convul- sions now suddenly manifested itself; the limbs became relaxed, and after a long, deep-drawn inspiration the pulsations of the heart and arteries were again perceptible ; consciousness and the power of speech were also restored, but the articulation was imperfect. After about fifteen minutes the patient was again seized with a shivering fit, followed by general tetanus, which soon terminated in a state of asphyxia, and death took place an hour and a half after the poison had been taken. {American 3Ied'ical Intelligencer, ii. 28.) The following case of recovery is related by Dr. Powel. {Lancet, Aug. 1861, 169.) A woman, aged twenty-eight years, took not less than two or three grains of strychnine on an empty stomach. When first seen by the physician, over half an hour afterward, she was lying on her back on the floor, quite sensible ; the arms and legs were stretched out to their fullest extent ; hands clinched ; toes flexed ; legs close together, and the body in a state of opisthotonos. The countenance was livid and anxious ; the eyes staring and fixed, pupils widely dilated, conjunctivae highly injected ; teeth firmly clinched. The breathing was irregular, and at times almost ceased; skin hot, and bathed in perspiration ; pulse rapid and scarcely per- ceptible. The spasms relaxed at times, but did not entirely cease for one minute. On the slightest touch of the body or legs, or on an attempt to give her drink, she would cry out, "My legs! my legs! hold me ! hold me I" then utter a shriek, and quickly relapse into a most violent spasm involving the entire body. Under the adminis- tration of chloroform the convulsions became less severe. While under the influence of the anaesthetic, an emetic was administered, and produced some vomiting. For some hours the spasms recurred about every five minutes, but with decreasing severity, and finally the woman fully recovered. In a few of the reported cases of strychnine poisoning, the first symptom observed was the utterance of a loud cry or shriek; and at least two instances are recorded in which the tetanic symptoms were preceded by vomiting. (Dr. J. St. Clair Gray, Strychnia, 1872, 46.) In an instance of the former kind, in which we were recently consulted. 546 STRYCHNINE. a woman about her ordinary work suddenly exclaimed, Oh! and quickly fell, saying her feet had given out ; violent tetanic symptoms speedily ensued, followed by death. The time within which the symptoms first manifest themselves in strychnine poisoning has varied from a few minutes to some hours ; but they do not often appear much before fifteen minutes, nor are they often delayed much beyond half an hour. In a case reported by Dr. G. F. Barker {Amer. Jour. 3Ied. Sci., Oct. 1864, 399), a young, healthy, married woman had administered to her, with criminal intent, not exceeding six grains of strychnine, and violent symptoms were present in th^^ee minutes afterward ; these were succeeded by several convulsive paroxysms, and death during a paroxysm in thirty minutes after the poison had been taken. In this instance the strychnine was taken in its dry state into the mouth and washed down with water. This is perhaps the most rapid case, in regard to the a})pearance of the symptoms, yet recorded. In the case of Dr. Warner, of Ver- mont, who by mistake took, it is believ^ed, something less than half a grain of the poison, well-marked symptoms were present within five minutes, and death occurred in about eighteen minutes. In at least three other cases the symptoms were about equally prompt in appearing. On the other hand. Dr. H. G. Thomas, of Alliance, Ohio, has reported a case in which a man swallowed jive grains of strychnine, and one hour and three-quarters elapsed before any symptoms mani- fested themselves ; and, under the use of emetics, the patient recov- ered. One of the most remarkable cases of this kind yet recorded is the following, reported by Dr. T. Anderson. A gentleman took by mistake, believing it to be a salt of morphine, three grains and a half of strychnine, and experienced no particular symptoms until two hours and a half afterward, when he suddenly fell backwards ; but, on being immediately raised, he was able to walk home, although exceedingly nervous and alarmed. He soon felt better, and in five hours after taking the dose he again took a similar quantity. In less than ten minutes after taking the last dose he was seized with violent tetanic spasms, which continued, with the usual intermissions, for several hours, after which he entirely recovered. {Amer. Jour. Med. Sci., April, 1848, 562.) The form in which the poison is taken, and the condition of the stomach, may to some extent determine the time at which the symptoms first appear ; but several instances are re- EFFECTS OF EXTERNAL APPIJCATION. 647 conlod ill wliicli the symptoms were delayed niiieli beyond the orili- nary period, even under conditions apparently the most favorable for their development. It need hanlly be remarked that the effects of strychnine may be nnuh modified by the ])resenoe of another poison. A case of tills kind, in which tiu'ee grains of strychnine and one drachm of opium were taken and no serious symptoms appeared for nearly twelve hours, has already been mentioned (Introduction, 39). The fol- lowing somewhat similar case may also be cited. A yoimg drug- gist, with suicidal intent, swallowed, at half-past eight o'clock in the evening, between eight and ten grains of nitrate of strychnine in an ounce of bitter-almond water. A little later, he took an additional dose of twelve grains of strychnine. Feeling nothing peculiar, he took at nine o'clock ten grains of acetate of morphine dissolved in an ounce of bitter-almond water, and then lay down in bed. Ten minutes later, to hasten his death, he poured some chloroform on his pillow. Partial insensibility now manifested itself, and continued for about an hour and a half, when he was seized with violent cramps and cessation of respiration, but without pain. Loss of con- sciousness then supervened, but he soon revived, and had another attack of convulsions. Emetics and tannic acid were now admin- istered ; and iu two days afterward no trace of the poisoning re- mained. {Amer. Jour. Med. Sci., Jan. 1863, 259.) Recovery in this case has been ascribed to the fact that the patient, before taking the poison, had partaken freely of a soup made with flour and a species of cranberries. These latter contain tannin, an agent which is said to neutralize strychnine ; and the farinaceous matters, by enveloping the poison, may have prevented its absorption. In another case, a young woman having taken about one grain and a half of strychnine, and immediately afterward two ounces of lauda- num, symptoms of opium poisoning appeared in four hours; but the effects of the strychnine did not manifest themselves until about eight houis after the poison had been taken. Under treatment, the woman entirely recovered. {3Iedical Times, Dec. 1882, 175.) The extei^al application of strychnine may be attended with serious and even fiatal consequences. In a case related by Dr. Schuler, something less than the twelfth of a grain of pure strych- nine was introduced into the corner of the eye of a man affected with amaurosis. In less than three or four minutes the patient's 548 STRYCHNINE. face became livid, and he was seized with spastic yawnings and vertigo. These symptoms increased, and loss of speech and pulse, with convulsive respiration and violent tetanic shocks, ensued. Death seemed inevitable, but, under the action of remedies, all the symptoms passed off in less than half an hour. [Amer. Jour. Med. Sci., Oct. 1861, 573.) It was formerly believed that strychnine, when given in fre- quently repeated small doses, never accumulates in the system ; but this result has occasionally been observed. Thus, Dr. Dutgher re- lates a case in which he administered to a middle-aged woman, affected with partial paralysis of the muscles of deglutition, the fifth of a grain of strychnine daily, in divided doses, for nine days, with- out any effect other than a gradual improvement of the paralytic condition. But on the morning of the tenth day the patient was seized with pretty severe tetanic spasms, which continued, at inter- vals of about twenty minutes, for several hours, when they ceased, and the patient recovered without any vestige of the paralysis re- maining. [Med. and Surg. Reporter, Philadelphia, July, 1865, 2.) It will be observed that the entire quantity of strychnine taken in this case did not exceed two grains. A fatal case apparently of this kind was communicated, by Mr. Cooper, to the late Dr. Pereira. [Mat. Med., ii. 548.) A Swede, affected with general paralysis, was given one-eighth of a grain of strychnine three times a day for several weeks. The dose was then increased to one-quarter of a grain, and afterward to half a grain, with the same frequency, for many days, without any marked effect. But one morning the patient was found insensible, the face and chest of a deep purple color ; the respiration had ceased, and the whole body was in a state of tetanic spasm and rigid. The symptoms passed off, and the man became apparently sensible ; but another paroxysm soon occurred, and proved rapidly fatal. In regard to the dia^gnosis of strychnine poisoning, the only dis- ease with which its symptoms could be confounded is tetanus arising from ordinary causes. But there is rarely any difficulty in deter- mining the true nature of the case. Thus, in poisoning the symp- toms appear suddenly in a violent form ; the muscles of the hands are the first, and those of the jaws the last, to become affected ; there is usually a complete intermission in the symptoms ; and they rapidly run their course, rarely lasting over a few hours at most. On the PERIOD WHEN FATAL. 549 other hand, in the disease the symptoms are slowly developed; the muscles of the jaws are the first, and those of the hands the last, to become involved ; there is at most only a remission of the rif:;id state of the system; and death rarely occurs within twenty-four hours, the case often being protracted for several days. Dr. Ham- mond states that in ordinary tetanus, epigastric pain, due to spasm of the diaphragm, is an early and prominent symptom ; whereas in strychnine poisoning this symptom is absent. {Diseases of (he Nenmis System, 555.) Pain in the epigastrium has, however, been present in strychnine poisoning; and also in several instances of poisoning by nux vomica. Period when Fatal. — A case is recorded in which a young man, through the ignorance of a druggist, took one grain and two-thirds of strychnine, with the same quantity of nux vomica, and " he very soon afterward complained of some extraordinary sensations, and almost immediately expired." {Amer. Jour. Med. Sci., April, 1854, 537.) In a case privately communicated to Dr. Taylor, ten grains of strychnine, given in mistake for sulphate of quinine, proved fatal in ten minutes. {On Poisons, 781.) In the case of Dr. Warner, already mentioned, death occurred in about eighteen minutes after the poison had*been taken. Dr. Geoghegan, of Dublin, relates an instance in which five grains proved fatal in from twenty to twenty- five minutes; and in Dr. Barker's case, already cited, six grains caused death in about thirty minutes. In a case described by Dr. Theinhart, in which nearly thirty grains of the poison were taken, violent symptoms appeared in about fifteen minutes, and, after four convulsive paroxysms, death occurred in half an hour. {Amer. Jour. Med. Sci., Jan. 1848, 303.) Dr. Gray mentions an instance in which death. occurred in five minutes after the invasion of the symptoms. On the other hand, in the well-known case of Cook, poisoned by Palmer, the symptoms were delayed for nearly an hour, and death occurred in about an hour and a quarter after the poison had been taken. We have elsewhere recorded a case in which a man named Freet took an unknown quantity of the poison, and violent symp- toms appeared Jn about half an hour, but death did not take place until an hour later. {Ohio Medical and Surgical Journal, March, 1864, 95.) In a case described by Dr. Steiner, — that of Dr. Gardi- ner, of Washington City, — death did not occur until after the lapse of three hours and a half, although violent symptoms were present 550 STJRYCHNINE. shortly after the poison had been taken. {Report on Strychnia, Phila- delphia, 1856.) A still more protracted case has been reported by Dr. Paley, in which death did not occur until after the lapse of about tive hours. (Med.-Chir. Rev., Oct. 1860, 382.) Dr. J. J. Eeese, of Philadelphia, reports the case of a woman, in which death was de- layed for from five to six hours. {Amer. Jour. Med. Sd., Oct. 1861, 409.) At a subsequent trial of this case, as personally informed by Wm. H. Miller, Esq., who was engaged in the trial, it fully appeared in evidence that the deceased had taken from five to six grains of the poison, and death was delayed something over six hours. The most protracted case in this respect yet reported is related by M]\I. Tardieu and Roussin [Ann. d'Hyg., July, 1870, 128j, in which an abandoned young woman survived the effects of a large dose of the poison for a period of about eighteen hours after the symp- toms first appeared, the woman being intoxicated when first seen. On inspection, eleven grains (.71 gramme) of solid strychnine were found adherent to the mucous membrane of the stomach ; about three grains of the absorbed poison were extracted from the tissues. Fatal Quantity. — There seems to be much difference in the sus- ceptibility of different persons to the action of strychnine. Dr. G. B. Wood mentions an instance in which a lady was thrown into violent and even alarming spasms, almost threatening suffocation, by one- twelfth of a grain of strychnine. [Therapeutics, i. 834.) In a case related by M. Duriau, one-sixth of a grain taken by a woman, aged twenty-eight years, produced in ten minutes afterward violent* tetanic convulsions, in which the whole body became rigid ; similar attacks ensued at intervals of a few minutes between each, and these were succeeded by a sense of burning in the epigastrium and. pharynx, and great irritability of the stomach, which lasted for not less than six weeks. [Amer. Jour. Med. Sci., Oct. 1862, 562.) In the case of Dr. Warner, it is believed that not over half a grain of sulphate of strych- nine had been taken. This seems to be the smallest quantity that has yet proved fatal to an adult. In a case reported by Dr. Ogston, three-quarters of a grain destroyed the life of a man in three-cj^uarters of an hour; and Dr. Watson relates an instance in which a similar quantity caused the death of a girl, aged twelve years, in about one hour. Mr. Bennett describes a case in which one grain and a half caused the death of a girl, aged thirteen years, in two hours and a half {Lancet, Aug. 1850, 462); and Mr. C. Bullock relates a case FATAr, (QUANTITY. 551 {Amer. Jour. Phai^n., July, 1870, 309) in wlilch a similar quantity proved fatal. Dr. Pcreira {Mat. Med, ii. 549) cites the instance of a ladv who died in less than two hours from the effects of between two and three grains ol' the jmison. Recovery has not unfrcciucntly taken place after comparatively large quantities of strychnine had been taken. A case of this kind in which five grains were taken, and another in whi(rh seven grains were taken in two doses of three and a half grains each at an interval of five hours, have already been cited. Wharton and Stille quote three instances of recovery in each of which four grains of the poison had been swallowed {3fed. Jur., 624) ; and a fourth case of this kind is reported by Dr. Lescher, of Illinois, and still another by Dr. AValler {MecL and Surg. Reporter, Philadelphia, Oct. 1865, 277). In another instance, related by Dr. Givens, a young man swallowed, with suicidal intent, two large pills containing not less than ten or twelve orains of strvchnine. Violent tetanic spasms soon ensued, and continued for five hours. In seven iiours the spasms entirely subsided, leaving the patient quite prostrated, with much distention and tenderness of the epigastrium, and stricture and soreness of the throat, and of the muscular system in general. These effects gradu- ally passed off, and in less than a week the patient >vas nearly well. Soon after the patient had taken the poison, vomiting occurred, but it is not certainly known that the pills were ejected. [Med.-Chir. Rev., April, 1857, 502.) In a case reported by Dr. Wilson [Amer. Jour. Med. ScL, Jidy, 1864, 70), a young man, twenty-two years of age, recovered in about fifteen hours, although it is believed that he had taken forty grains of strychnine. There is, however, in this instance niucli uncer- tainty as to the quantity of poison really taken; moreover, there seems to have been very early vomiting. In a case reported by Dr. Clark, a man laboring under delirium tremens swallowed over twenty grains of the poison, and eighteen hours afterward he was convales- cent. {Buffalo Med. and Surg. Jour., Nov. 1866, 135.) In this case, also, there was early vomiting. After the action of the emetics, the patient was kept under tiie influence of chloroform for eight con- secutive hours, during which time all attempts to suspend its use were attended with a recurrence of the convulsions. In a more re- cent case, a young man, aged nineteen, voluntarily swallowed over thirty grains (two grammes) of crystallized strychnine at midnight 552 STRYCHNINE. after a full meal. When iirsl seen, at five o'clock the next morning, he was found in tetanic convulsions. Olive-oil, brandy, laudanum, and other remedies being employed, the patient was completely re- stored four days after taking the poison. (New Remedies, April, 1879, 117.) in a case recently reported by Dr. W. T. Parker, Assistant Surgeon U.S.A., a colored soldier, aged twenty-three years, fully recovered after having eaten, it is believed, about fifteen grains of solid strychnine. {Medico-Legal Journal, Dec. 1884, 375.) Treatment. — This consists in the speedy administration of an emetic or the employment of the stomach-pump. As an emetic, finely-powdered mustard or zinc sulphate may be employed. The action of the emetic should be aided by the free use of warm demul- cent drinks. On account of the difficulty of swallowing, or the rigid state of the jaws, it is sometimes impossible to resort to the use of emetics or the stomach-pump. Of the various remedies that have been proposed, the internal administration of chloroform, as first employed by Dr. Dresbach, of Tiffin, Ohio, seems to be much the most efficient. In a case in which a man had by mistake swallowed a solution of three grains of strychnine, and most violent symj)toms were present in twenty minutes, Dr. Dresbach administered two drachms of chloroform, and there was complete relief in less than twenty minutes afterward. {Amer. Jour. Med. Sci., April, 1850, 546.) In another instance, related by Dr. J. E.. Smith, the inhala- tion of the vapor of chloroform was attended with similar results. [Ibid., July, 1860, 278.) Another case of this kind, in which four grains of strychnine had been taken, is reported by Dr. Bly. {Neio York Jour, of Med., Nov. 1859, 422.) So, also, in a case communi- cated to Dr. G. B. Wood, in which a robust young man had taken four grains of the poison and was seized with the most violent tetanic spasms, complete recovery took place under the use of chloroform, given both internally and by inhalation. (Z7. >S'. Dispensatory, 1865, 1357.) In this case it is stated that it was necessary to keep the patient under the influence of the chloroform for thirteen consecutive hours, during which two pounds were consumed by inhalation. Two drops were given every five minutes by the stomach, when the mouth could be opened. In a case related by Dr. G. W. Copeland, a man knowingly took five grains of strychnine, and was fully restored under the inhalation of chloroform continued for eleven hours. At no time in this instance was there vomiting, although twenty grains ANTIDOTES. 553 of zinc siilplKitc liad been given. {Lancet and Observe)-, Cincinnati, Jan. 1874, 41.) As a choniical antidote, tannic acid lias been strongly advised ; and Dr. Kurzak, of N'ienna, luis performed a series of experiments upon inferior animals, iVoin wliidi it wonld apiu'ar that this substance, if administered early, has the property of suspending the action of tlie poison. He states that about twenty-five parts of tannin are required for one part of strychnine. In the absence of tannin in its pure form, a strong infusion of powdered gall-nuts or of green tea might be exhibited. {North American Med.-Chir. Rev., July, I860.)" The utility of this acid is supposed to depend upon its uniting with the poison to form tannate of strychnine, which is in- soluble in water, but readily soluble in acids. M. Bouchardat recom- mends, as an antidote, a solution of iodine in potassium iodide. The precipitate produced by this mixture is somewhat less soluble in diluted acids than that occasioned by tannic acid. It need hardly be remarked that neither of these substances should be relied on to the exclusion of emetics or the stomach-pump. Among the other sub- stances that have been recommended as antidotes may be mentioned chlorine, bromine, animal charcoal, camphor, and lard, or fat. A case in which four grains of strychnine had been taken and recovery took place under the use of emetics and camphor, is related by Dr. Rochester. {Buffalo Medical Journal, March, 1856.) Upon physiological grounds, Prof. Houghton was led to believe that strychnine and nicotine (the active principle of tobacco) might be mutually antidotal, and he cites a few experiments on frogs in support of this view. And Dr. O'Reilly, of St. Louis, has related an instance in which, acting upon this suggestion, he adminis- tered, in divided doses, an infusion of an ounce and a quarter of tobacco to a man who had taken six grains of strychnine, and the patient recovered. {3Ied.-Chir. Review, Oct. 1859, 387.) Since, however, in this instance, previous to the administration of the alleged antidote, an emetic had been given and operated, it is not certain that the recovery was in any way due to the effects of the tobacco. Another instance in which an infusion of tobacco was employed, and the patient recovered, has been reported by Dr. Chevers, of Calcutta. {Ibid., Jan. 1867, 243.) But in this instance, also, there seems to have been vomiting prior to the administration ), the strychnine reaction may still be obtained, provided only a small quantity of the mixture be employed ; but in the presence of fhrc<' parts of morphine the reaction is no longer niarked, even with a minute quantity of the mixture. When these alkaloids exist in the same solution, they may be separated by rendering the mixture alkaline and agitating it with chloroform, in which the strychnine is very freely soluble, whilst the morphine is almost wholly insoluble, especially in the presence of a free alkali. It is therefore obvious that when strychnine has been extracted from organic mixtures by means of chloroform in the manner to be pointed out hereafter, this interference on the part of morphine to the color test does not exist. Experiments show that this is true, under certain conditions, of the chloroform extract obtained from a strongly alkaline mixture containing one hundred parti of morphine with only one part of strychnine, even when only 1-lOOOth grain of the latter alkaloid is present. It is obvious, from what has been stated, that a given quantity of chloroform could extract from an alkaline mixture .of strychnine and morphine only a very minute and limited trace of the morphine, whether only that trace or very many times that quantity of the alkaloid was })resent : hence, if that minute quantity (or more) of morphine was present with only a still less quantity of strychnine, the chloroform residue might then fail to respond to the color test for strychnine. Since morphine is still less soluble in pure ether than in chloro- form, this liquid may equally be employed for the separation of these alkaloids, especially if after the addition of the alkali the mixture be allowed to stand some minutes before being agitated with the liquid. It should be remembered, however, that strychnine is much less soluble in ether than in chloroform. For the separation of strychnine and morphine, it has been proposed to precipitate the strychnine by a solution of potassium dichromate. But as this reagent also jiroduces precipitates in strong solutions of salts of morphine, especially after standing some time, and, also, as the chromate of strychnine is but little less soluble in water than the pure alkaloid, it is obvious that we might have a 568 STRYCHNINE. mixture of these alkaloids the precipitate from which would consist largely, or even entirely, of chromate of morphine ; and, moreover, that even under the most favorable circumstances a given quantity of the strychnine would reinain in solution, and thus entirely escape detection. In the presence of a free alkali potassium dichroraate is converted, in part at least, into the monochromate, which is a more ' delicate precipitant of morphine than of strychnine. Brucine, the alkaloid associated with strychnine in nux vomica, has the property even perhaps to a greater extent than morphine of disguising the color reaction of strychnine. Thus, a residue consisting of 1-lOOth grain each of strychnine and brucine fails to give, under the test, any indication of the strychnine ; a mixture of 1— 1000th grain each yields only a faint reaction ; but a mixture of l-10,000th grain each of the alkaloids yields very satisfactory evi- dence of the presence of strychnine. So, also, 1-1 0,000th grain of strychnine with 1-lOOOth grain of brucine yields little or no colora- tion ; but 1-lOOth grain of strychnine with 1-1 000th grain of brucine yields a very marked reaction, although somewhat masked. This interference on the part of brucine applies equally whether potassium dichromate, potassium ferricyanide, or manganese dioxide be era- ployed as the oxidizing agent. Although commercial strychnine generally contains more or less brucine, the latter is perhaps never present in sufficient proportion to interfere seriously with the color test for strychnine. These alka- loids may, at least for the most part, be separated, if not in only minute quantity, by treating a strong aqueous solution of their sulphates or acetates with very decided excess of ammonia, when the strychnine will be precipitated, whilst the brucine will remain in solution. Or, the alkaloids may be dissolved in hot absolute alcohol, which on cooling will deposit the strychnine, the brucine remaining in solution. Messrs. Dunstan and Short have recently advised a method, based upon the difference in the solubility of the ferro- cyanide of strychnine and brucine, for the separation of the two alkaloids. {Amer. Jour. Pharm., Nov. 1883, 579.) This method, however, applies only when comparatively large quantities of the alkaloids are present. Nitrates, such as potassium nitrate, interfere with the normal reaction of the test to nearly or about the same extent as morphine; and the interference applies equally to the different color-developing COLOR TEST: 1 AI.LACIKS. 569 ai>;cMits. Ill ivt:;:ir(l to the iiilluciice oi" tartar emetic, our own ohscrva- tioiis fully coiilinn those of Mr. Hagcn {Chem. Gaz., 1857, :i97), iiamelv, that this substance may be present even in very large excess without exerting any very marked inlluence; yet, when the mixture contains twenty or thirty parts of the compound, it may entirely disguise the ordinary reaction of the test. These observations are equally applicable in regard to the modifying influence of sugar. Since the nitrates, tartar emetic, and sugar are insoluble in chloro- form and in ether, neither of these substances could be present with strychnine when the alkaloid is extracted from organic mixtures by either of these liquids. A much more serious interference to this test than any yet men- tioned is the presence of certain undefined organic substances fre- quently extracted from complex mixtures by chloroform and by ether. It is no unusual occurrence thus to obtain extracts which fail to reveal the presence of strychnine, even when comparatively large quantities of the alkaloid are purposely added. In f\ict, this is so frequently the case when only a very minute quantity of the poison is present, that, should a suspected extract fail to indicate the presence of strychnine, before concluding that the latter is entirely absent it may be best to add to a separate portion of 'the extract a very minute quantity of the pure alkaloid and determine whether the failure might not be due to this cause. The method for sepa- rating substances of this kind will be considered hereafter. Fallacies. — It has been objected to this test that under its action various other substances, as aniline, curarine, cod-liver oil, pyrox- anthine, papaverine, narceine, veratrine, and sokinine, yield colors somewhat similar to or even identical with those produced from strychnine. When, however, the test is properly applied and ob- served, these objections have little or no practical force. Thus, all these substances, except aniline, unlike strychnine, yield their colors, or at least are colored, by sulphuric acid alone; and, furthermore, none of them, except curarine and cod-liver oil, even by the con- joined action of the acid and color-developing agent, yields, like strychnine, a series or quick succession of colors. Should, however, potassium permanganate be employed as the oxidizing agent, a more or less blue or violet coloration may be developed, in the absence of strychnine, by various other organic sub- stances besides those just mentioned. According to W. T. Sedgwick 570 STRYCHNINE. {Amer. Chem. Jour., Dec. 1879, 369), even bits of filter-paper, woody- fibre, and shreds of cloth may produce under this reagent colors closely resembling those produced by strychnine. From an infusion of JEujjatoj'ium perfoUatwn (boneset) this observer obtained, under the action of the permanganate, a magnificent bluish-purple color, whilst potassium dichromate and manganese dioxide produced no blue coloration whatever. The general chemical nature of some of the foregoing fallacious substances may now be briefly considered. Aniline, in its pure state, is a colorless liquid, having a rather pleasant odor, and a sharp, acrid taste : it is obtained from coal-tar, and by the action of potassium hydrate upon indigo ; it may also be obtained by various other methods. When treated with concentrated sulphuric acid, it undergoes no change of color, but throws down, if present in notable quantity, a white precipitate of aniline sulphate. The salts of this base are colorless, nearly tasteless, and, for the most part, readily crystallizable. The sulphate has been employed as a therapeutic agent. Pure aniline is readily soluble in chloroform, but its salts are almost wholly insoluble in this liquid. When the salts of aniline are treated with concentrated sulphuric acid, they, like the salts of strychnine, yield no coloration ; but when a crystal of potassium dichromate, or a small portion of any of the other oxidizing agents, is stirred in the acid mixture, the latter slowly acquires a yellowish or greenish tint, then presents bluish streaks, and after a little time assumes a beautiful deep blue color, which undergoes little or no change for half an hour or even much longer, but finally becomes nearly or entirely black. It is thus obvious that the reaction of this substance bears but little similarity to that of strychnine, about the only resemblance being in the pro- duction of a deep blue color. But in the case of strychnine, as re- marked by Dr. Guy, this color is the first produced, and is developed either immediately or at most within a few moments, and is quickly followed by other characteristic colors, it being itself exceedingly transient; whereas in the case of aniline this color is but slowly developed, is preceded by other colors, and when once established is exceedingly persistent, and ultimately becomes black. Dr. Letheby reports {Chem. News, v. 71) two cases of accidental poisoning by nitro-benzole, in which he found that it was changed in the animal body into aniline. Curarine is the name applied to the active principle, or alkaloid. COLOR TKST: FALLACIES. 571 found ill Woorara, or Ciirara, tlio substiince employed by the Indians of South America for poisoning their arrows. Much doubt exists as to the true nature of woorara. Accordini; to Waterton, it is pre- pared from several dilferent ])lants, two species of poisonous ants, and the rani2;s of certain snakes; while S(^homl)urgk states that it consists of vegetable matter alone, and chiefly of an extract of the bark of the Strychnos toxifera, a tree found native in Guiana. Vari- ous other statements have been made in regard to its com{)osition. Tliat there are at least several varieties of this substance current among the dilferent tribes of Indians seems to be fully established by the investigations of Drs. Hammond and Mitchell {Amer. Jour. Med. Sci., July, 1859, 13-61); and it is even probable that each tribe hiis its own method for preparing the poison. It was formerly believed that the poisonous properties of woorara \yQve due to the presence of strychnine; but this alkaloid has not been found in any of the specimens yet examined. In fact, the physiological effects of this substance are the very opposite to those of strychnine, and it has even been advised as an antidote in poisoning by that alkaloid. Woorara is usually described as a hard, black or nearly black, brittle, resin-like solid, of an intensely bitter taste ; in the state of powder it has a dark brown color. It is, for the ra9st part, readily soluble in water and in alcohol, but is only very slightly acted upon by ethev and chloroform, even in the presence of a free alkali. The statements in regard to the chemical properties of this substance have been somewhat conflicting. The active principle, or curarine, as ob- tained by MM. Roulin and Boussingault, who were the first to isolate the alkaloid, was in the form of a transparent solid, having a pale yellow color and an exceedingly bitter taste. It, as well as all its salts, was uncrystallizable. According to Bernard, curarine dissolves in concentrated sulphuric acid with the production of a beautiful carmine color; and Pelikan states that under the combined action of this acid and a color-developing agent, as potassium dichromate or a current of electricity, it yields a brilliant red color. It would appear that M. Preyer obtained curarine, as well as its soluble salts, in the crystalline form. [Chem. News, London, July, 1865, 10.) According to this observer, the pure alkaloid yields with concentrated sulphuric acid a magnificent and lasting blue color ; while with this acid and potassium dichromate it yields much the same series of colors as strychnine. With strong nitric acid it yields a purple coloration. 572 STRYCHNINE. A specimen of ordinary woorara, kindly furnished us in liberal quantity by Dr. S. Weir Mitchell, has the following properties, its physical appearances being the same as those just described. When treated in its crude state, with concentrated sulphur ie acid, it slowly yields, without entirely dissolving, a reddish-brown solution, which, when stirred with a small portion of potassium dichromate, or any other oxidizing agent, gives a series of colors very similar to that produced from a very impure mixture of strychnine. Concentrated nit7-iG acid dissolves it, witii evolution of nitrous fumes, to a deep reddish-brown solution. It is for the most part readily soluble in water, especially upon the application of heat ; the insoluble portion consists apparently of vegetable fragments. The filtered aqueous solution has a deep brownish color, an intensely bitter taste, and a just perceptible acid reaction. It is about equally soluble in strong alcohol. The concentrated aqueous solution yields with a solution of potassium dichromate a yellow, amorphous precipitate, which, when washed and treated with a small quantity of concentrated sul- phuric acid, yields a series of colors not to be distinguished from that produced under similar circumstances from the chromate of strychnine. This precipitate, however, differs from the strychnine compound in being uncrystallizable, and rather readily soluble in water. When a strong aqueous solution of several grains of an alcoholic extract of the crude poison is rendered strongly alkaline with potas- sium hydrate and agitated with chloroform, this liquid remains color- less, and leaves, upon spontaneous evaporation, a slight, yellowish, gum-like residue, having an intensely bitter taste. When a minute portion of this residue is touched with a drop of sulphuric acid, it acquires a red color, and very soon dissolves to a solution of the same hue; if a small crystal of potassium dichromate be now stirred in the solution, it produces a series of colors the perfect counterj)art of that from strychnine, with perhaps the exception that the blue and purple colors are somewhat more persistent than those from an equal quantity of the latter substance. Under the action of nitric acid, the chloroform residue assumes a red color, and dissolves to a reddish solution ; this color is discharged by heat, and the cooled liquid remains unchanged on the addition of stannous chloride. The alkaline solution from which the chloroform extract was obtained has an intensely bitter taste, and yields with a solution of potassium COLOR TKST: FA M,A('I KS. 573 iliclii'otiiiito ;i I'atlu'i' coijious aiii()i'|)li()iis jd'ccipitati', liuvinj^ tlie same properties as tlie precipitate (Vdim an aqueous solution of the crude poison. When a small quantity of tlie alkaline solution is treated with sulphuric acid, it acquires a i)eautii"ul purple color, which on the addition of a crystal of potassium dichromate is changed to a deep !)Iue, followed by purple and the other characteristic colors. The alkaline solution also yields other reactions, indicatint; that but little of the active j)rinciple had been removed by the chloroform. Various efforts were made to obtain this princi})le, and some of its compounds, in the crystalline state, but in all cases without success. Tt thus apjiears that this sample of woorara contains a principle having certain chemical properties in common with strychnine. Thus, like strychnine, it has an intensely bitter taste; yields under the combined action of sulphuric acid and an oxidizing agent a ])articular series of colors; and its potassium dichromate precipitate yields, with this acid alone, similar results. But these are about the only respects in which it resembles that alkaloid. Among the dif- ferences existing between this ])rinciple, at least in the sample under consideration, and strychnine, may be mentioned the following: it and all its compounds are uncrystallizahJe ; it is colored by sulphuric acid alone; its potassinm dichromate precipitate is rather readily soluble in water, and is araorj)hous; it is almost wlwlly mso/u6?e in chloroform, and readily soluble in potassium hydrate; and its solu- tions are not precipitated by the caustic alkalies. Three grains of the above woorara administered in solution to a young cat produced no appreciable eflFect whatever ; although the animal w^as closely watched for twelve hours. But a very small quantity of the paste introduced under the skin of the inside of the thigh of a similar animal produced almost immediate stupor, and in eight minutes complete prostration; this condition continued, with occasional convulsive movements, for some hours, after which the animal completely recovered. Cod-liver oil has also been mentioned as a source of fallacy. This substance when treated with sulphuric acid alone yields a series of colors which might be confounded with that produced from strych- nine by the combined action of this acid and an oxidizing, agent. But as strychnine yields no coloration with sulphuric acid alone, it is obvious that when the acid is applied first and its action observed, all grounds for objection, so far as this oil is concerned, are at once 574 STRYCHNINE. removed. Moreover, the physical state of cod-liver oil would at once distinguish it from strychnine, or any of its salts, in the solid state. The objections in regard to the other substances heretofore men- tioned have already been answered, namely, that they are colored by sulphuric acid alone, and under no circumstance do they yield a quick succession of colors. Thus, pyroxanthine, which has a bright red color, yields with the acid a blue solution ; papaverine, a purple ; narceine, a reddish-yellow or brownish ; veratrine, a yellow, slowly becoming crimson ; and solanine, an orange-brown mixture. It may be remarked that the exact tint of color produced by the acid with at least some of these substances is more or less modified by the quantity of material employed. In addition to the substances now considered, there are a number of alkaloids and other organic proximate principles which, when treated either with sulphuric acid alone or with this acid and potas- sium dichromate, give rise to more or less coloration. The action of this test with a number of these substances was first examined by M. Eboli {Chem. Gazette, 1856, 251); then by Dr. T. E. Jenkins, of Louisville, Ky., who extended the investigation to about fifty of these principles {Semi- Monthly Med. News, April, 1859, 214) ; and still more recently by Dr. Guy, of London (Chemical News, Aug. 1861, 113), who added some sixteen substances to those examined by Dr. Jenkins. But of all the substances thus and since examined, exclusive of some already mentioned, none gave results resembling the reactions of strychnine, even to the extent of those already considered. Galvanic Test. — This in principle is the same as the preceding method, only that the oxygen is rendered nascent by a current of voltaic electricity, instead of being evolved from a metallic oxide, by means of sulphuric acid. It may be applied, according to Dr. Letheby, who, we believe, first advised the process (Lancet, June, 1856, 708), by placing a drop of the strychnine solution in a cup- shaped depression made in a piece of platinum-foil, evaporating the liquid at a low temperature, and moistening the residue with a small drop of concentrated sulphuric acid. The foil is then connected with the platinum pole of a single cell of Grove's or Smee's battery, and the acid liquid touched with the platinum terminal of the negative pole. In a moment the violet coloration manifests itself in great intensity. POTASSIUM IODIDE TEST. 575 III reo;ar(l to the doHcaoy of this method, it is much the same as that of tlie test as ordinarily applied. Thus, according to our own ex|)eriments, the 1-1 0,000th of a grain of strychnine yields a fine display of colors; and the l-100,000th of a grain, a distinct re- action. Since, however, this process is not so readily applied, and is about equally open to the interferences and so-called fallacies that hold against the ordinary method, it seems to possess no advantage over the latter. In fact, for the detection of very minute traces of strychnine it is less satisfactory than the ordinary method. 3. Potasmim Sulphocyanide. This reagent throws down from solutions of salts of strychnine, when not too dilute, a white crystalline precipitate of strychnine sul- phocyanide, which, according to Nicholson and Abel, has the com- position CojH^vjNoOjjHCyS. The precipitate is insoluble in excess of the precipitant, and but sparingly soluble in diluted acetic and hydrochloric acids. 1. Yw gi'sin of strychnine, in one grain of water, yields an imme- diate crystalline deposit, and in a few moments the mixture becomes a nearly solid mass of crystals, of the forms shown in Plate X., fig. 2. 2. YoVu grain : on stirring the mixture, in a very little time it throws down crystals, and soon there is a very satisfactory deposit. 3. 57nro grain yields, especially if the mixture be stirred, after some minutes, a satisfactory deposit of crystalline needles. Potassium sulphocyanide also produces white crystalline precipi- tates in solutions of several other alkaloids. 4. Potassium Iodide. Somewhat strong solutions of salts of strychnine yield with potas- sium iodide a white crystalline precipitate, which is insoluble in excess of the precipitant and in the free alkalies, and only slowly soluble in large excess of acetic, nitric, and hydrochloric acids. The formation of the precipitate is much facilitated by stirring the mixture with a glass rod. 1. Yoo" gi'^in of strychnine: in a few moments the mixture becomes a nearly solid mass of crystals, of the same forms as those pro- duced by the preceding reagent (Plate X., fig. 2). 576 STEYCHJS^INE. 2. YWWQ gi'^^" • after a few minutes, especially if the mixture be stirred, a quite good deposit of stellate groups of crystals. 3. g-oVo" gi'aiu : after several minutes there is a quite satisfactory crystalline deposit. The precipitates produced by this and the preceding reagent cannot readily be confirmed by the color test. 5. Potassium Dichr ornate. This reagent produces in solutions of salts of strychnine a bright yellow precipitate of strychnine chromate, which almost immediately becomes crystalline. The precipitate is insoluble in excess of the precipitant, and in acetic acid, and only very sparingly soluble in diluted nitric acid, but readily soluble in the concentrated acid. The fixed caustic alkalies slowly decompose the precipitate, with the elimination of pure strychnine, which, unless from dilute solutions, assumes the crystalline form, and may be extracted by chloroform. This liquid will also extract portions of the pure alkaloid from aqueous mixtures of the chromate, without dissolving a trace of the latter. From dilute solutions of strychnine the reagent produces no immediate precipitate, but the latter separates after a time in the crystalline form; under these circumstances the formation of the precipitate is much facilitated by stirring the mixture with a glass rod. 1, ^A_ grain of strychnine yields a very copious precipitate, which in a very little time becomes a dense mass of bush-like crystals. 2, g^ grain : an immediate deposit, and very soon a copious, crys- talline precipitate. If after the addition of the reagent the mixture be allowed to remain quiet, the precipitate, after a little time, forms beautiful dendroidal groups of crystals, Plate X., fig. 3. 3, ^^1^^ grain yields no immediate precipitate, but very soon crystals appear, and in a few minutes there is a quite good deposit. If the mixture be stirred, it quickly yields a very good crystalline precipitate. 4, yJL^ grain : on stirring the mixture for a few moments it yields streaks of granules along the path of the glass rod, and soon a quite good deposit of octahedral and bush-like crystals, Plate X., fig. 4. 5, ^-JL_^ grain : if the. mixture be stirred, after some minutes a very POTASSIUftr DICHROMATE TEST. 577 satisfactory deposit of small octahedral crystals and plates ap- pear. ^' Tff.ro'o y;'"dii : when treated with a small quantity of reagent and the mixture stirred, it yields, after several minutes, small granules; after about twenty minutes there is a very satisfac- tory microscopic crystalline deposit of long plates, granules, and small octahedral crystals. If the supernatant liquid be decanted from any of the above deposits, and the dried crystals touched with a small drop of concen- trated sulphuric acid, they immediately assume a magnificent blue color, quiclvly changing to purple or violet, and dissolve to a purple or violet solution, which, passing through various shades, becomes red, then slowly fades iu color. In other words, these crystals may be confirmed by the color test by the simple addition of suljihuric acid. The precipitate obtained from the l-10,000th of a grain of strychnine, iu solution in one grain of water, will, in this manner, yield a magnificent display of colors; and even the least microscopic crystal of the compound, when touched under this instrument with a very minute drop of the acid, will yield a very distinct coloration. It must, however, be borne in mind that a solution of strychnine may be too dilute to yield any precipitate whatever with this reagent, and yet have a distinctly bitter taste, and leave up6n spontaneous evaporation, even of a single drop of the solution, a residue, which when examined by the color test in the ordinary manner, will yield very satisfactory results. Statements have been made in regard to the delicacy of this test which are well calculated to lead to erro- neous conclusions. For the separation of the precipitate, for the application of this confirmatory reaction, from dilute solutions of the alkaloid, it is best to stir the mixture, by means of a glass rod, in a watch-glass, and then allow it to repose for about half an hour, when the crystallized deposit M'ill be found strongly adherent to the glass, and thus permit the ready separation of the supernatant liquid by decantation. Or, the mixture may be allowed to evaporate spontaneously to dryness, and the residue touched with a drop of pure water, which will readily dissolve any excess of the reagent present, while the attached crystals of the strychnine compound will remain. As potassium dichromate also produces yellow crystalline precipi- tates with brucine, narceine, codeine, and some few other principles, 37 578 STRYCHNINE. and amorphous deposits with morphine, narcotine, and a number of other substances, it is obvious that the mere production of even a crystalline precipitate by this reagent is not in itself positive evidence of the presence of strychnine. However, the crystalline form of the strychnine compound as usually produced is somewhat peculiar; and when the crystals yield a positive reaction with sulphuric acid, the results are perfectly unequivocal. Even a positive reaction by this acid from an amorphous deposit would exclude every other known substance, except the active principle of certain kinds of the woorara poison. By this method, therefore, the two most charac- teristic tests yet known for the recognition of strychnine may be applied to the same quantity of the poison. Chroinate of Strychnine which had been preserved for some years, when touched with sulphuric acid failed to yield satisfactory colora- tions; but on the addition of a mineral alkali and extraction with chloroform, the alkaloid was recovered unchanged. Potassium Monochromate occasions no precipitate in neutral solutions of salts of strychnine, unless they be very concentrated. But with acidulated solutions — provided they do not contain very large excess of a mineral acid — it produces results similar to those by the dichromate, due to the fact that the free acid converts the reagent, in part at least, into the latter salt. One grain of a 1-lOOth neutral sohition of the alkaloid yields, especially after a little time, a quite good crystalline deposit, very similar to that produced by potassium sulphocyanide (Plate X., fig. 2). This, however, is very nearly the limit of the reaction of the reagent under these conditions. 6. Auric Chloride. Trichloride of gold produces in solutions of salts of strychnine, even when highly dilute, a yellowish, amorphous precipitate, which after a time becomes more or less crystalline. The precipitate is insoluble in acetic acid, and only sparingly soluble in diluted nitric acid ; when treated with potassium hydrate, it slowly assumes a dark color. 1. Y^ grain of strychnine, in one grain of water, yields a very copious deposit, which at first has an orange-yellow color, but soon becomes yellow and more or less crystalline, forming groups of bush-like crystals and granules. If the precipitate contains even but little foreign matter, it may remain amorphous. PLATINIC CHLORIDE TEST. 579 2. xif(rtr ?^''f^''> ' '^ copious, yellow precipitate, which in a little time becomes converted into jrroups of crystals, Plate X., fij^. 5. 3. "nj-.Voir gi''*'" ' a very satisfactory, yellowish deposit, which soon yields small crystalline groups. 4. -j-s-.ViTiJ g''ii'" • '<^ very satisfactory turi)i(lity. 5. 3-(7.^0-^(5- grain yields a very distinct cloudiness. When the precipitate from ten grains of a l-5000th or more dilute solution of the alkaloid is boiled in the mixture, the deposit dissolves to a clear yellow solution, and it is redeposited with little or no change as the liquid cools; the precipitates from stronger solu- tions, when treated in this manner, do not entirely dissolve, but undergo more or less decomposition, with the deposition of metallic gold uj)on the sides of the tube. Potassium hydrate dissolves the precipitate from a l-5000th solution to a clear liquid ; but the deposit from stronger solutions is not readily soluble in this mineral alkali. Upon the application of heat, the potassium solution acquires a purplish color and throws down a precipitate. Auric chloride also produces yellow precipitates with many other substances, but the crystalline form of the strychnine deposit is some- what peculiar. The formation of these crystals, however, as already intimated, is readily interfered with by the presence of foreign matter. The true nature of the strychnine precipitate, when in not too minute quantity, may be established by gently evaporating the mix- ture to dryness, treating the residue with a small drop of sulphuric acid, and then stirring in the mixture a minute crystal of potassium dichromate, when the strychnine series of colors will be developed. The residue from 1-lOOth grain of strychnine will in this manner readily yield satisfactory results; but 1-lOOOth grain yields little or no coloration. This reaction is much interfered with by the presence of large excess of the gold reagent. 7. Platinio ChloHde. This reagent produces in solutions of salts of strychnine a pale yellow, amorphous precipitate of strychnine chloroplatinate, 2C2iH22X202)HCl ; PtCI^, which soon becomes crystalline. The precii)itate, especially when it has assumed the crystalline form, is insoluble in acetic and diluted nitric acids: it is unchanged in color and only sparingly soluble in the caustic alkalies. 580 STRYCHNINE. 1. YDTT grain of strychnine yields a very copious precipitate, which soon becomes a mass of crystals. 2. YWTo gi'aij'i • a very good deposit, which is soon converted into beautiful crystals, Plate X.,. fig. 6. 3. QQ-QQ grain : on stirring the mixture it yields after a few moments a granular deposit, and after a few minutes a quite good crystal- line precipitate. 4. 3-g-,VoT gJ^aiii yields after a little time, if the mixture has been stirred, a quite satisfactory deposit of stellate groups of crystals and granules. This reagent also produces yellow crystalline precipitates with nicotine, potassium compounds, and ammonia; a granular deposit with morphine; and amorphous precipitates with a number of sub- stances ; but the strychnine precipitate is usually readily distinguished from these by its crystalline form. In mixtures containing much foreign organic matter, however, the strychnine compound may not assume the crystalline state. Palladium Chlotide throws down from solutions of salts of strych- nine a yellow precipitate, which assumes the same crystalline form as that produced by the platinum reagent ; the limit of the reaction is also the same. 8. PicriG Acid. An alcoholic solution of this acid occasions in solutions of salts of strychnine a yellow precipitate of strychnine picrate, which is only sparingly soluble in large excess of acetic acid and in alcohol. The precipitate is readily soluble, to a colorless solution, in sulphuric acid, and the mixture, when treated with a color-developing agent, yields the peculiar strychnine-series of colors ; not, however, in the same intensity as many of the other salts of the alkaloid. 1. Y^ grain of strychnine yields a very copious, amorphous precipi- tate, which slowly becomes converted into a mass of irregular crystalline tufts. 2. Yrro gi'^in • ^ very good precipitate, which soon becomes changed into crystals, having the very singular forms illustrated in Plate XL, fig. 1. 3. i-Q.Voo" grain • on stirring the mixture it yields, after a little time, a very satisfactory granular deposit. 4. -2-6,VoT grain yields after a little time, if the mixture has been stirred, a quite perceptible granular precipitate. POTASSIUM lODOIIVmt AROYRATE TEST. 581 Picric acid also protluces crystal line precipitates with various other substances. The crystalline form, however, of the strychnine coni|)ound is somewhat peculiar. 9. CoiTosive Sublimate. Mercuric chloride throws down from stroni!; neutral solutions of salts of strychnine a white, amorphous precipitate of the double cldoridc of strychnine and mercury which is readily soluble in acids, even acetic acid. After a time the precipitate becomes crystalline. 1. yJt gJ'^i" <^f strychnine yields a very copious precipitate, which in a little time becomes somewhat granular, then changes into groups of radiating crystals, usually attached to a granular nucleus, and aggregations of large granules, Plate XI., fig. 2. The general form of these crystals is readily modified by slight circumstances. 2. 3-J-^ grain: after some minutes the mixture yields a quite satis- factory precipitate of stellate crystals. In solutions but little more dilute than the last-mentioned, the reagent fails to produce a precipitate, even after long repose. 10. Potassium lodohydrargyrate. This reagent may be prepared by dissolving one part of pure corrosive sublimate in one hundred parts of water and then adding just sufficient potassium iodide to redissolve the scarlet precipitate first produced, which will require very nearly four parts of the iodine compound. A small quantity of this mixture throws down from solutions of salts of strychnine a dull white precipitate of the double iodide of strychnine and mercury, which is insoluble in excess of the precipitant and in the caustic alkalies, as well as in acetic and hydrochloric acids. The precipitate is also insoluble in alcohol ; con- centrated sulphuric acid readily decomposes it, with the production of a reddish-brown or purplish color. 1. Yoir gr^^^ of strychnine, in one grain of water, yields a very copious curdy precipitate, which after a little time becomes partly converted into granules and short, crystalline needles. If the reagent contain an excess of potassium iodide, the precipitate assumes the same crystalline form as when this salt alone is employed as the precipitant. 2. Y^^ grain yields a rather copious precipitate. 582 STRYCHNINE. 3. ^Q^^QQ grain : a quite good precipitate, which in a little time becomes converted into opaque granules and short, irregular needles. On the addition of a few drops of acetic or hydro- chloric acid, the precipitate is soon changed into irregular groups of rather long needles. 4. -so-.Too" grain yields a quite distinct precipitate, and in a little time a very satisfactory deposit. This deposit is very similar in appearance to that produced from dilate solutions of atropine by bromohydric acid, as illustrated in Plate XII., fig. 6. 6, YoT/oTo" gi"^iD '• ^^ immediate change, but in a very little time the mixture becomes cloudy, and soon yields a very satisfactory deposit of opaque granules and short, irregular needles. The production of a white precipitate by this reagent is common to solutions of most, if not all, of the alkaloids. 11. Potassium Ferrieyanide. This reagent produces in quite strong neutral solutions of salts of strychnine a yellowish, amorphous precipitate, which in a little time becomes crystalline. The precipitate is only slowly soluble in acetic acid, but readily soluble in the stronger acids, and is, therefore, not produced in their presence. 1. YFo gJ^ai^ of strychnine yields a quite copious precipitate, which in a few moments becomes converted into a mass of beautiful groups of crystals, Plate XL, fig. 3. 2.' -g^ grain : a very good crystalline precipitate. 3. yqTq g^s-i''^ yields little or no indication of the presence of the strychnine, even after the mixture has stood half an hour or longer. When a small portion of the precipitate, occasioned by this re- agent, is treated with a drop of concentrated sulphuric acid, it, like that produced by potassium dichromate, dissolves with the produc- tion of the same series of colors as obtained by the color test as ordinarily applied. The least visible crystal of the deposit will re- spond to this reaction. It will be observed, however, that as a precipitant for strychnine, potassium ferrieyanide in point of deli- cacy is far inferior to potassium dichromate. Sodium Nitroprusside throws down from neutral solutions of salts of strychnine a white or dirty-white precipitate, which assumes the same crystalline form as that produced by potassium ferrieyanide, IODINE TEST. 583 and the limit of the reaction is about the same. Bnt, notwithstand- ing^ the contrary has been asserted, this precipitate, unlike that occa- sioned by potassium ferricyanide, dissolves without change of color in concentrated sulphuric acid. Pofasmim Fcrroci/anide fails to precijiitate solutions of salts of strychnine, unless very concentrated and perfectly neutral. One grain of a 1-lOOtli solution of the alkaloid will yield a quite good crystalline deposit; but this is very nearly the limit of the reaction. 12. Iodine in Potassium Iodide. An aqueous solution of iodine in potassium iodide produces in solutions of salts of strychnine, even when highly diluted, a reddish- brown, amorphous precipitate, which is readily soluble in alcohol, but only very sparingly soluble in acetic acid. The precipitate is readily soluble in potassium hydrate, but it is soon replaced by a white deposit. Dr. W. B. Herapath has shown [Chem. Gaz., 1855, 320) that an alcoholic solution of strychnine yields with iodine, crystalline compounds having very peculiar optical properties. 1. Yoo" grain of strychnine yields a very copious deposit, which after a time becomes more or less crystalline. 2. YWW5 grain : a copious precipitate, which after a time becomes, in part at least, converted into crystals, Plate XI., fig. 4. These crystals are most readily obtained when large excess of the reagent is avoided. 3. YO","oTo gi'ain yields a very good precipitate, which readily dis- solves to a colorless solution in potassium hydrate, but after a little time the mixture becomes turbid. The precipitate is slowly converted into crystalline nodules. 4. 3i5-,-g-(nr grain yields a very satisfactory deposit. 5. TTTtT/Diru" gi'3'Jn furnishes a very distinct turbidity. This reagent also produces precipitates with various organic sub- stances, and with certain inorganic compounds, but the character of the strychnine crystals is quite peculiar; their formation, however, is readily interfered with by the presence of foreign matter. The strychnine may be recovered from the washed precipitate by dissolving the latter in strong alcohol, and treating the solution with slight excess of silver nitrate, which will precipitate the iodine as silver iodide; this is removed by a filter, and the excess of the silver reagent precipitated from the filtrate by the cautious addition 584 STRYCHNINE. of diluted hydrochloric acid ; the silver chloride thus produced is then separated by a filter, and the filtrate evaporated to dryness on a water-bath, when the strychnine will be left in its pure state. This method will serve for the recovery of even extremely minute quan- tities of the alkaloid. 13. Bromine in Bromohydrie Acid. A strong aqueous solution of bromohydrie acid saturated with bromine occasions in solutions of salts of strychnine, even when very dilute, a yellow, amorphous precipitate, which is readily soluble in alcohol, and in acetic acid. The precipitate remains amorphous. 1. YTo g'^^i'^ of strychnine yields a very copious, bright yellow deposit, which after a time disappears, but it is reproduced upon further addition of the reagent. 2. YFoT gr^^i^ yields a copious precipitate. 3. Yo'.oTo' grain : a very good deposit. 4. -g-Q-.^-oT gi^ain yields a very satisfactory, yellow precipitate. 5. yotVfo grain yields a distinct turbidity, which after a time dis- appears, and is not reproduced upon further addition of the reagent. The reaction of this reagent is common to a large class of organic substances. 14. Physiological Test. Dr. Marshall Hall proposed to take advantage of the extreme sensibility of frogs to the effects of strychnine as a means of detect- ing its presence. He advised to immerse the frog in a solution of the poison ; when sooner or later, according to the strength of the solution, the animal is seized with violent tetanic convulsions, in which the extremities become extended to their uttermost and the whole body perfectly rigid. By this method Dr. Hall states that he was enabled to detect l-5000th of a grain of strychnine. More recently Dr. Harley proposed to inject the strychnine solution into the thoracic or abdominal cavity of the animal ; and he states that 1— 16,000th of a grain of strychnine acetate introduced into the lungs of a very small frog will render it violently tetanic in about ten minutes. In the following examinations of this test, about two grains of the strychnine solution were taken up by a pipette, the filled end of PirYSIOT.OOIPAI^ TKST. 585 whicli was (hen iiitnitliiccd into the stomiu^li of the frooj, and the liqiiul (lischari^ed by blowing through tlie tube. The animals were then placed under an open glass receiver. The frogs were fresh, and varied in weight from fifteen to fifty grains. The results for each quantity of the poison are based upon numerous exj)eriments, and chiedy upon the species of animal known as Rana Ilalecina. 1. 1-lOOth solution — equal to about l-50th grain of strychnine — usually produces immediate and violent spasms, and death in about eight minutes. 2. 1-1 000th solution : the symptoms generally manifest themselves in three or four minutes, and death usually takes place in from fifteen to thirty minutes. 3. l-10,000th solution: in some instances the symptoms appeared within ten minutes, while in others they were delayed as long as half an hour. 4. l-20,000th solution generally produces characteristic symptoms in from thirty to forty-five minutes; but in some few instances the results were not well marked, even after long periods. 5. l-30,000th solution, or l-15,000th grain of strychnine : in most instances, especially when very small animals were employed, the symptoms appeared within fifty minutes ; but in some cases there were no marked effects, even after some hours. In applying this test, the frogs should always be fresh from the pond. Occasional agitation of the animal hastens the action of the smaller quantities of the poison ; and frequently a violent paroxysm may be induced by a sudden noise, such as clapping of the hands. From experiments made at different times, we are strongly inclined to believe that the sensibility of this animal to the effects of strych- nine differs somewhat with the seasons of the year. The spring and early part of the summer seem to be the most favorable for the application of the test. It may be remarked that, in regard to weight, l-20,000th of a grain of strychnine bears about the same relation to a frog weighing twenty-five grains that two grains do to a man weighing one hundred and forty pounds. When, therefore, the foregoing experiments are taken in connection with the known effects of strychnine upon the human subject, it would appear that the frog is relatively somewhat less sensitive than man to the action of the poison. This physiological test certainly affords a very valuable means of 586 STRYCHNINE. corroborating the chemical evidence of the presence of strychnine, and at the same time, as we have just seen, it is extremely delicate; yet it should never be employed to the exclusion of at least some of the chemical tests. In regard to delicacy of action, for the pure alkaloid, it is much inferior to the color test, the latter yielding satisfactory results with a quantity of the poison that would produce no appreciable effect upon a frog, even of the smallest size. Other Reagents. — Chlorine gas passed into somewhat strong solu- tions of salts of strychnine produces a white, amorphous precipitate. Ten grains of a 1-1 000th solution of the alkaloid yield a quite good deposit, which is unchanged upon the addition of ammonia ; a similar quantity of a 1-10, 000th solution yields a distinct milkiness, which quickly disappears on the addition of ammonia. Tannic add, jphosphomolyhdie acid, phosphoantimonic acid, meta- tungstic acid, and Nessler's test for ammonia also precipitate strych- nine from solutions of its salts, even in some instances when very highly diluted. But, as the reactions of these reagents are common to a large class of organic compounds, the results have little or no positive value. Gallic acid fails to produce a precipitate, even in highly concentrated solutions of salts of strychnine. Separation from Organic Mixtures. From Nux Vomica. — Strychnine may be separated from powdered nux vomica by digesting the powder for some time at a moderate heat with a small quantity of water slightly acidulated with acetic acid ; the cooled liquid is filtered, and the filtrate concentrated over a water-bath to a small volume. The concentrated solution, which will have the intensely bitter taste of the alkaloid, is treated with slight excess of potassium or sodium hydrate, and violently agitated with about its own volume of chloroform. After the liquids have completely separated, the chloroform is carefully withdrawn and allowed to evaporate spontaneously in a watch-glass, when the alka- loid will be left usually in its amorphous state, together with more or less foreign matter. The residue thus obtained may either be examined at once by the chemical tests for strychnine, or be further purified by dissolving it in a very small quantity of acidulated water, rendering the solution alkaline, and again extracting with chloroform. After examining a SEPARATION FROM ORGANIC MIXTURES. 587 portion of the residue by the color test, any reniaininj^ portion may be (lissolveil in a small quantity of water containing a trace of acetic acid, and the solution tested by potassium dichromate, or any of the other liquid tests for the alkaloid. A single grain of powdered nux vomica, when treated after the above method, will yield very satisfactory evidence of the presence of strychnine. If the nux vomica or vegetable infusion contains a comparatively large proportion of hrucine, this may interfere with the color reaction of the strychnine. These alkaloids may be sepa- rated by one or other of the metliods already described. Suspected Solutions and Contents of the Stomach. — Any organic solids present in the mixture presented for examination are cut into small pieces, and the mass, after the addition of water if necessary, treated with about half its volume of strong alcohol and sufficient acetic acid to give it a distinctly acid reaction. The acidu- lated mixture is digested at a moderate heat on a water-buth, with frequent stirring, for about half an hour or longer. It is then, after cooling, thrown upon a wet linen strainer, and the solid residue well washed with diluted alcohol and strongly pressed. The mixed strained fluids are concentrated at a moderate temperature to a small volume, again strained, then filtered, and evaporated on a water-bath to about dryness. Any strychnine present will now be in the residue, in the form of acetate, mixed with more or less foreign matter. The residue thus obtained is thoroughly stirred with a small ()iis evaporation leaves the alkaloid in its crystalline state. rhysiolof/icnl 7^ec/.s'.— The effects oi" hnicinc on tin; animal economy arc precisely the same in kind as those of strychnine ; but it is less energetic in its action than the latter alkaloid, having only about one-twelfth the power of that substance. Dr. Christison cites two instances of poisoning by this substance; and Prof. Casper relates three cases in which death resulted from the taking of a mixture of arsenic and brucine. {Forensic Medicine, ii. 102.) In a case related by Dr. T. S. Sozinskey {Med and Surg. Rep., Aug. 1882, 194), two grains of brucine taken by a man produced most alarm'ing symptoms, essentially the same as those produced by strych- nine : under active treatment the patient entirely recovered. The ordinary medicinal dose of brucine is from half a grain to one grain, repeated two or three times a day. General Chemical Natuee.— Brucine is a white, odorless solid, having an intensely bitter taste, very similar to that of strych- nine. In its pure state it is readily crystallizable, forming beautiful groups of very delicate, transparent needles ; when the crystals are only slowly produced, they usually appear in the form of bold, colorless, four-sided prisms : the crystals contain four molecules, or about 15.45 per cent, of their weight, of water of crystallization, their composition being CssH^eNA-^H.O. When moderately heated, the crystals fuse and become anhydrous ; and at a higher temperature the residue takes fire and burns with a dense smoky flame. Brucine may be sublimed unchanged. According to Prof. Guy, the alka- loid fuses at 115.5° C. (240° F.) and sublimes at 204.4° C. (400° F.), the sublimate being generally amorphous. {Forensic Medicine, 1881, 576.) Brucine is unacted upon by the fixed caustic alkalies, but it is readilv decomposed by concentrated nitric acid. The salts of brucine are colorless, except when they contain a colored acid, and are for the most part easily crystallizable. They have the bitter taste of the pure alkaloid, and are readily decora- posed by the caustic alkalies, with the elimination of the brucine. In regard to its basic properties, brucine is somewhat inferior to strychnine, it being displaced from its saline combinations by that alkaloid. Solubility.— When excess of pure powdered brucine is frequently agitated with pure water at the ordinary temperature for twenty-four 602 BEUCINE. hours, one part of the crystallized alkaloid dissolves in 900 parts of the liquid : this corresponds to one part of the anhydrous alkaloid in about 1050 parts of the menstruum. It is much more soluble in hot water, from which, however, the greater part of the excess sepa- rates as the solution cools. Its solubility in this liquid is somewhat increased by the presence of foreign organic matter. Absolute ether, when frequently agitated for several hours at the ordinary temperature with excess of the powdered alkaloid, dissolves one part of the anhydrous base in 440 parts of the liquid. Chloro- form readily dissolves the alkaloid in nearly every proportion. It is thus obvious that this liquid is better adapted than ether for the separation of the alkaloid from alkaline aqueous mixtures. The alkaloid is also readily soluble in nearly every proportion in absolute alcohol. But it is insoluble in the fixed caustic alkalies, and only sparingly soluble in large excess of ammonia. Most of the salts of brucine are freely soluble in water and in alcohol. Special Chemical Properties. — Concentrated sulphuric acid dissolves brucine and its salts with the production of a faint rose-red color. If the acid contains nitric acid — as is frequently the case — the alkaloid dissolves to a deep red solution. If a small crystal of potassium dichromate be stirred in the sulphuric acid solution, the liquid acquires an orange or brownish-orange color, which slowly changes to a greenish hue, due to the separation of chromium oxide. This reaction at once distinguishes brucine from strychnine. Con- centrated nitric acid dissolves the alkaloid, as well as its salts, to a deep red solution, the color of which slowly fades to yellow. The statement of Sonnenschein, that under the action of nitric acid bru- cine is converted into strychnine, has not been confirmed by more recent observers. Brucine is readily soluble in concentrated hydro- chloric acid without change of color. In the following examination of the reactions of solutions of brucine, the pure crystallized alkaloid was dissolved, by the aid of just sufficient acetic or sulphuric acid, in pure water. The fractions employed indicate the fractional part of a grain of the crystallized alkaloid in solution in one grain of water; and the results, unless otherwise indicated, refer to the behavior of one grain of the solution. One grain of pure crystallized brucine corresponds to 0.845 of a grain of the anhydrous alkaloid. nitrk; acid and stannous chloride test. 603 1 . The Caustic Alkalies. The fixed caustic alkalies and ammonia produce in concentrated solutions of salts of hrucine a white, amorj)lious |)r(!cipitate of the pure anhydrous alkaloid, which after a little time, by the assimilation of water, assumes the crystalline form. The precipitate is readily soluble in free acids, even in acetic acid; but it is insoluble in large excess of cither potassium or sodium hydrate. In its amorphous state the precipitate is rather freely soluble in large excess of ammonia; but wlien it has assumed the crystalline form it is only very sparingly soluble in that liquid. 1. ^_^ grain of brucine, in one grain of water, yields with either of the fixed alkalies an immediate amorphous precipitate, which in a very little time gives rise to very beautiful groups of exceed- ingly delicate crystalline needles, Plate XI., fig. 5 ; and soon the mixture becomes converted into a nearly solid mass of crystals. Ammonia produces a similar precipitate, but it does not usually appear until after some little time ; it then separates in the crys- talline form. If large excess of ammonia be added, the precipi- tate may fail to appear, even after several hours. 2. -g-^ grain yields with a fixed alkali an immediate' cloudiness, and soon a very good crystalline precipitate. The formation of the precipitate is much facilitated by stirring the mixture. Very- similar results may be obtained by ammonia, provided it be added in very minute quantity. Solutions of salts of brucine but little more dilute than the last- mentioned fail to yield a precipitate hy either of the caustic alkalies. The alkali carbonates behave with solutions of salts of brucine in much the same manner as the free alkalies. The true nature of the precipitate produced by the caustic alkalies may be confirmed by either of the two next-mentioned tests, 2. Nitric Acid and Stannous Chloride. If a few crystals of brucine or of any of its colorless salts, in the dry state, be treated with a drop of concentrated nitric acid, they im- mediately assume a deep blood-red color, and quickly dissolve to a solution of the same hue ; on heating this solution its color is changed to orange-yellow or yellow. If, when the solution has cooled, a drop of a solution of stannous chloride be added, the mixture immediately 604 BRUCINE. acquires a beautiful 'purple color, which is discharged by large excess of either nitric acid or of the tin compound, as also by sulphurous oxide gas. The red color of nitric acid solutions of brucine contain- ing a quite notable quantity of the alkaloid is changed to a faint purple on the addition of the tin solution alone, without the appli- cation of heat: but the intensity of the color, as thus obtained, is much inferior to that obtained from the brucine solution after it has been heated; and if only a minute quantity of the alkaloid be present, without the application of heat, the purple color entirely fails to appear. The following quantities of brucine were obtained by evaporating one grain of the corresponding solution of the acetate to dryness on a water- bath. 1. YWQ gi'&i^i of brucine dissolves in a drop of nitric acid to a deep red solution, which, when heated and allowed to cool, and then treated with the tin compound, acquires an intense purple color. 2. y-^oo" grain : the drop of acid acquires a very satisfactory red color, which upon the addition of the tin salt, after the solution has been heated, is changed to a beautiful lilac. 3. xFiWo" gi^'ai" : on the addition of a very small drop of the acid the deposit assumes a very decided red color, and dissolves to a faint red solution ; the tin salt produces a quite distinct lilac coloration. To obtain the latter color the acid and tin compound must be well apportioned, otherwise the reaction may entirely fail to manifest itself. This is about the limit of the tin reaction. 4. 5o-,oT¥ grain, when moistened with a minute trace of the acid, assumes a quite perceptible red color; if this njixture be evapo- rated to dryness, on a water-bath, it leaves a very satisfactory red deposit. 5. YF^iroir gi'aiu, when treated as under 4, leaves a quite distinct red residue. These reactions of nitric acid and stannous chloride, when taken in connection, are quite characteristic of brucine ; and at the same time, as we have just seen, are exceedingly delicate. In these respects this test bears much the same relation to brucine that the color test does to strychnine. Xitric acid also produces a red color with morphine and with several other substances besides brucine ; but the subsequent addition of stannous chloride fails to produce, with any of these fallacious solutions, a purple coloration. The red color POTASSIUM SUI-IMIOCVANIDK TKST. 005 of (lu- acid solution of moritliine is hut little afreotcd l)y tin; tin coni- poiuul, at most beini^ changed to ycillow; when the acid sohuioii lias been heated and allowed to cool, the tin salt produces no visible change. 3. Sulphwic Acid and Potassium Nitrate. Briieine and its salts, as already pointed out, dissolve in concen- trated sulphuric acid with the production of a rose-red color. If a crystal of potassium nitrate be stirred in the solution, the mixture acquires a deep oi||nge-red color, due to the action of the nitric acid of the nitre. This test, therefore, is very similar in its action to the one just considered. 1. ^^ grain of brucine, when treated with a small drop of concen- trated sulphuric acid, dissolves to a solution having a faint rose color, which on the addition of a small crystal of nitre is changed to deep orange-red. 2. .^-^ grain : on the addition of the acid the deposit assumes a quite perceptible rose- red color, and dissolves to a colorless solu- tion, which on the addition of the nitre acquires a beautiful orange color. 3. j-^-^ grain : the acid dissolves the deposit with little or no change of color; but the solution, when treated with the potassium salt, acquires an orange color, which soon changes to yellow. 4. -^^-^-Q-jj- grain : when the acid solution is treated with the nitre it yields only a faintly yellow coloration. But if a small crystal of nitre be moistened with the acid and then stirred over the dry brucine deposit, the crystal acquires a distinct orange color. The production of these colors is quite peculiar to brucine. Sul- phuric acid solutions of narcotine, opianyl, and morphine, when treated with potassium nitrate, yield colors somewhat similar to that produced from brucine; but neither of these substances dissolves in the acid with the production of a rose-red color. 4. Potassium Sulphoeyanide. This reagent throws down from quite concentrated solutions of salts of brucine a white precipitate of brucine sulphoeyanide, which is insoluble in acetic acid. As produced from very concentrated so- lutions, the precipitate is in the amorphous form, but it soon becomes more or less crvstalline. From somewhat more dilute solutions the 606 BRUCINE. precipitate does not appear until after some time, and it then sepa- rates in the form of small granules. The formation of the precipi- tate from solutions of this kind is much facilitated by stirring the mixture with a glass rod. One grain of a 1-lOOth solution of the alkaloid yields no im- mediate precipitate, but in a few moments comparatively large groups of minute granules appear, and after a few minutes there is a quite good deposit of these groups, with occasionally small transparent crystalline plates, Plate XI., fig. 6. A similar quantity of a l-500th solution fails to yield a precipitate, even when theguixture is allowed to stand for some hours. 5. Potassium Dichromate. Potassium dichromate throws down from solutions of salts of brucine, even when highly diluted, a yellow precipitate of bruciue chromate, which is insoluble in acetic acid. The precipitate is readily soluble, with the production of a deep red color, in con- centrated nitric acid, and in sulphuric acid, with the production of a reddish-brown color. 1. yig- grain of brucine, in one grain of water, yields a quite copious amorphous precipitate, which in a few moments becomes con- verted into crystalline group? of the forms illustrated in Plate XIL, fig. 1. ' 2. YWoT g^-'^^^ ■ i^ ^^^^ mixture be stirred, it immediately yields streaks of granules and small crystals along the path of the rod, and in a little time there is a quite copious crystalline deposit. 3. gQ^QQ grain yields after a little time, especially if the mixture has been stirred, a quite satisfactory crystalline precipitate. 4. 3-0,^-0-0 grain : after several minutes a quite distinct precipitate, and after about half an hour a very satisfactory deposit of crystalline needles. The crystalline form of the precipitate, as produced from some- what strong solutions of the alkaloid, together with the subsequent reaction of nitric acid, serves to distinguish the chromate of brucine from all other precipitates produced by this reagent. Potassium monochromate produces in solutions of the alkaloid results very similar to those occasioned by the dichromate, only that the reaction is not quite so delicate. AURIC CHLORIDE TEST. 007 6. Platinic Chloride. Solutions of salts of hnicine yield with platinic cliloriile a yel- low j)rec'i|)itate of the double chloride of ])latinuni and briiciiie, 2C23H2,5N204,HC1 ; PtCl.,, which is uiichaiigcd by acetic acid, l)Ut readily decomposed by tiie caustic alkalies. 1. y\-^ tiTain of brucine yields a very copious deposit, which almost immediately becomes a mass of irregular crystalline needles. The precipitate is slowly soluble in nitric acid, yielding an orange- red solution. 2. -Y-iijT) grain : an immediate light yellow, crystalline precipitate, which in a little time becomes converted into irregular needles, Plate XII., fig. 2. 3. -suVo grain : very soon crystals appear, and after a little time there is a quite good crystalline deposit. 4. YTj-.VoTT gi'ain : if the mixture be stirred, it immediately yields crystalline streaks, and very soon a quite fair deposit. 5. yg-.VFo grain: after a few minutes, if the mixture has been stirred, crystalline needles appear, and after a little time there is a quite satisfactory deposit. This reagent also produces yellow crystalline precipitates with various other substances, but the form of the brucine deposit is somewhat peculiar. 7. Auric Chloride. This reagent produces in solutions of salts of brucine a vellow, amorphous precipitate which has the composition C23H2j;N204,IICl, AuClg, and which in a little time acquires a flesh color. The pre- cipitate is but sparingly soluble in acetic acid ; the caustic alkalies cause it quickly to assume a dark color. 1. 370^ grain of brucine, in one grain of water, yields a very copious deposit. 2. y^Vo gi'iiiu yields a greenish-yellow precipitate, which soon becomes yellow ; the deposit is readily soluble to a clear solu- tion in potassium hydrate. 3. Yo.Voir gi'iiin = a quite good, yellowish deposit. 4. i2^,Vuir griiin yields in a very little time a distinct turbidity, and after a few minutes a quite satisfactory precipitate. 5. ^-o.-gird grain : after* some minutes a quite distinct deposit. 608 BRUCINE. All these precipitates remain amorphous. The reaction of this reagent is common to a large class of substances. 8. Picrio Acid. An alcoholic solution of picric acid throws down from aqueous solutions of salts of brucine a yellow precipitate of brucine picrate, which is but sparingly soluble in large excess of acetic acid. 1. Y^ grain of brucine yields a very copious precipitate, which after a time becomes, in part at least, crystalline. The formation of these crystals is readily prevented by the presence of foreign organic matter. 2. Y^ro g'^&i'^i yields a very good precipitate, which after a time is converted into groups of aggregated granules, similar to those produced by potassium sulphocyanide (Plate XL, fig. 6). 3. 3-o-,Vro g^^^ii^ yields after several minutes, especially if the mix- ture has been stirred, a quite distinct precipitate. The reaction of this reagent is valuable only in so far as it confirms tne reactions of the other tests for brucine. 9. Potassium Ferricyanide. Concentrated neutral solutions of salts of brucine, when treated with this reagent, yield a light yellow, crystalline precipitate, which is readily soluble in the mineral acids. The formation of the pre- cipitate is readily prevented by the presence of a free acid, even of acetic acid, but after the crystals have formed they are only very sparingly soluble in large excess of acetic acid. 1. yi-^ grain of brucine yields an immediate precipitate, and in a few moments there is a very copious deposit of crystals, grouped in various and most beautiful forms, Plate XII., fig. 3. These crystalline groups are, perhaps, the most brilliant polariscope objects yet known. The production of these crystals is quite characteristic of brucine. 2. -g-l-Q- grain : after stirring the mixture it yields in a very little time a copious granular deposit. 3. YrQ-g- grain : after some time a slight turbidity. Potassium ferrocyanide produces no precipitate with a 1— 100th solution of brucine, even if the mixture be allowed to stand for some time. SPECIAL CHEMICAL PROPERTIES. 609 10. Iodine in Potassium Iodide. A solution of iodine in potassium iodide produces in normal solutions of salts of brucinc, even when very liigiily diluted, an orange-brown, amorphous precipitate, which is insoluble in acetic acid. 1. yJ-jj- grain of brucine yields a very copious deposit, which is decomposed by large excess of ])otassium hydrate, with the production of a dirty- white precipitate. 2. Yjyjj- grain : much the same results as 1. 3. X(7,-o-irir gi'^^'i yields a quite good, brownish precipitate, which is soluble to a clear solution in a caustic alkali. 4. -s-g-.^ouir gi'^'w yields a yellowish deposit. 5. Ti5-ij,oirir grain : a very distinct, dirty-yellowish turbidity. 6. -sij-o^^y-o grain yields a perceptible cloudiness. It need hardly be remarked that this reagent produces similar precipitates in solutions of most of the alkaloids and of various other organic substances. 11. Bromine in Bromohydrlc Acid. A strong aqueous solution of bromohydric acid saturated with bromine produces in solutions of salts of brucine, when not too dilute, a deep brown, amorphous precipitate, which after a time dis- solves, but is reproduced upon further addition of the reagent. The precipitate is soluble in acids, even acetic acid, and in potassium hydrate. 1. Y^ grain of brucine yields a very copious, deep brown deposit, which soon acquires a yellow color, then a bright yellow, and after some minutes dissolves. 2. ythmj- grain : much the same results as 1. 3. YTj.^inr grain yields a yellowish precipitate, which after a time disappears, and is not reproduced upon further addition of the reagent. 4. ■2^,Vgt grain yields a greenish-yellow deposit, which soon dis- solves. The brown color of the brucine deposit distinguishes it from the precipitates produced by this reagent with other alkaloids. Other Bcadions. — S. Cotton has shown that when a icarmed nitric 39 610 BEUCINE. acid solution of brucine is treated with a concentrated solution of sodium hydrosulphide, the mixture assumes a beautiful violet color, which is changed to g^'een by large excess of the reagent. This color is not atfected by the alkalies, but diluted acids change it to rose- red, sulphuretted hydrogen being evolved. [Jour. Pharm. et Chim., July, 1869, 18.) The reagent may be prepared by saturating a strong solution of sodium hydrate (1 : 8) with sulphuretted hydrogen gas. To apply this test, a few drops of the brucine solution, placed in a small test-tube, are treated with a few drops of nitric acid, the mixture warmed to 40° or 50° C. (about 115° F.), and then a drop or two of the reagent added. In this manner a 1-1 000th solution of brucine will yield a deep violet coloration, which under excess of the reagent is changed to green. A l-10,000th solution yields a very good violet or purple coloration, passing to deep green under excess of the reagent. Even a l-1 00,000th solution will yield a distinct purple, followed by a perceptible green coloration. Strych- nine yields no color under this test, and morphine fails to yield a similar coloration. Mereurous nitrate, free from excess of nitric acid, occasions no coloration with solutions of salts of brucine in the cold ; but if the mixture be heated on a water-bath, a beautiful carmine color is grad- ually developed, which is permanent on evaporating the liquid to dryness. This coloration is very intense in a few drops of a 1-1 00th solution of brucine; and the residue from a similar quantity of a l-10,000th solution has a well-marked pinkish hue. According to F. A. Fhickiger, who first observed this reaction, strychnine, the alkaloids of opium and cinchona, veratrine, caffeine, and piperine, })roduce no color under these conditions; but albumin and phenol yield similar colorations. Prof. DragendorfP has lately shown (1878) that if brucine be dissolved in diluted sulphuric acid (1 : 10), and a minute quantity of a very dilute aqueous solution of potassium dichromate be then added, the mixture acquires a beautiful red color, changing to red- dish-orange, then to brownish- orange, the reaction being one of oxidation. Under this reaction a coloration will manifest itself, as claimed by Dragendorfi', in a 1-1 0,000th solution of the alkaloid. According to Watson Smith, if solid brucine be let fall upon antimony trichloride heated to fusion, a beautiful red or purple-red SEPARATION FROM ORGANIC MIXTURES. Oil color is developed, oven when only the minutest trace of the alkaloid is employed. {C/ievi. Neios,Ju\y, 1879.) Mr. Smith states (hat this reaction is peculiar to hrucine. Corro.sii'c tiiib/iinatc thi'ows down from a 1-lOOth solution of salts of hrucine a quite j2; ing ill wliicli lie oniploycd repeated draclini doses of tincture of dijjjitMlis with trivat advantaj^e. PosT-MOKTKM A I'l'HARAN'CES. — Tlic iiiost comtiioii morbid ap- pearances, ill death from aconite, are an injected condition of the l)h)od-vessels of the brain and of its membranes, and contrestion of the lungs and liver, with more or less redness of the mucous mem- brane of the stomach and intestines. The stomach and small intes- tines are frequently found empty. The right cavities of the lieart usually contain more or less blood ; the blood throughout the body is generally fluid and of a dark color. It need hardly be remarked that none of these appearances are peculiar to death from this sub- stance. In two cases of fatal poisoning by a tincture of the root of aconite, quoted by Dr. Beck, the only morbid appearances observed on dissection were great redness of the lining membrane of the stomach and small intestines. In au instance quoted by Orfila {Toxicologie, ii. 443), in which five persons swallowed each a glass of brandy in which the root of aconite had been macerated, and three of them died, death taking place in about two hours, the following appearances were observed. The cesophagus, stomach, and intestines were found much inflamed, and the blood-vessels, especially the veins, of the' digestive tube much injected. The mesentery was also inflamed. The cavity of the peritoneum contained a large quantity of yellowish serum. The lungs were dense, of a bluish and violet hue, slightly crepitant, and gorged with blood. The pericardium contained a large quantity of serum ; the heart and large vessels presented nothing remarkable. The brain was healthy, but its blood-vessels somewhat injected. In the case of the child, already cited, in which the leaves of aconite had been eaten and life was prolonged for about twenty hours, the body presented the following appearances sixty hours after death. The abdomen externally was much discolored; and patchy discolorations were visible on the thighs and legs, but the spots were not so apparent as during life. The stomach was highly inflamed throughout its whole extent; it contained a little fluid of a lightish-brown color, but no food, nor any traces of leaves or other vegetable matter. Various parts of the small intestines presented patches of intense inflammation, in some places approaching to gangrene. The large intestines presented nothing particular. The bladder was full of urine ; the spleen somewhat congested. The peri- 624 ACONITINE. cardium contained about half an ounce of bloody serum. The heart was full of uncoagulated blood, and the blood throughout the body- was thin and fluid. The other parts of the body were nearly or al- together normal. In the case of Dr. Meyer, who had taken the nitrate of aconitine, there was found great paleness of the body, and the pupils were somewhat dilated. The stomach, lungs, and especially the small intestines, were much congested ; but the colon and rectum were pale, as was also the bladder. The heart was dilated, and the right side contained a little liquid blood. The vessels of the membranes of the brain were distended, and at certain points exudations under the arachnoid were present; the ventricles contained a bloody serous effusion, and there was a bloody exudation on the choroid plexus. The blood throughout the body was liquid and of a bright cherry- red color. In the Lamson case, sixty-four hours after death, the pupils were dilated, and the lips pale, as was also the tongue. The membranes of the brain and the brain itself were slightly congested. The lungs, liver, spleen, and kidneys were more or less congested. The heart was very flaccid, and its cavities almost empty. The mucous mem- brane of the stomach was congested throughout, and presented in places small, slightly raised, yellowish-gray patches. The stomach contained three or four ounces of fluid. The first portion of the duodenum was greatly congested, and patches of congestion were present in other parts of the small intestine. The bladder contained three or four fluid-ounces of urine. {Guy^s Hosp. Rep., xxvi. 312.) Chemical Properties. In the Solid State. — Aconitine, in its pure state, is a trans- parent, odorless solid, Avhich crystallizes with difficulty, forming either colorless rhombic or hexagonal tables, or small four-sided prisms. It has an acrid taste, followed by a sense of tingling and numbness of the tongue ; applied in the form of solution to the skin, it causes a persistent feeling of heat and numbness. These effects are produced by even extremely minute quantities of the alkaloid. Applied in the form of ointment to the eye, it causes much the same effects, with, according to Dr. Pereira, contraction of the pupil. Aconitine is unchanged by exposure to the air. When moderately heated in a tube, it fuses to a transparent liquid, which, CHEMICAL PROPERTIES. G25 as the lieat is increased, becomes brown, then black, and is finally rcducod to a solid carbonaceous mass. Heated in the air on a i)icce of j)<)rcehiin, it undergoes a similar chanire, and leaves a black cinder, which is but slowly consumed. According to Dr. Guy, aconitine melts at G0° C. (140° F.), and at 204.4° C. (400° F.) yields subli- mates which are amorphous. As found in the shops, aconitine is usually amorphous and more or less colored, and very variable in strenjjth, some of the samples being almost wholly inert. Dr. Pereira states that he met with a French preparation of which he took one grain without perceiving the least effect either on the tongue or otherwise. And of three samples prepared by different German manufacturers that we have examined, one contained only a mere trace of the alkaloid, and the other two appeared to consist entirely of foreign matter. The aconitine prepared by Mr. Morson is usually in the form of a dull white powder, consisting chiefly of small granules and thin, trans- parent plates. This manufacturer, Mr. Grov^es, and others, have obtained the alkaloid in the form of large, well-defined crystals. A sample of Duquesnel's aconitine in our possession is in the form of large, colorless crystals, many of them weighing about 1-lOth grain each. Aconitine has strongly basic properties, completely neutralizing acids to form salts, several of which have been obtained in the crys- talline form. When touched in the drv state with concentrated sul- phuric acid, jjure aconitine slowly dissolves, without any coloration whatever, to a colorless solution, which remains unchanged for many hours. A small crystal of potassium nitrate stirred in a sulphuric acid solution of the alkaloid produces no visible change, even on the application of a moderate heat; if a crystal of potassium dichro- mate be stirred in the solution, the mixture slowly acquires a green color, due to the separation of chromium sesquioxide. Concentrated nitric acid dissolves the alkaloid to a colorless solution, which is un- changed by a moderate heat, and by a solution of stannous chloride. The alkaloid is also dissolved to a colorless solution by hydrochloric acid. SoJuhility. — When excess of Morson's aconitine is kept in contact with imre icater at a temperature of about 15.5° C. (60° F.) for ten hours, one part dissolves in 1783 parts of the fluid. On evaporating the solution to dryness, the alkaloid is left in the form of a hard, 40 626 ACONITINE. transparent, colorless, vitreous mass, which, when broken up, presents the appearance of crystalline plates. The recently precipitated alka- loid is much more soluble in water than just stated. A sample of DuquesneFs crystallized aconitine had about the same degree of solubility in water as that of Morson. Absolute ether kept in contact with excess of aconitine for several hours, at the ordinary tempera- ture, takes up one part in 777 parts of the menstruum. On allowing the solution to evaporate spontaneously, the alkaloid is left as a transparent glacial mass. Chloroform readily dissolves the alkaloid in nearly every proportion, and leaves it on spontaneous evapora- tion in the form of a vitreous mass. It is also freely soluble in alcohol. The salts of aconitine are, with few exceptions, readily soluble in water. They are also soluble in alcohol, but insoluble in ether. Of Solutions of Aconitine. — In the following investigations in regard to the behavior of solutions of aconitine, pure aqueous solutions of the hydrochloride were employed. The fractions in- dicate the fractional part of a grain of the pure alkaloid present in one grain of liquid ; and, unless otherwise stated, the results refer to the behavior of one grain of the solution. 1 . The Caustic Alkalies. The fixed caustic alkalies and ammonia throw down from some- what concentrated solutions of salts of aconitine a dirty-white, floccu- lent precipitate of the hydrate of the alkaloid, which is nearly wholly insoluble in excess of the precipitant, but readily soluble in free acids, even acetic acid. 1. YQ-g- grain of aconitine, in one grain of water, yields a rather copious precipitate, which is insoluble in large excess of the reagent. 2. -g-^-g- grain yields a quite good precipitate, which dissolves, not readily, however, in several drops of the precipitant. 3. YWo" g^^^i" • 1^0 satisfactory indication. The alkali carbonates fail to produce a precipitate with a 1-1 00th solution of the alkaloid. 2. Auric Chloride. Trichloride of gold produces in solutions of salts of aconitine, even when highly diluted, a yellow, amorphous precipitate, consisting BROMINE IX BROMOIIYDRIC ACID TEST. G27 of ncoiiitinc liydroclilorido and aiiric; oldorido, which is hiil very sparingly sohihlc in hydrochloric acid. 1. Ykfi grain of aconitino yields a very copious precipitate. 2. yx,V(r gi'ain yields a quite good deposit, which is readily soluble to a clear solution in potassium hydrate. ''^- :7(M)(i g'"^i'i yields in a very little time a quite fair precipitate. 4. x^(i.|,yo grain yields after a little time a quite perceptible deposit. 5. ijif.Vinr gi"^'" • after some time a just perceptible turbidity. 3. Picric Acid. An alcoholic solution of picric acid occasions in solutions of salts of aconitine a yellow, amorphous precipitate, wliich is insoluble in ammonia. 1. y-J-jj- grain of aconitine, in one grain of water, yields a very copious precipitate. 2. YijVij- grain yields a quite fair, greenish-yellow deposit. 3. g ^(^ Q grain : after a little time a quite perceptible precipitate. 4. Iodine in Potassium Iodide. An aqueous solution of iodine in potassium iodide throws down from solutions of aconitine and of its salts, even when highly diluted, a reddish-brown or yellowish, amorphous precipitate, which is readily decomposed by the caustic alkalies. 1. -j-OTT gi'ain of aconitine yields a very copious precipitate, which on the addition of potassium hydrate is changed to a white deposit. 2. YoVo" grain: a copious, yellowish precipitate, which is soluble in the caustic alkalies, but immediately replaced by a white deposit. 3. xo.^ij-j)- grain : a quite good precipitate. 4. 3-g-,V(r(r grain yields a quite distinct deposit. 5. xTo.VuT gi'ain : the mixture becomes distinctly turbid. 5. Bromine in Bromohydric Acid. A strong aqueous solution of bromohydric acid saturated ^vith bromine produces in solutions of salts of aconitine, and of the free alkaloid, a yellow, flocculent precipitate. 1. -j-^ grain of aconitine, in one grain of water, yields a copious precipitate. 2. YdVo" gi'ain : a quite good deposit. 628 ACONITINE. 3. 3-0,^-00" grain : a quite fair precipitate. 4. 2T,"ooT gi'^ii^ yields a distinct cloudiness. Other Reagents. — Corrosive sublimate produces in one grain of a 1-lOOth solution of salts of aconitine a quite good, dirty-white, caseous precipitate, which is readily soluble in hydrochloric acid. A similar quantity of a l-500th solution of the alkaloid fails to yield a precipitate. Potassium sulphocyanide and tannic acid pro- duce a perceptible cloudiness in a 1-lOOth solution of salts of the alkaloid. AVith stronger solutions these reagents produce distinct precipitates. Pliospho-molyhdic acid throws down a precipitate from solutions of the alkaloid even when highly diluted. Platinic chloride, potassium chroraates, potassium iodide, and potassium ferro- and ferri-cyanide, fail to produce a precipitate with a 1-lOOth solution of the hydrochloride of the alkaloid. FaUacies. — None of the chemical reactions now described are in themselves characteristic of aconitine, they being common to many of the alkaloids and certain other organic principles; nor is there at present any chemical reaction known that in itself is peculiar to this substance. By, however, the concurrent reaction of several of these reagents, taken in connection with the peculiar effects of the alkaloid upon the tongue, its nature may be fully established, even when present only in very minute quantity. In fact, the symptoms pro- duced by this substance are usually so peculiar that they alone, when fully known, may enable the medical jurist to determine the cause of death, even when the chemical evidence has entirely failed. A case of this kind, in which the root of aconitine had been criminally administered and no trace of the poison was discovered in the body, is related by Dr. Geoghegan. [Dublin Medical Journal, July, 1841, 403.) Physiological Test. — Much the most characteristic test yet known for the recognition of aconitine is its peculiar physiological action when applied to the tongue or in the form of solution to the skin. A drop of water holding in solution, in the form of a salt, only the 1-lOOOth of a grain of the alkaloid, when placed upon the end of the tongue, causes, as first observed by Dr. Headland, a very decided tingling and numbness of that organ, which continue for an hour or longer. According to Dr. Headland {Action of Medicines, 448), the 1-1 00th of a grain dissolved in alcohol and rubbed into the skin SKP.MJATIO.V Fi:(».M oltOANIC MIXTURES. G29 pidiliioes loss of feellnir, lasting for sonic time; and the l-50lli oi' :i grain will kill a small hinl almost instantly. Jn an exiK'rinieiit by Dr. T. Stevenson, l-3000tli grain of Mor- son'.s crystallized aconitine, subcutaneously injected, killed a large mouse in eighteen minutes. And our own exj)eriment.s with Du- quosncl's crystallized aconitine indicated it to be about equally potent, 1-WOOth grain proving fatal to a mouse, under violent retching followed by convulsions, in thirty-two minutes. A sample of Mor- son's ordinary aconitine was somewhat less active than the crvstal- lizeil alkaloid of Duquosnel ; as was also a sample of Trommsdorff's aconitine, which latter was in the form of a faintly colored, partially granular powder. Separation from Organic Mixtures. Suspecled Solutiom and Contents of the Stomach. — In suspected poisoning by aconite in its crude state, before proceeding to a chem- ical examination of the mixture presented for examination, the analyst should carefully examine it for any solid portions of the plant, which, if found, may be identified by their botanical char- acters. All parts of the plant have a bitter taste', which is soon followed by a persistent sense of numbness and tingling in the lips and tongue. Aconitine may be separated from the contents of the stomach, and like mixtures, in the same manner as heretofore described for the recovery of nicotine {ante, 447), or by the method of Stas. The alkaloid is more readily extracted from aqueous mixtures by chloro- form than by ether, it being much more soluble in the former than in the latter liquid. The residue obtained on evaporating the chloroform or ether extract should at first be stirred with a few drops of water containing a trace of acetic acid, and a small portion of the mixture applied to the end of the tongue. If this experiment indicates the presence of a very notable quantity of the poison, the remaining portion of the mixture may be dissolved in an appropriate quantity of acidulated M'ater and the solution examined by some of the chemical tests. Should, however, the portion applied to the tongue fail to indicate the presence of the alkaloid, another and larger portion should be examined in the same manner, even if the whole of the mixture be thus consumed, since without the corrobora- 630 ACONTTINE. tion of this physiological test, the chemical tests, at present known, would be of no avail. On applying the method heretofore pointed out for the detection of nicotine to the examination of the contents of the stomach of a dog, killed in fourteen minutes by a drachm of ordinary tincture of the root of aconite, the presence of aconite was very fully established. From the Blood. — Absorbed aconitine may be recovered from the blood by slightly acidulating the fluid with sulphuric acid and agi- tating it in a wide-mouthed bottle with something more than its own volume of diluted alcohol, until the mixture becomes homogeneous. It is then placed in an evaporating-dish and exposed for some time, with frequent stirring, to a moderate heat ; the cooled mass is trans- ferred to a moistened linen strainer, and the solids retained by the strainer well washed with diluted alcohol and strongly pressed. The liquid is now concentrated at a moderate heat, again strained, then evaporated to a small bulk, filtered through paper, and evaporated on a water-bath to about dryness. The residue thus obtained is well stirred with a small quantity of pure water, the solution filtered, then rendered alkaline, and thoroughly agitated with about two volumes of chloroform, which, after separation and decantation, is allowed to evaporate spontaneously, when the alkaloid will usually be left sufficiently pure for testing. About forty minims of the tincture of- aconite root were admin- istered to a small dog. The animal immediately indicated an uneasy sensation in the mouth and throat, and soon vomited a white frothy mucus, then lost the use of his legs, made repeated attempts to vomit, had spasmodic convulsions with slow breathing, and died in sixty- four minutes after the dose had been given. Twelve fluid-drachms of blood, taken immediately from the animal, were submitted to the foregoing method of analysis, and the chloroform residue stirred with two drops of water containing the merest trace of acetic acid. A drop of this mixture placed upon the tongue gave, in a little time, perfectly unequivocal evidence of the presence of aconitine. The remaining drop of the mixture was diluted with two drops of pure water, and examined in three separate portions by picric acid, auric chloride, and a solution of bromine, all of which produced precipi- tates very similar in quantity with those produced from a 1-1 500th solution of the alkaloid. The entire quantity of the poison recovered could hardly have exceeded the l-300th of a grain, and may have ATROPINE. 631 been even nuich less than this, since it is ))y no means certain that the precipitates produced hy the reagents were perfectly pure. Twenlv-live minims of the ssanie tincture of aconite were given to a hcaltliv cat. The animal was soon seized with violent vomiting, lost the power of walking, frothed at the mouth and nose, and died under violent symptoms within thirly minutes. The chloroform residue obtained from one ounce of blood from (his animal, when stirred with a few drops of acidulated water and examined by auric chloride and a solution of bromine, gave reactions similar to those produced from a quite dilute solution of aconitine; yet about one- half of the residue, when applied to the tongue, failed to produce any decided effect u])on that organ. In the Lamson case, Drs. Stevenson and Dupre found aconitine in extracts from the viscera, the vomit, and the urine of the victim, the presence of the alkaloid l)eing determined by the general chemical nature of the extract, its effect upon the tongue, and its action upon mice. The ireneral method of analysis followed in this case was to re- peatedly extract the substance with alcohol slightly acidulated with tartaric acid, and then evaporate the filtered alcoholic extract to dry- ness at 35° C. (95° F.). The residue thus obtained was exhausted with tepid water, and the filtered liquid, while still acid, repeatedly agitated with ether. The aqueous liquid was then rendered alkaline by sodium carbonate, and extracted with a mixture of ether and chloroform ; the ethereal mixture was evaporated to dryness, and the residue examined for aconitine. Section II. — Atropine. Belladonna. History. — Atropine is the active principle, or alkaloid, of Atropa Belladonna, or Deadly Nightshade. It exists in the root, leaves, and berries of the plant. The existence of this principle was first an- nounced in 1819, by Brandes; but it was first obtained in its pure state by Mein, a German pharmaceutist, in 1833. Its composition, according to the analyses of Planta, is 0,71123X03. Atropine is a white crystal I izable solid, and a most virulent poison. Preparation. — Atropine may be obtained, according to M. Ra- bourdin, in the following manner. The fresh leaves of the plant are 632 ATROPINE. well bruised and submitted to pressure to extract the juice; this is theu heated to about 85° C, (185° F.), in order to coagulate the albu- men, and filtered, after which it is rendered alkaline by potassium hydrate, and thoroughly agitated for a few miuutes with chloroform. In about half an hour, the latter fluid, holding in solution the atro- pine and having the appearance of a greenish oil, will have subsided to the bottom of the mixture. The supernatant liquid is then de- canted, and the chloroform solution washed with successive portions of water as long as this liquid becomes colored. The chloroform solution is then transferred to a tubulated retort, and distilled in a water-bath until all the chloroform has passed into the receiver, when the residue is treated with a little water acidulated with sulphuric acid, which will dissolve the atropine, leaving a green, resinous matter. The solution thus obtained is filtered, the filtrate treated with slight excess of potassium carbonate, and the precipitated atropine collected on a filter, washed, and dissolved in rectified alcohol, which upon spontaneous evaporation will leave the alkaloid in beautiful groups of acicular crystals. In the absence of the fresh plant, M. Rabourdin recommends to employ the extract of belladonna. Thirty parts of the extract are dissolved in one hundred parts of water, and the filtered solution agitated for about a minute with two parts of potassium hydrate and fifteen parts of chloroform. The subsequent steps of the process are the same as directed above, except that the washed chloroform solu- tion, instead of being distilled, is allowed to evaporate spontaneously. The product obtained by either of these methods, if not perfectly colorless, may be further purified, as fii^st advised by Prof. Procter, bv redissolviug it in water acidulated with sulphuric acid and extract- ing the foreign organic matter by chloroform ; the aqueous solution is then rendered alkaline, and the liberated alkaloid extracted with fresh chloroform, which on spontaneous evaporation will leave it in its pure state. M. Lefort has advised the use of ether, instead of chloroform, for the extraction of the alkaloid, the latter being first extracted from the leaves of the plant by boiling water containing one per cent, of tartaric acid. Mein, in his experiments, obtained twenty grains of atropine from twelve ounces of the fresh root of belladonna; and Luxton, between five and six grains from one thousand grains of the fresh leaves. On an average, perhaps, the green root and leaves do not contain over PHYSIOLOGICAL EFFECTS. 63.'i nboiit one-third of one per (rut, of the alUidoid. Accord iii^ to the aL!;e of the phint, yonng roots l^eing richer in the alkaloid tlian the rottts of plants more than two or three years oKl. The ordinary medicinal dose of alrojune, and its salts, is about one-liftieth of a grain. Tlie pharmaceutical extracts and tincture of belladonna are each subject to great variation in strength. The dose of the former, for an adult, is at first from one-fourth to one-half a grain; that of the latter, from fifteen to twenty-five minims. Poisoning by atropine in its i)ure state has been of rather rare occurrence; but numerous instances of poisoning by the berries and some of the preparations of belladonna are recorded. With few exceptions, however, these cases have been the result of accident, most of them having been occasioned by the berries being eaten through ignorance of their properties. The berries have considerable resemblance to cherries, and a sweet but mawkish taste. Symptoms. — The most constant symptoms occasioned by poi- sonous doses of belladonna are dryness of the mouth and throat, difficulty of deglutition, dilatation of the pupils, impaired vision, and delirium, succeeded by drowsiness and stupor. The delirium is generally of a pleasing character, but sometimes of a furious nature. These effects are usually attended with a sense of burning and con- striction of the throat, impaired articulation, great thirst, giddiness, numbness of the limbs, a staggering gait, nausea and sometimes vomiting, spectral illusions, and great mental excitement. The pulse becomes quick and small, and sometimes the face red and turgid, and the eyes wholly insensible to light. The secretions are usually in- creased ; irritation of the urinary organs has sometimes occurred ; and in some instances a scarlet eruption has appeared on the skin. In fatal cases, death is usually preceded by coldness of the extremities, a rapid and intermittent jiulse, deep coma, and sometimes, though rarely, convulsions. The following symptoms were observed in one hundred and fifty French soldiers, who had eaten the berries of the ])lant : Dilatation and immobility of the pupil, with total insensibility of the eye to the presence of external objects, or at least confused vision ; bluish injection of the conjunctiva; great prominence of the eye; dryness of the lips, tongue, and throat; difficult and in some cases impossi- 634 ATEOPIXE. ble deglutition; nausea, but no vomiting; great weakness, with difficulty or impossibility of standing; continual movement of the hands and fingers; lively delirium, accompanied with a silly laugh; aphonia, or confused sounds uttered with difficulty; and ineffectual attempts to empty the bowels. These effects were followed by very gradual return to health and reason, without any recollection of the preceding state. {Orfila's Toxicologie, 1852, ii. 478.) The symptoms produced by belladonna, as usually developed, could not readily be confounded with those of any other substance, except stramonium and hyoscyamus (Pereira). The symptoms usually manifest themselves within an hour after the poison has been taken ; but they have frequently been delayed for several hours, especially in poisoning by the berries. Of the numerous recorded cases of poisoning by this substance, comparatively few proved fatal, and in these the time of death varied from a few hours to some days. The effects in non-fatal cases are frequently very slow in disappearing, sometimes lasting for several days or even weeks. A healthy man ate of a pie made with the berries of belladonna and apples. A few minutes after taking his dinner he complained of feeling drowsy ; the lethargy soon increased, his countenance changed color, the ])upils became dilated, and he experienced a strange coppery taste in his mouth. On going up-stairs, he staggered, and, upon entering his room, fell, and became insensible. He sub- sequently became delirious and convulsed, and died the following morning. A child to whom a })ortion of the pie had been given died on the same day. {New York Jour, of Med., viii. 284.) In another case, in which a child had eaten the berries of the plant, narcotic symptoms appeared in two hours, and death took place in nineteen hours, being preceded by coma and a temperature of 43.3° C. (110° F.) for several hours before the fatal result. [Med. Times, Nov. 1882, 94.) In four cases in which some boys had eaten a quantity of the extract of belladonna, in one instance as much as a drachm, the following symptoms were observed in one of the cases. When first seen by a physician, the patient was quite delirious, the delirium being of a fantastic character ; he could neither hear nor speak plainly, and labored under hallucinations, but was otherwise uncon- scious. The pupils were widely dilated, and the eyes had a staring PHYSIOLOGICAL EFFECTS. 635 look. At first he complained of some i)aiii in tlie throat and of his imperfect slight, ohjeets ap|)earing white to him. The pulse was very feehle, and ahnost countless; and there was threat difficulty of swal- lowing. Under active treatment, including the use of an emetic, the delirium, having lasted eighteen hours, gradually passed away; but it was not until the lapse of forty hours that he was perfectly rational. Much the same symptoms were present in the three other cases. All the patients finally recovered. {Lancet, 1860, i. 133.) Dr. Ilibbert Taylor reports a case {British Med. Jour., Nov. 1869, 555) in which a youth, aged sixteen years, swallowed by mis- take about a drachm of the extract, and died from its effects three hours and three-quarters thereafter. In this instance, violent symp- toms suddenly manifested themselves about an hour after the extract had been taken. About an hour before death the patient became comatose, and so continued until he died. The following instance of recovery is related by Dr. H. M. Gray. {New York Jour, of Med., Sept. 1845, 182.) A child, between two and three years of age, swallowed from eight to twelve grains of the extract of belladonna. Something- over half an hour after taking; the poison, the expression of the patient was that of terror ; the pupils were widely dilated and immovable, the conjanctiva highly injected, and the whole eye prominent and very brilliant. The face, upper extremities, and trunk of the body exhibited a diffuse scarlet eflBorescence studded with innumerable papillae, very closely resem- bling the rash of scai'latina. The skin was hot and dry; the pulse much increased in force and frequency ; the respiration anxious, and attended with the stridulous sound of croup. There was also a constant but unsuccessful effort at deglutition, with spasmodic action of the muscles of the throat and pharynx ; and paroxysms of violent motion and rapid automatic movements, attended with convulsive laughter. Under the action of an emetic the alarming symptoms passed off in about three hours, and the child soon recovered, with the exception of a moderate diarrhoea and a slight enlargement of the pupil. Dr. Stevenson reports a case {Guy's Hosp. Rep., xiv. 267) in which a child, less than three years of age, recovered after having taken five grains of the extract. The external application of belladonna, and its administration in the form of an enema, have in several instances given rise to serious and even fatal results. A case is related in which an injection of a 686 ATEOPINE. decoction of the root caused the death of au adult in five hours ; and another, in which only two grains of the extract, administered in the same manner, gave rise to alarming symptoms. Dr. Lyman relates an instance in which the application of a small belladonna plaster to the chest of a nervous woman produced all the usual symptoms of poisoning by that substance, from which the patient did not entirely recover until after four or five days. Two cases of this kind, in which a lotion of belladonna had been applied, are mentioned in the Chemical News (London, Nov. 1866, 216). In a case reported by Dr. Smith [Boston Med. and Surg, Jour., Dec. 1879, 895), an application of belladonna ointment to the neck of the womb of a woman in labor was followed in less than fifteen minutes by dizziness, succeeded in quick succession by great thirst, dryness and burning of the mouth and fauces, nausea and ineffectual attempts to vomit, spasmodic movements of the arms, and striking at imaginary objects. There were short intervals of repose, then sudden convulsive movements ; the pulse became feeble, the extremi- ties cold, and the pupils widely dilated. Under the subcutaneous injection of a third of a grain of morphine the convulsive move- ments soon subsided ; but the thirst and dryness of the throat re- mained for ten or twelve hours. Labor-pains did not again appear for ten days, when the woman was safely delivered. Atropine. — The symptoms produced by atropine in its pure state are the same in kind as those occasioned by belladonna, but they are usually much more prompt in appearing. In a case related by Dr. Schmid, a stout, healthy man swallowed from one-sixth to one-fourth of a grain of the alkaloid in solution. An hour afterward, the patient was in a state of fearful excitement ; the tongue was swollen and pro- jected between the teeth, and he incessantly moved it and his lips in a stammering manner, but without emitting a single intelligible word. The eyes were staring; the head hot, and the countenance livid; the pupils dilated to their utmost, and insensible to light ; the pulse was rapid, full, and strong, and there was a constant desire, but without the power, to make water. During the following hour the excitement continually increased, when the subcutaneous injection of one-fifth of a grain of morphine acetate into the right temple was soon succeeded by a state of calm. After two hours more, the excitement had again attained almost its former height, but it was again subdued by a repe- tition of the morphine injection. The patient now gradually recovered, PHYSIOLOGICAL EFFECTS. 637 the only symptoms remaining about twenty-four hours after the oc- currence being extreme weakness, dryness of the tliroat, slight twitch- ings of the limbs, and a dilated state of the pupils. [Amer. Jour. Med. /&/., July, 18(J6, 269.) Dr. S. W. Gross reports a case [Amer. Jour. Med. ScL, Oct. 18G9, 401) in which a healthy woman, aged forty-three years, througii the mistake of a druggist, took some pills containing {/tree grains of atrojiine, and died from the effects of the poison in about fifteen hours after taking the dose. The symptoms in this case began in about fifteen minutes after the pills had been taken, there being at first vio- lent agitation, soon followed by pleasant delirium, in which the patient picked at her clothes, tried to get out of bed, and imagined she was sewing, or nursing her child, or engaged in shopping with her sister. Dr. Andrew, of Edinburgh, relates an instance in which two-thirds of a grain, taken in mistake by a female, produced most violent symp- toms, from which the patient did not entirely recover for more than a week. (Wharton and Stills, Med. Jur., 639.) And in a more recent case, a similar quantity of the sulphate of the alkaloid, taken by a lady, caused most alarming symptoms during a period of eighteen hours, although the contents of the stomach had been early evacuated by means of the stomach-pump. {Amer. Jour. Pharm., July, 1871, 324.) An instance is mentioned in which a solution of oidy one- twelfth of a grain of atropine taken in mistake by a physician caused his death in about thirty hours. [Gaillard's Med. Jour., May, 1880, 583.) On the other hand, Dr. Roux has reported an instance in which a lady, in a fit of despair, swallowed a solution containing nearly two grains of atropine, and entirely recovered, not, however, with- out suffering the most severe symptoms. The treatment employed in this case consisted of emetics, followed by a strong decoction of coffee and M. Bouchardat's solution of iodine in potassium iodide. The employment of atropine in the form of subcidaneous injec- tion has in repeated instances been followed by very serious and even fatal results, even when injected in very minute quantity. Dr. Eulenberg relates an instance in which he employed in this manner, in the case of a ladv affected with facial neuralo:ia, l-48th of a frrain of the alkaloid, and alarming symptoms of poisoning soon appeared. The patient threw herself about the bed entirely unconscious, and from time to time broke out in furious delirium; the limbs, and also 633 ATROPINE. the head, were shaken with convulsive jerkiugs. The pupils were moderately dilated, the pulse small, and somewhat increased in fre- quencv. An immediate injection of one-third of a grain of morphine into the temporal region, in close proximity to the former place of injection, was followed within about three minutes by a cessation of the twitchings, and in ten minutes the patient fell into a hea%y, peace- ful sleep, from which she awoke in eight hours without any symptom of the poison being present. [Amer. Jour. Med. Sci., April, 1866, 434.) In another case, related by Dr. Lorent, less than the 1-lOOth of a grain of the alkaloid, employed in this manner, produced very alarming results. Dr. Arnold mentions an instance in which death resulted in five minutes from the one-thirtieth of a grain of atropine given hypodermically. {Baltiraore Med. Jour., March, 1871, 169.) On the other hand, Dr. T. B. Jewett relates a case in which recovery took place after the subcutaneous injection of a solution of one grain of atropine, three grains of morphine having been administered hypodermically soon after the atropine had been injected. [Proc. Connecticut Med. Soc, 1879, 82.) The external application of atropine may speedily produce death. In an instance reported by Dr. Ploss, of Leipsic, an ointment com- posed of fifteen parts of atropine sulphate to seven hundred parts of lard, applied as a dressing to a blistered surface on the neck of a man, caused death, under the most violent symptoms of belladonna poison- ing, within two hours after the application had been made. [Amer. Jour. Med. Sci., April, 1865, 541.) A few drops of an aqueous so- lution containing two-thirds of a grain of the alkaloid to the ounce of fluid, applied to the eye of a man affected with cataract, produced violent constitutional effects, with constant hallucinations, and inabil- ity to pass urine; the violent delirium continued during the ensuing night, and it was some days before the patient entirely recovered. Teeatment. — This consists, in case the poison has been swal- lowed, in the speedy administration of an emetic or the employment of the stomach-pump. Of the various chemical antidotes that have been proposed may bo mentioned tannic acid, a solution of iodine in potassium iodide, hydrate of magnesia, and animal charcoal. If either of these substances be employed, it should only be in connec- tion with emetics or the use of the stomach-pump. As a physiological antidote, morphine, administered either by the mouth or by subcutaneous injection, has been found very beneficial, PA'nioLoCilCAl, KFFKCTS. 039 as ill sonic of tlie instances already cited. In a case of recovery men- tioned by Dr. J. B. Cox, in which one grain of atroiiine liad been taken, it is said that from sixteen to eighteen grains of morphine were injected hypodermically without there being at any time symp- toms of narcotism from the use of the mor|)hine. [Med. Times, Feb. 188-1, 377.) rUocarpinc, employed subcutaneously, has also been strongly advised in atropine poisoning. Dr. Purjesz relates a case in which about two grains and a half of atropine had been taken, and under the use of repeated injections of a salt of pilocarpine, using in all about 6.4 grains of the salt, the toxic symptoms gradually subsided, and at the end of three hours after taking the atropine the patient had quite recovered, even the dilatation of the pupils having passed off. Post-mortem Appearances. — These, as in death from most of the vegetable poisons, are subject to considerable variation. The more constant appearances are a dilated state of the pupils, more or less redness of the raucous membrane of the stomach and small intes- tines, fulness of the cerebral vessels, and congestion of the lungs. The blood is usually dark-colored and liquid. Instances are related, however, in which this poison produced death without leaving any notable morbid change in the body. In the case reported by Dr. H. Taylor, in which a drachm of the extract of belladonna had been taken, eighteen hours after death, the pupils were found greatly dilated. The lungs were much engorged ; and the pleural cavities contained a little dark blood. The heart was empty, except the right auricle, which contained about six drachms of dark, semi-coagulated blood. The stomach was fragile and softened in texture. AH the other abdominal organs appeared healthy. In Dr. Gross's case, in which three grains of atropine had been taken and proved fatal in about fifteen hours, thirty-eight hours after death the pupils were somewhat dilated, and the face was livid. The vessels of the pia mater Avere turgid with blood, and there was great subarachnoid effusion ; the brain-tissue was greatly softened. The lungs were congested ; the heart was very soft, and its cavities contained fluid blood. The intestines were pale, but the stomach presented suggillations at its cardiac extremity; the kidneys were congested ; and the bladder was empty. 640 ATROPrN'E. Chemical Peopeeties. Ix THE Solid State. — Atropine, in its pure state, is a white^ odorless solid, Avhich crystallizes in the form of transparent prisms, usually aggregated into beautiful tufts or stellated groups. It has a bitter, acrid taste, ^'hen heated in a tube, it readily fuses to a color- less, transparent liquid, which ascends the sides of the tube ; upon cooling, the liquid becomes a clear gummy mass, and ultimately con- cretes to a vitreous solid. ^Yhen gradually heated on porcelain, it fuses and is slowly dissipated, giving rise to dense white fumes. Ac- cording to Planta, the fusing point of atropine is 90° C. (194° F.), and at 140° (284° F.) it is volatilized, partially unchanged, the greater part undergoing decomposition. When rapidly heated, it melts, puffs up, then evolves dense white fumes, and takes fire, burning with a bright flame, and leaving a shining black cinder, which may be entirely consumed. Heated in contact with a fixed caustic alkali, it readily undergoes decomposition, with the evolution of ammonia. Atropine has strongly basic properties, and completely neutralizes even the most powerful acids, forming salts, several of which are readily crystallizable. Concentrated nitriG acid dissolves the pure alkaloid without change of color, even upon the application of heat : the subsequent addition of stannous chloride produces no visible change. So, also, concentrated sulphuric acid dissolves it to a color- less solution, which is unchanged by a crystal of potassium nitrate; on the addition of a crystal of potassium bichromate, the acid solu- tion slowly acquires a green color, due to the formation of chromium sesquioxide. Solubility. — A sample of atropine examined by Planta was solu- ble in 299 parts of water at the ordinary temperature; but a single experiment in our own hands indicated that the alkaloid requires 414 parts of that liquid for solution, even after several hours' diges- tion. It is readily soluble in nearly every proportion in alcohol and in chloroform, and is freely soluble in absolute eihe:)\ Upon sponta- neous evaporation, it separates from either of these liquids in the crystalline form. A saturated aqueous solution of the alkaloid has a well-marked alkaline reaction. Most of the salts of atropine are freely soluble in water and in alcohol ; but they are almost wholly insoluble in ether and chloroform ; at least this is the case with the sulphate and hvdrochloride. BROMINE IN BROMOHYDRIC ACID TEST. G41 Op Solutions op Atropine. — The following result's, in regard to the beliiivior of solutions of atroi)ine, are based upon the exam- ination of two apj)arcntly perfectly pure specimens of the alUaloid, pre[)arecl by (litlc'rent well-known European manufacturers, one of the samples being employed in the form of sulphate, and the other as hydrochloride. The fractions em|)l()yed indicate the fractional part of a grain of the pure alkaloid i)resent in one grain of water; and the results, unless otherwise indicated, refer to the behavior of one grain of the solution. 1. Tlie Caustic Alkalies. The fixed caustic alkalies throw down from concentrated aqueous solutions of salts of atropine a white, amorphous precipitate of the pure alkaloid, which is readily soluble in free acids, and also in large excess of the precipitant. After a time, especially if the mixture lias been stirred, the precipitate assumes the crystalline form. The presence of foreign organic matter readily prevents the formation of crystals. One grain of a 1-lOOth solution of the alkaloid yields a quite copious precipitate, which on being stirred with a glass rod becomes in a little time a mass of crystals, of the forms illustrated in Plate XII., fig. 4. Solutions but little more dilute than this fail to yield a precipitate. Ammonia produces in solutions of salts of the alkaloid the same precipitate as occasioned by the fixed caustic alkalies ; but the deposit is much more readily soluble in excess of the preci})itant. Potassium carbonate produces in a 1-lOOth solution of the alka- loid a distinct turbidity ; but the carbonates of sodium and ammonium fail to produce in a similar solution any visible reaction. 2. Bromine in Bromohydric Acid. An aqueous solution of bromohydric acid saturated with free bromine produces in solution of salts of atropine and of the free al- kaloid, even when highly diluted, a yellow, amorphous precipitate, which in a little time becomes crystalline. The precipitate from somewhat strong solutions of the alkaloid after a time disappears; but it is immediately reproduced upon further addition of the re- agent. The precipitate is insoluble in acetic acid, and only very sparingly soluble in large excess of hydrochloric, nitric, and sulphuric 41 ' 642 ATROPINE. acids, and in the fixed caustic alkalies : it is even produced from solutions of the alkaloid in concentrated sulphuric acid. 1. -j-^ grain of atropine, in one grain of water, yields a very copious, bright yellow, amorphous precipitate, which very soon, begin- ning along the margin, becomes a mass of crystals, Plate XII., fig. 5. After several minutes most of the crystals dissolve, but they may be reproduced, even several times, by further addition of the reagent. 2. 5oVo grain yields a copious, yellow deposit, wdiich soon furnishes crystals having the forms illustrated above. 3. YTT.Voo" g^^'" • a quite good, yellowish precipitate, which in a few moments becomes granular and crystalline, and presents the appearance figured in Plate XII., fig. 6. 4. 9-5-,Viro grai" • i^ a very little time a quite satisfactory deposit of short crystalline needles and granules. 5. -g-o-.^-oir grain : after some minutes a few granules appear, but the result is not satisfactory. The production of the above crystals is quite characteristic of this alkaloid. Although the reagent produces yellow precipitates with most, if not all, of the other alkaloids, and with certain other organic substances, yet all these deposits, with the exception of that from opianyl, unlike the atropine precipitate, remain amor- phous. The crystallized atropine deposit is readily distinguished from the opianyl compound by its form. It may here be remarked that the reagent produces a similar crystalline precipitate with daturine, and also with hy oscy amine ; but, as we shall see hereafter, there are strong reasons for believing these alkaloids to be identical with atropine. We have found the bromine precipitate to become crystalline in the presence of even comparatively large quantities of foreign organic matter. In the absence of a solution of bromohy- dric acid, an alcoholic solution of bromine may be employed as the reagent. 3. Picric Acid. An alcoholic solution of picric acid occasions in somewhat strong solutions of salts of atropine a yellow, amorphous precipitate, which is readily soluble in acids, even in acetic acid. After a time the precipitate becomes more or less crystalline. 1. jYU grail of atropine yields a copious, light yellow deposit. If the mixture be stirred with a glass rod, it soon yields streaks of IODINE TEST. G43 granules along the jxith of tiic rotl, and in a little time the deposit becomes entirely crystalline, the crystals being princi- ])ally in the form of transparent plates, and these more or less aggregated into very beautiful groups, Plate XIII., fig. 1. 2. Y^(i^ grain : within a few moments a slight, greenish-yellow pre- cipitate appears, and in a little time there is a quite good deposit. If the mixture be stirred, it soon yields a fine crystalline deposit. 3. s^Vo" ^'■'^'•1 • upon stirring the mixture, it yields after a little time caseous streaks over the bottom of the watch-glass con- taining the mixture; but the reaction is not very satisfactory. This reagent also produces crystalline precipitates with various other substances, but the forms illustrated above are quite peculiar to atropine. 4. Aiiric Chloride. This reagent produces iu solutions of salts of atropine, when not too dilute, a light yellow, amorphous precipitate of atropine chloro- aurafe, Ci7H23N03,HCl,AuCl3, which after a time becomes converted into crystals. The precipitate is insoluble in potassium hydrate, and but sparingly soluble in acetic and hydrochloric acids. 1. YDT gi'^in of atropine yields a copious precipitate, which soon becomes a mass of crystals having the peculiar forms shown in Plate XIII., fig. 2. " 2. ytjVo" grain yields a good deposit, which soon, especially if the mixture be stirred, assumes the crystalline form. 3. g J(j „ grain yields no indication, even after the mixture has stood some time. The crystalline form of the double atropine salt, as figured above, readily distinguishes it from other substances. The formation of these crystals, however, is readily prevented by the presence of foreign organic matter. 5. Iodine in Potassium Iodide. A solution of iodine in potassium iodide throws down from solu- tions of salts of atropine, and of the free alkaloid, a reddish-brown, amorphous precipitate, which is insoluble in acetic acid, and only sparingly soluble in potassium hydrate. 1. Yoo" grain of atropine yields a very copious precipitate, which dissolves to a clear solution in about three drops of a saturated solution of potassium hydrate. 64:4 ATROPINE. 2. YoVcT gi'ain : a quite copious precipitate. 3. xo",Tjro" gi'^iii yields a very good deposit. 4. 5-0-,^-oT g'^'^iii yields at first a yellowish turbidity, and after a little time a distinct, reddish-brown precipitate. 5. YoifhrTo g""^!'^ yields a very distinct turbidity. The reaction of this reagent is common to a laro-e class of sub- stances. Other Reagents. — Dr. D. Vitali has lately shown (1880) that if atropine or any of its salts in the solid state, placed in a porcelain capsule, be heated with a few drops of nitric acid, and then the liquid evaporated at a moderate temperature, the cooled colorless residue on being touched with a drop of a concentrated cdcoholiG solution of potassium hydrate will assume a splendid violet or purple color, even if only a minute quantity of the alkaloid be present. After a little time this color disappears; but it maybe reproduced upon the further addition of the alcoholic solution of the caustic alkali. We find that under this test 1-1 000th grain of atropine will yield a fine purple coloration, which may be reproduced on adding a second drop of the alkaline alcoholic solution. And the l-25,000th of a grain yields a perfectly satisfactory purple coloration. A marked purple coloration may be obtained from even the l-50,000th of a grain of the alkaloid, especially if the alkaline alcoholic solution be added to the nitric acid residue while still warm. The reaction of this test is common, we find, to atropine, datu- riue, hyoscyamine, and duboisine. Of some sixty other alkaloids examined under this test by Dr. D. Vitali, he found none to give the same reactions as atropine and daturine. According to Dr. A. W. Gerrard [Pharm. Jour, and Trans., March, 1884, 718), if a little atropine in a test-tube be treated with a small volume of a 5 per cent, solution of mercuric chloride in 50 per cent, alcohol, and the mixture gently warmed, a brick-red pre- cipitate will be produced. The precipitate has, according to Dr. Gerrard, the composition Cx7H23N03,HCl,2HgCl2, and may be ob- tained in the crystalline state. The precipitate, however, does not appear in dilute solutions of the alkaloid. Dr. Gerrard found this reaction to be also common to daturine, hyoscyamine, duboisine, and 8KPARATION FROM ORGANIC MIXTURES. G45 li()m;i(roi)Iiu' ; Imt of a ntiiiihor of otlier alkaloids examined lujne gave a red precipitate. Tannic acid produces in solutions of salts of atroj)ino a dirty- white, anior|)lioiis precipitate, wliicli is readily solnhle in tiie canstic alkalies and in free acids. One grain of a 1-lOOth solntion of the alkaloid yields a copions dejjosit ; and a similar quantity of a 1-lOOOth solution a <|uite distinct reaction. Phdinic chloiide and jjalladic chloride throw down from concentrated solutions of salts of the alkaloid dirty-brown, amorphous precipitates. Strong solutions of salts of atropine, when treated with a stream of chlorine gas, become slightly turbid, and yield on the subsequent addition of ammonia a white precipitate. Potassium iodide, potassium sulphocyanide, potassium chromates, mercuric chloride, mercurous nitrate, potassium ferro- and ferri- cyanide, and gallic acid fail to precipitate even concentrated solu- tions of salts of atropine. Physiological Test. — The property possessed by atropine of di- lating the pupil of the eye has been proposed as a means of detecting its presence. Dr. Headland states [Actioji of Medicine, 294) that the l-3000th of a grain of the alkaloid dropped, in the form of solution, into the eye of an adult will answer this purpose. It must be borne in mind, however, that this property is also possessed by daturine, hyoscyamine, duboisine, and certain other alkaloids. Separatiox from Organic Mixtures. Suspected Solutions and Contents of the Stomach. — These should first be carefully examined for the presence of any solid portions of the plant or the seeds, which, if found, may be identified by their physical and botanical characters. On account of the indigestible nature of the seeds and berries, they may remain in the alimentary canal for some days without undergoing any change. Dr. Christison cites several instances {op. cit., 644) in which the seeds and frag- ments of the fruit were discharged from the bowels and bv vomitingr even several days after they had been taken. Atropine is separated with considerable difficulty from complex organic mixtures, especially when it exists in the form of portions of the plant. The suspected mixture, after comminution of any solids present, and dilution if necessary, is treated with about an equal volume of strong alcohol, slightly acidulated with sulphuric acid, 646 ATROPINE. and exposed for about half an hour to a gentle heat; when cool, the liquid portion is strained through muslin, the residue washed with alcohol, and the strained liquid and washings concentrated to a small bulk, at a moderate temperature, on a water-bath. If during the evaporation much insoluble matter separates, it is removed by a strainer. The cooled concentrated liquid is passed through a moist- ened filter, then washed by agitating it with about twice its volume of pure ether, which, after repose, is carefully decanted and reserved for future examination, if necessary ; the aqueous solution may again be washed with a fresh portion of ether, and this removed as before. The aqueous liquid is now rendered slightly alkaline by potassium hydrate or carbonate, and thoroughly agitated with about twice its volume of pure cldoroform, which will dissolve the liberated alkaloid, if present ; after the liquids have completely separated, the chloro- form is carefully removed to a glass capsule and allowed to evaporate spontaneously. The residue thus obtained is stirred with a little water contain- ing a trace of sulphuric acid, and the solution, after filtration if necessary, examined by some of the liquid tests for atropine. As the bromine test is one of the most characteristic yet known for the identification of the alkaloid, it should first be applied to a single drop of the solution. Another drop of the solution may be evap- orated to dryness and the residue examined by Vitali's test. If the bromine reagent should fail to produce a crystalline precipitate, it is quite-certain that neither of the other liquid tests would produce crystals, without which the results are common to a large class of organic substances. It must not, however, be expected that the bro- mine reagent will always produce a crystalline deposit containing all the forms obtained from a perfectly pure solution of atropine: most frequently, under the present conditions, the precipitate consists of short, opaque, irregular needles and granules, but these are charac- teristic of the alkaloid. In case the bromine reagent produces a precipitate which will not crystallize, the remaining portion of the solution may be ren- dered alkaline, and the alkaloid again extracted by chloroform. This fluid may now, upon spontaneous evaporation, leave the alka- loid, if present in very notable quantity, in the crystalline state. A portion of the residue may be submitted to the physiological test for the alkaloid. DATURINE. 047 Oil applying tlio niotliod now considered to the oxiunination of the contents of the stoniaciis of animals to whicli comparatively small qnantities of a flnid extract of belladonna had been adde under the conditions just stated, dissolves with a just perceptible brownish tint to a colorless solution. The production of this series of colors, in connection with the formation of the precipitate, is quite characteristic of solanine. Even the 1-lOOOth of a grain of the alkaloid, as just pointed out, will yield very satisfactory results. If a little solanine be treated with a few drops of a warm mix- ture of equal volumes of concentrated sulphuric acid and alcohol, as first observed by Dr. Helwig, a beautiful rose-red color is quickly developed ; this color may remain unchanged for several hours. Even a very minute quantity of the alkaloid will manifest this coloration. This reaction is not interfered with by the presence of morphine, even in relatively large quantity. 3. Iodine in Potassium Iodide. An aqueous solution of potassium iodide containing free iodine causes somewhat concentrated solutions of salts of solanine to assume a deep orange-red color, and throws down an orange-brown precipi- tate, which is unaffected by diluted acids. 1. YTS grain of solanine, in solution in one grain of water, yields the results just stated. The precipitate is readily soluble in potassium hydrate to a colorless solution, from which after a time a dirty-white precipitate separates. 2. YiJoT grain : an orange-brown solution and a slight precipitate. 3. gQ^OQ grain : the mixture assumes a yellowish-brown color, but fails to yield a precipitate. The reactions of the first two mentioned solutions are peculiar to solanine ; but with more dilute solutions the results are uncertain, since the reagent itself imparts a more or less yellowish-brown color even to pure water. It must also be borne in mind that the reagent produces reddish-brown precipitates with most of the other alkaloids and with certain other organic substances. 4. Potassium Chromate. This reagent produces in solutions of salts of solanine, when not too dilute, a yellow, amorphous precipitate, which is insoluble in excess of the precipitant, but readily soluble in acetic acid. If the 680 SOLAJiflNE. mixture containing the deposit be treated with several drops of concentrated sulphuric acid, the precipitate quickly dissolves, and the solution slowly acquires a bluish or bluish-green color, which remains unchanged for several hours. The production of this color is peculiar to the precipitate produced from solutions of solanine. 1. yi^ grain of solanine, in one grain of water, yields a very copious precipitate, which, when treated with sulphuric acid, undergoes the changes just described. 2. YWTo grain : the mixture immediately becomes turbid, and after a little time yields a quite fair, yellow, flocculeut precipitate. If the precipitate be dissolved in a few drops of sulphuric acid, the solution soon acquires a quite distinct bluish-green color. 1 grain : after a time a slight deposit of yellowish flakes. "•5 00 Potassium dichromate produces much the same reactions as the monochromate, but the precipitate does not appear in quite as dilute solutions, since it is somewhat soluble in the chromic acid eliminated by the reaction when this reagent is employed. 5. Bromine in Bromohydric Add. An aqueous solution of bromohydric acid saturated with free bromine throws down from solutions of solanine salts an orange- yellow or yellow, amorphous precipitate, which is sparingly soluble in diluted acetic acid. After a time the precipitate acquires a dirty- wbite color, and slowly disappears. 1. Yo^ grain of solanine, in one grain of water, yields a very copious orange-yellow precipitate. 2. YWU^ grain : a quite good, yellow deposit. 3. g-oVo gi'^JQ yields only a just perceptible turbidity. The reaction of this reagent is common to solutions of various other organic substances besides solanine. Other Reagents, — Picric acid produces in concentrated solutions of salts of solanine a copious, yellow, gelatinous precipitate, which is readily soluble in excess of the precipitant. Tannic acid occasions a white, flocculent precipitate. Ammonium oxalate and sodium phos- phate produce, in similar solutions, white, gelatinous precipitates. Neither of the following reagents produces a precipitate, even in concentrated solutions of salts of the alkaloid : potassium sulpho- SEPARATION FROM ORGANIC MIXTURES. 681 cyanide, potassium f'erro- and ferri-cyanide, the chlorides of gold, platinum, and jnilladiuni, potassium iodido, and free chromic acid. Separation from Organic Mixtures. Although there is no difficulty in identifying even a minute trace of solanine when in its pure state, yet when ])resent in only minute quantity in complex organic mixtures its separation in a state suffi- ciently pure for testing is attended with considerable difficulty, and is sometimes impossible, at least by any method at present known. As the alkaloid is nearly wholly insoluble both in ether and in chloro- form, it is obvious, as heretofore stated, that neither of these liquids will serve to separate it from organic mixtures. The suspected mixture, as the contents of the stomach, after being carefully examined for the presence of any solid portions of the poisonous i)lant, is very slightly acidulated with a drop or two of sulphuric acid, and gently heated with diluted alcohol for about half an hour. The mass is then allowed to cool, transferred to a linen strainer, and the strained liquid concentrated on a water-bath to a small volume, after which it is filtered. The filtrate is evapo- rated, at a temperature not exceeding 49° C. (120° F.), to almost dryness, the residue well stirred with a small quantity of pure water, and the solution filtered. Any solanine present will now exist in the filtrate in the form of sulphate, and may, if not in too minute quantity, be separated by either of the following methods, the first of which is based upon the principles first applied by Wackenroder for the preparation of the alkaloid, and the second upon those first announced by Uslar and Erdmann. According to the first of these methods, the clear filtrate is treated with slight excess of powdered calcium hydrate, and the mixture allowed to repose in a cool place for from twelve to twenty-four hours, in order that the eliminated solanine may completely subside. The precipitate is then collected on a filter and allowed to drain, then washed with a small quantity of cold water containing a trace of ammonium carbonate, and, while still moist, gently warmed with about half an ounce of strong alcohol, which will dissolve the alka- loid, whilst the calcium sulphate and any excess of caustic lime employed will remain, being insoluble in this liquid. The alcoholic solution, after filtration, is gently evaporated to dryness, the residue treated with a small quantity of water very slightly acidulated with 682 SOLANINE. acetic acid, and the solution filtered. A drop of the filtrate may now be examined by the sulphuric acid test, and, if it yields satis- factory evidence of the presence of solanine, other portions of the solution by some of the other tests for the alkaloid. Should, how- ever, the sulphuric acid test fail, the filtrate is concentrated and another drop examined in the same manner before applying any of the other tests. Or, secondly, the filtrate, supposed to contain the sulphate of solanine, may be agitated with an equal volume of warm amyl alcohol, which, after the liquids have completely separated, is de- canted, and the operation repeated with a fresh portion of the alco- hol. By this treatment much of the coloring matter will be removed, while the alkaloidal salt will remain in the aqueous solution. This solution is then treated with slight excess of ammonium carbonate, and agitated with hot amyl alcohol, which will now dissolve the liberated alkaloid. The alcoholic solution is decanted, the aqueous liquid washed with a fresh portion of the hot alcohol, and the mixed alcohols evaporated to dryness on a water-bath. The residue is stirred with strong, ordinary alcohol, the solution filtered and evap- orated to dryness. The residue thus obtained is treated with a small quantity of water containing a trace of acetic acid, and the filtered solution examined in the manner above described. On following the methods now considered, for the examination of complex organic mixtures each containing two drachms of Thayer's fluid extract of dulcamara, — the medicinal dose of which is from half a drachm to one drachm, — we recovered by each a very notable quantity of solanine, in its very nearly pure state, especially when precipitated from the final aqueous solution by an alkali. The first- mentioned method furnished somewhat the best results; however, the quantity of the alkaloid recovered by either process was several times more than sufficient to establish fully the presence of the poison. GELSEMINE. 683 CHAPTEE YL Gelsemine. Gelsemic Acid. (Yellow Jessamine.) History. — Gelsemine, or gelsemia, is the active principle of Gelse- mium sempei-virens, popularly known as yellow jasmine. Gelsemine was first obtained in its pure state, and examined chemically, by the author, in 1870. {Amer. Jour. Pharm., xlii. 1.) At the same time it was shown that the plant contained a non-nitrogenized principle, having an acid reaction, which was named gelseminic, or gelsemic, acid. M. Sonnenschein has claimed that this latter principle is identical in composition and chemical properties with the glucoside cesculin, found in the bark of the horse-chestnut, and in certain other barks ; but we have elsewhere shown that this claim is quite erroneous. {Ibid., July, 1882.) MM. Sonnenschein and Robbins assigned to gehemine the com- position C11H19NO2; but, according to A. W. Gerrard, its for- mula is C12H14NO0, and that of the hydrochloride 2C12H14NO,; HCl. [Pharm. Record, March, 1883, 67.) Preparation. — The finely-powdered root of the plant is thoroughly extracted with a mixture of equal volumes of strong alcohol and water, and the clear liquid concentrated at a moderate heat to a volume something less than the weight of the root employed. The liquid is then allowed to stand until the resinous matter has deposited, after which it is filtered. The filtrate is treated with slight excess of ammonia, and thoroughly agitated with something more than its volume of rectified ether, which will readily take up both the gelse- mic acid and the alkaloid. The ether is decanted, and the extraction repeated two or three times with fresh portions of ether. a. Gelsemine. — The ether thus employed is treated with slight excess of hydrochloric acid, added drop by drop, and the mixture allowed to stand some hours. The alkaloid will thus be precipitated 684 GELSEMINE. in the form of the hydrochloride, more or less granular and crystal- line, and adherent to the sides of the vessel. After decanting the ether, the residue is washed with a little fresh ether, then dissolved in just sufficient water, and the filtered solution treated with slight excess of ammonia, which will precipitate the greater portion of the alkaloid as a pure white, curdy mass. This is quickly collected on a filter, washed with a little cold water, and allowed to dry. To recover the gelsemine still remaining in the foregoing filtrate, the latter is concentrated, first by a moderate heat, then spontaneously, when the alkaloid, displacing in part the ammonia of the ammonium chloride present, will separate chiefly in the form of bold groups of prismatic crystals of the hydrochloride of gelsemine, Plate XV., fig. 1. These may be washed with a mixture of alcohol and ether. If the concentration has been carried to dryness, the residue may be washed with a little water, to remove any ammonium chloride present. b. Gelsemic Acid. — On evaporation of the ether from which the alkaloid was precipitated by hydrochloric acid, the organic acid will be left in the form of comparatively large tufts and groups of crystals, Plate XV., fig. 2. These are washed with a little absolute alcohol, which will readily dissolve, in part at least, any coloring matter present. The crystals, if still colored, may be further purified by dissolving them in hot alcohol, which on cooling will deposit the excess in the form of delicate colorless needles. From the dried root of the plant we have obtained, as the average of several different methods employed, about 0.25 per cent, of gelsemine and 0.5 per cent, of gelsemic acid. These principles seem to be present only in the bark of the root, the woody portion being entirely free. Physiological Effects. — Gelsemine is an exceedingly active poison. One-eighth of a grain of the alkaloid being administered hypodermi- cally to a cat, the animal soon exhibited signs of great distress, and in forty minutes there was great prostration, with difficulty in moving, the legs giving way, and the movements being frequently backwards. The respiration became greatly reduced, the pupils dilated to their fullest extent, and death took place in one hour and a half after the poison had been administered. One -third of a grain of the alkaloid administered subcutaneously to a rabbit produced within ten minutes great weakness, then tremors of the body, backward movements, violent clonic convulsions in PHY8I0IX)QICAL EPFEOTS. 685 which the animal turned a complete backward somersault; followtd by gasping respiration and death within twenty-two minutes after the administration. A like quantity administered to a frog pro- duced similar symptoms, with falling of the jaw and death in twenty minutes. Two grains of gelsemic acid administered subcutaneously to a large rabbit produced no marked effect whatever. So, also, one-fifth of a grain produced no effect upon a pigeon. But one-half grain of the acid being administered hypodermically to a frog, quickly produced deep fluorescence of the eyes, great agitation, general pros- tration, and death in forty minutes. In another experiment, a like quantity of the acid caused a complete cataleptic condition and death within ten minutes. Repeated experiments with varying quantities of gelsemic acid indicated it to be very poisonous to frogs. These results confirm those previously obtained by Dr. J. Ott. Gelsemium Preparations. — The preparations of gelsemium at present officinal are the fluid extract, one hundred parts of which represent one hundred parts of the dried root ; and the tincture, one hundred parts of which correspond to fifteen parts of the root. The medicinal dose of the former preparation is from two to four minims ; that of the latter, from fifteen to twenty-five minims. The only preparation of the drug officinal prior to the United States Pharmacopoeia of 1880 was the fluid extract, each fluid-ounce of which represented 480 grains of the dried root. The tincture then found in the shops had usually one-fourth, but sometimes only one-eighth, the strength of the fluid extract. A concentrated tincture representing 480 grains of the fresh root per fluid-ounce was also employed. The present fluid extract is five per cent, weaker than that for- merly directed. In a series of examinations of various samples of the fluid extract as formerly prejDared, we found it to contain quite uniformly about 0.2 per cent, of gelsemine and 0.4 per cent, of gelsemic acid. Poisoning by gelsemium preparations has of late years been of not unfrequent occurrence, but chiefly as the result of accident or ignorance, there being, so far as we know, only tw^o or perhaps three cases in which it was criminally administered. Symptoms. — The symptoms produced by poisonous doses of gelsemium are impaired sight, double vision, and sometimes total 686 gelsemhste. blindness, with falling and loss of control of the upper eyelids; the face is congested, and the lips livid, but the face may be pale. The pupils are dilated, and usually insensible to light; the eyes fixed and more or less staring. There may be falling of the lower jaw, the mouth being sometimes wide open. Speech is impaired or entirely lost, and the tongue appears thick. The gait is staggering ; the skin warm and moist, with occasionally free perspiration. The pulse is small, feeble, irregular, and intermittent, but it has been observed full and strong. There is great muscular relaxation, with general prostration and diminished sensibility, and the extremities are cold. The breathing is slow, labored, spasmodic, and sometimes stertorous. Violent spasms of the throat, resembling those of hy- drophobia, have been present in a few cases. The mind usually remains clear, but unconsciousness has been present even when recovery followed. The time within which the symptoms first appear has varied from a few minutes to about two hours, but they usually manifest themselves within half an hour. In a case related by Dr. W. W. Seymour, in which a teaspoonful of the fluid extract of gelsemium was given to a lying-in woman in mistake for ergot, ten minutes afterward she was extremely prostrated, almost pulseless, and the respiration was failing. She finally recovered. [Boston Med. and Surg. Jour., Dec. 1881, 590.) Dr. R. P. Davis reports a case in which a delicate man, having taken a tablespoonful of Tilden's fluid extract of gelsemium, was found soon after lying upon his left side, the face somewhat congested, the pupils dilated, but respond- ing to light; eyelids half closed, with inability to move them; the lower jaw drooping, and the tongue thick ; his skin was warm and moist ; the pulse small and feeble, and the respirations diminished in number. An emetic being administered failed to act. A little later, the patient was totally unconscious, the pupils widely dilated, the breathing spasmodic, the surface cold and congested ; pulse almost imperceptible, and death took place in two hours and a half after the poison had been taken. (Amer. Jour. Med. Sci., Jan. 1867, 271.) In a case reported by Dr. J. E. Blake {New Yoi^h Med. Jour., April, 1875), a strong man took, by mistake, about two drachms of the tincture of the plant. Besides the usual effects, such as dimness of vision, prostration, diminished action of the heart and respiratory - / PERIOD WHEN FATAL. 687 organs, the patient, about Iialf an hour after taking the dose, had synij)toms closely resembling those observed in the frightful spasms of ]iy(lro])hobia. At short intervals the most distressing paroxysms of dyspnoea occurred, during which he both clutched at his throat and beat the air with his hands. lit; finally recovered, being much relieved by morphia hypodermieally administered. In another in- stance, related by Dr. J. T. Boutelle {Boston Med. and Surg. Jour., Oct. 1874, 321), a young man, aged twenty-four years, suffering from neuralgia, took at 1 a.m. a teaspoonful of the fluid extract, and in fifteen minutes repeated the dose. The pain was soon relieved, and his eyes felt heavy, and in about half an hour he complained of choking, and soon arose struggling for breath, pushing his fingers into his throat, as if trying to tear it open. He staggered, as if intoxicated, threw himself upon the floor, and became unconscious. At 4 A.M. the respirations were gasping, the pulse was rapid and feeble, and the patient could not be roused. The pupils were dilated and insensible to light ; the body was relaxed, the lower jaw drooping, the skin moist, the extremities cold, and, the pulse becoming slower and weaker, death took place at 4.45 a.m. We have elsewhere reported' a case in which three teaspoonfuls of the fluid extract were administered to a young, healthy married woman, several weeks advanced in pregnancy. Tn two hours after taking the dose, she complained of pain in the stomach, nausea, and dimness of vision. These symptoms were soon followed by great restlessness, ineffectual eiforts to vomit, and free perspiration over the body. After five hours, the pulse was feeble, irregular, and intermittent; there was great prostration, with irregular and slow breathing, and the skin was dry. The extremities were cold, the pupils dilated and insensible to light; the eyes were fixed, and con- trol over the eyelids was lost. The vital powers rapidly gave way, and death occurred in seven hours and a half after the poison had been taken. {Amer. Jour, Pharm., Jan. 1870, 14.) Period when Fatal. — Of twenty-five cases of gelsemium poison- ing that we have collected, thirteen proved fatal, and the fatal period varied from one hour to seven hours and a half. In a case communi- cated to me by Dr. M. P. Hatfield, of Chicago, fifteen grains of the resinoid "gelsemin" proved fatal to a woman in one hour. Tlie three following cases are briefly related by Dr. J. N. Freeman, of Brooklyn. {Lancet, Sept. 1873, 475.) A boy, three years old, took. 688 GELSEMINE. by mistake, about fifteen minims of tincture of gelsemium (made by- macerating four ounces of the root in a pint of dilute alcohol), and died from its effects in two hours. The first symptoms noticed were double vision and a staggering gait, soon followed by complete mus- cular relaxation. In the second case, a girl, aged nine years, took a dessertspoonful of the tincture. Soon after taking the dose, she complained of dimness of sight, double vision, and loss of muscular power, and died in less than two hours. In the third case, a boy, about three years old, was ordered every two hours a teaspoonful of a mix- ture containing ten grains of sulphate of quinine, one drachm of tinc- ture of gelsemium, and five drachms of syrup. After the first dose he became prostrated, and staggered in walking ; but in due time the dose was repeated. About half an hour after taking the second dose the body was perfectly flaccid, the pupils were dilated, there was froth at the mouth, the heart was beating feebly and slowly, and the pulse was imperceptible at the wrist. Death took place half an hour later. In a case reported by Dr. W. W. Seymour, a strong man, aged twenty-eight years, took a quantity of the tincture, variously stated from three drachms to two ounces, and died from its effects, under the usual symptoms, in six hours 'after the physician was called. {Boston 3Ied. and Surg. Jour., Dec. 1881, 590.) Fatal Quantity. — At present 4t is impossible to indicate the least fatal quantity of this drug. Prof. Seymour, of Troy, states that he has seen repeated instances in which two minims of the fluid extract, given three times a day, affected the sight; and four minims, three times a day, produced weakness of the legs and staggering. In a case reported by Dr. Freeman, cited above, a quantity of the tincture equivalent to about twelve minims of the fluid extract proved fatal to a boy, aged three years. And a case is related in which thirty- five drops of a tincture of the drug caused death in one hour and a half. A physician took, as we are privately informed, a mixture containing fifteen minims of the fluid extract, and repeated the dose at short intervals. After the fourth dose the usual symptoms of the poison appeared, and terminated fatally in less than four hours. In another instance, a physician, suffering from facial neuralgia, took ten minims of the fluid extract, and repeated the dose in half an hour. In fifteen minutes after the second dose there was great drowsiness, and pain over the frontal region ; the pulse was weak and intermittent, the body cold and shivering; the pupils were TREATMENT. 689 slightly contracted, and there was a general feeling of collapse. After vomiting freely, the patient rapidly recovered. {Med. Times, March, 1881, 382.) In a case mentioned by Dr. Seymour, a teaspoonful of the fluid extract proved fatal to a young lady. And in a Ciise already cited, two teaspoonfuls of the fluid extract, given in divided doses, proved fatal to a young man in less than four hours. Half a teaspoonful of a preparation of gelsemiura, being given to each of two children, was soon followed by the ordinary symptoms, and death in less than three hours. [Eckct'iG Med. Jour., May, 1879, 222.) Dr. A. L. Hall reports a case {Med. Record, Jan. 1882, 65) in which a strong woman took eight grains of "gelsemin," in two-grain doses repeatetl every three hours, and died from its effects within an hour after takinor the last dose. The same writer cites three other instances in which two, three, and four grains respectively of the same prepara- tion produced very alarming symptoms. The following cases of recovery may be mentioned. A lady took, by mistake, a teaspoonful of the fluid extract. Dimness of vision came on in an hour, and was followed by paralysis of the muscles of the lower jaw and tingling of the extremities. Five and a half hours later, she believed herself to be dying. There was great diffi- culty in swallowing, faintuess, and difficult articulation ; the mouth was wide open ; the pupils were greatly dilated, and insensible to light ; the pulse was rapid and feeble. Under the administration of carbonate of ammonium, and the use of electricity, she slowly recovered. (Dr. F. W. Goss, Boston Med. and Surg. Jour., July, 1879, 16.) In a case reported by Dr. R. P. Davis, a man recovered after taking a teaspoonful of the fluid extract. The treatment in this case consisted of an emetic, which acted freely, followed by large doses of quinine and brandy. {Amer. Jour. Med. Sci., Jan. 1867, 271.) Treatme2sT. — Xo chemical antidote for this poison is yet known. The contents of the stomach should be evacuated as speedily as possible, and then internal and external stimulants em- ployed. In several instances the application of electricity has been found very beneficial. A striking instance of this kind is reported by Dr. J. T. Main, who through mistake swallowed one drachm of the fluid extract of gelsemium. [Boston Med. and Surg. Jour., April, 1869, 185.) After a time he became nearly blind; control over the eyelids was almost entirely lost ; the flexor muscles of the 44 690 GELSEMINE. hands and arms were paralyzed, whilst the extensors were nearly so. Sensation in the hands and arms was blunted, but not in propor- tion to the loss of motion. The speech was somewhat affected, and a very disagreeable sensation was felt in the head, even before the muscles came under the influence of the drug ; but the mind was clear. In this condition he requested the poles of a galvanic battery to be applied to his hands, which being done, he was instantly relieved. The relief was not only instantaneous, but perfect and permanent. Dr. Main states that he has since tried the same remedy upon persons pretty well under the influence of gelsemium, and with like beneficial results. In a case reported by Dr. Seymour, the application of electricity was attended with great relief at first, but the patient finally died. The following remarkable case of recovery, in which morphine was employed, is reported by Dr. G. S. Courtright. {Lancet and Observer, Cincinnati, Nov. 1876, 961.) A physician took, by mis- take, from one to two teaspoonfuls of the tincture of the drug. Within a few minutes his vision was affected, and he soon lost entire control over the movements of his head ; the breathing was slow ; the pulse rapid and feeble. The face was congested, the lips were livid, the muscles of the lower jaw and of the eyelids completely paralyzed, the pupils dilated, and the eyes fixed. Two hours after the poison was taken, an emetic having failed to act, about three grains of morphine were injected into the arm, in divided doses, within a few minutes, and half a grain was given internally. Very quickly there was some improvement in the breathing ; the pupils became slightly contracted, the eyes less fixed, and there was slight control over the eyelids. Soon after, the patient vomited ; the pulse became stronger and less frequent, the paralysis gradually subsided, and in two hours he was able to give an account of the accident. In Dr. Blake's case, already cited, the hypodermic use of morphine was attended with good results. Post-mortem Appearances. — Nothing peculiar has been ob- served in the appearances after death from poisoning by this sub- stance. In Dr. Boutelle's case, in which a teaspoonful of the extract proved fatal in less than four hours, the examination was made five and a half hours after death. The body was well nourished ; rigor mortis marked. The blood was very fluid, of a dark color, and showed no tendency to coagulate or turn red upon exposure to the GELSEMIC ACID. 691 air, even after staiulinir some hours. The heart, lungs, spleen, and kidneys were normal. The liver was dark-colored and contained nuu-h liquid blood. The stomach contained four ounces af alight- colored fluid mixture mixed with glairy mucus. Its internal surface was deeply congested and marked by tortuous dilated vessels. The intestines were normal. The brain was rather pale, and the internal substance of the lobes was dotted here and there with small red points. In the case we have elsewhere reported, the body eight days after death presented the following appearances, as observed by Dr. Stephenson. The countenance was natural ; cadaveric rigidity very slight. The membranes and substance of the brain and medulla oblongata were normal. The adipose tissue was thick and highly tinged with bilious matter. The lungs were slightly collapsed, but natural in appearance, and the superficial veins were congested. The heart was normal in size, the external veins were injected, and the cavities greatly distended with dark grumous blood, inside of which was a well-defined membranous deposit. The stomach contained a small quantity of ingesta. The peritoneum, intestines, liver, and investing membrane were normal. The left kidney was congested. The cases just cited are, so far as we know, the only ones in w4iich the internal appearances in gelsemium poisoning have been observed. In Dr. Hall's case, soon after death, the external appearances were life-like. The skin was moist; the body warm, with slight coldness of the limbs; the eyelids were drooping, the pupils dilated; the lower jaw was relaxed, and the mouth presented an oval appearance. Chemical Properties. In poisoning hj gelsemium preparations the chemical examination should be directed to the recovery of both gelsemic acid and gelsemine, especially as the acid exists in the larger quantity in the plant, and so readily reveals its presence by its fluorescent properties. I. Gelsemic Acid. — In its pure state gelsemic acid is a color- less, odorless, nearly tasteless solid, which readily crystallizes, either in groups of prisms or tufts and single needles, or minute plates and scales. It has only a feeble acid reaction, and forms definite salts with but few of the metals. When gradually heated to about 692 GELSEMIC ACID. 163° C. (325° F.) it fuses to a clear liquid, which maj be vaporized without change of color or composition. If the vapors be received on a warm glass slide, they condense to brilliant crystals of the forms illustrated in Plate XV., fig. 3. Crystals may also be ob- tained by heating a small portion of the acid in a reduction tube. Solubility. In Water. — When excess of the finely-powdered acid is frequently agitated with water at the ordinary temperature for twenty-four hours, one part dissolves in 2912 parts of the liquid. Its solubility is greatly increased by the presence of coloring matters, and also of the associated alkaloid, even if only a trace of the latter be present. It is much more soluble in hot water, from which, however, as the solution cools the excess soon separates in delicate needles. Gelsemic acid is readily soluble both in ether and in chloroform. In ether of sp. gr. .728, one part of the acid quickly dissolves in 300 parts of the fluid. It is freely soluble in alcohol. CHEincAX, Reactions. — 1. Nitric acid. — If a small portion of gelsemic acid be treated with a drop of nitric acid, it dissolves with a yellow color to a yellow or reddish solution, the final color depend- ing upon the relative quantity of the organic acid present. On treating this solution with excess of aramonia, it acquires a perma- nent deep or blood-red color. These results may be obtained from the 1-lOOOth of a grain of the acid ; and even l-50,000th grain will yield, under the action of ammonia, a marked reddish coloration. This reaction, although exceedingly delicate, is not characteristic of gelsemic acid, since cesculin yields under the action of nitric acid and ammonia a similar red coloration. The distinctive characters of these substances will be pointed out hereafter. 2. Sulphuric acid. — Sulphuric acid slowly dissolves pure gelsemic acid under a yellow color to a yellow solution, which is unchanged by a moderate heat; even if the mixture be heated to 100° C. (212° F.) the acid is not decomposed. If the organic acid is impure, the cold sulphuric acid solution may have a reddish color, changed to deep brown by a moderate heat, .^culin, when pure, quickly dis- solves in sulphuric acid to a faintly yellow solution, which when moderately heated soon acqunes a chocolate color, then becomes charred. If a small crystal of potassium dichromate be stirred in a sulphuric acid solution of gelsemic acid, green oxide of chromium quickly appears. CHEMICAL PliOrEUTIES. 693 3. Sufplinric acid and Ammonia. — If a drop of aqueous am- monia be allowed to flow into a droj) of a sidphurio acid solution of gelsemic acid, the latter immediately separates as a mass of crys- talline needles, along the margin of contact of the two liquids. 1-lOOOth of a grain of the acid, under these conditions, will yield a very copious crystalline deposit, Plate. XV., fig. 4. And even l-10,000th of a grain, if only a minute drop of the mineral acid be employed and excess of ammonia be avoided, will yield perfectly satisfactory results. These crystals may be repeatedly re-examined, even when only in minute quantity and after long periods, by treat- ing the dry residue, after spontaneous evaporation, with a drop of water, which -will readily dissolve the ammonium sulphate present, whilst the gelsemic acid crystals will remain. This is one of the most delicate and characteristic reactions of gelsemic acid yet known, and it is not readily interfered with by the presence of foreign matter. JEsculin fails to respond to this test. 4. Hydrochloric acid fails to dissolve or act upon gelsemic acid, even when heated to 100° C. (212° F.). iEsculin is readily soluble in this acid. 5. Ammonia, and the fixed caustic alkalies, cause gelsemic acid to assume an intense yellow color, and quickly dissolve it to solutions having very striking fluorescent properties, even when greatly diluted. When the diluted solution is examined by transmitted light, it has a yellow color ; under reflected light, a deep bluish appearance ; and under condensed sunlight, an intense blue color along the path of the condensed rays. This fluorescence still manifests itself in solutions containing only l-100,000th of the acid. It may also be observed, on addition of an alkali, in the commercial preparations of gelsemium. The fluorescence of gelsemic acid is quickly destroyed by free acids. In regard to the fluorescent properties of gelsemic acid, it must be borne in mind that cesculin and certain other vegetable principles possess similar properties. The well-known fluorescence of quinine reveals itself only in the presence of a free acid, being quickly destroyed by an alkali. Solutions of Gelsemic Acid. — In the presence of a free alkali, gelsemic acid is freely soluble in water, forming the fluores- cent solutions just mentioned. From solutions in ammonia, when not too dilute, hydrochloric acid precipitates the acid in its crystalline 694 GELSEMINE. state, usually as delicate needles. In the presence of a fixed alkali, the acid is precipitated only from quite strong solutions. If a drop of the amraoniacal solution be allowed to evaporate spontaneously, the acid is left in its free state, as prisms and needles. Crystals may thus be obtained from a drop of a l-10,000th solution of the acid. The residue from a solution of the acid in a. fixed alkali has a greenish-yellow color and is amorphous. Solutions of the acid, prepared by the aid of just sufficient al- kali, yield precipitates with solutions of most of the metals. In some instances these precipitates are definite compounds of the acid and metal ; in others they are mixtures of the metallic oxide and free gelsemic acid ; whilst in still others they are due to the reducing action of the acid. 1. Acetate of lead throws down from a 1-1 00th solution of gelsemic acid a dense, dirty-yellow, amorphous precipitate, which is readily soluble in acetic acid, but is soon replaced by delicate crystalline needles. A 1-1 000th solution yields a very decided pre- cipitate. 2. Mercuric chloride, or corrosive sublimate, produces with a 1-lOOth Solution a copious, yellowish- white precipitate, from which the free acid quickly separates as tufts of crystals. Crystals may thus readily be obtained from even a drop of a 1-lOOOth solution of the acid. 3. Silver nitrate causes a brownish -yellow deposit, which soon darkens in color and finally becomes bluish-black, due to the reduc- tion of the silver salt. Even a drop of a l-50,000th solution of the acid after a time acquires a distinct purplish color. 4. Copper sulphate throws down from tolerably strong solutions of the acid a dii'ty-brown precipitate, which soon acquires a dull red color; after a time crystals of the free acid separate. 5. Auric chloride occasions with strong solutions a deep blue deposit, which soon assumes a green color. None of the above liquid reactions when taken alone is charac- teristic of gelsemic acid. In cases, however, in which the acid sepa- rates in the crystalline state, its true nature may be determined by some of the preceding tests. II. Gelsemixe. — In its pure state, gelsemine is a colorless, odor- less, difficultly crystallizable solid, having a persistent bitter taste. CHEMICAL PROPERTIES. G95 It lias a strong alkaline reaction, and eoinj)lot(;ly neutralizes acids, forming; sa/fs, most of which are readily soluble in water and in alco- hol. The hydrochloride rather readily crystallizes in groups of ])risins, Plate XV., fig. 1. The snlphale, nitrate, and hydrohroniide may also he obtained in the crystalline form. When heated, gelsemine fuses, according to Dr. Gerrard, at 45° C. (113° F.), to a colorless, viscid liquid, which on cooling solidifies to a transparent, vitreous mass. At a higher temperature, the alka- loid is dissipated without residue, in the form of white fumes, from which we failed to obtain crystals. Solubiliti/. — In its free state, gelsemine requires, at the ordinary temperature, 644 parts of water for solution, even when excess of the alkaloid is kept in contact with the fluid for many hours. Gelsemine is freely soluble in chloroform and in ether: one part of the alkaloid is quickly dissolved by twenty-five parts of the latter liquid. It is also readily soluble in alcohol. Reactions in the Solid State. — 1. Sulphuric acid. — When a small portion of pure gelsemine is treated with a drop of sulphuric acid, it slowly dissolves, with little or no change of color, even when the solution is moderately heated. AVhen, however, the alkaloid is not perfectly pure, it dissolves with a more or less reddish or brown- ish color to a solution which after a time assumes a pinkish hue, and which when heated acquires a purple or chocolate color. If a minute portion of powdered potassium dichromate be slowly stirred in a sulphuric acid solution of gelsemine, or of any of its colorless salts, a beautiful reddish-purple or cherry-red color manifests itself, and the liquid quickly acquires a bluish-green or blue color. If only minute quantities of the acid and powder be employed, the l-10,000th of a grain of the alkaloid will yield satisfactory results ; and even the l-100,000th of a grain may develop, at least, the reddish-purple coloration. If, in this test, the dichromate of potassium be replaced by eerie oxide, manganic oxide, or potassium ferricyanide, similar results may be obtained. If the sulphuric acid solution of the alkaloid be heated on a water-bath for some minutes, it no longer responds to the color reaction of the oxidizing agent ; but the alkaloid is not destroyed, since it may be recovered by neutralizing the solution with barium hydrate and extraction with ether. This color reaction of gelsemine resembles somewhat that pro- 696 GELSEMINB. duced by strychnine, especially as obtained from very minute portions of the latter alkaloid. When, however, the strychnine reaction is well marked, the primary blue and rapid succession of colors readily distinguish it from gelsemine, 2. Nitric acid. — This acid dissolves perfectly pure gelsemine, and any of its colorless salts, with little or no color ; but on spon- taneous evaporation of the liquid, a permanent bluish-green stain is left on the porcelain, even if only a minute trace of the alkaloid be present. In the state in which gelsemine is usually obtained, especially as an ether or chloroform residue, nitric acid causes it to assume a yellowish or brownish-green color, which quickly changes to deep green. About the least visible quantity of the alkaloid, if quietly touched with a minute drop of the acid, may develop this green coloration in a marked degree. Strychnine and the other alkaloids fail to yield a bluish-green or green coloration under the action of this acid. If the nitric acid residue from gelsemine be treated with a minute quantity of sulphuric acid and potassium dichromate, the reddish-purple coloration of the alkaloid will be developed. The nitric and sulphuric acid tests may thus be applied to the same portion of the alkaloid. Hydrochloric acid readily dissolves gelsemine, if pure, to a color- less solution. The caustic alkalies have little or no action upon the solid alkaloid. Solutions of Gelsemine, — Solutions of the salts of gelsemine, when pure, are colorless, and have a bitter taste, which is still well marked in a drop of a 1-1 000th solution of the alkaloid. On spon- taneous evaporation of a drop of the hydrochloride solution, the salt may be left in its crystalline state. 1. Ammonia and the fixed alkalies precipitate gelsemine from tolerably strong solutions of its salts as a white, amorphous deposit, which after a time becomes more or less changed into minute gran- ules and crystalline plates. The precipitate is somewhat soluble in excess of the precipitant. A drop of a 1-1 00th solution of the alka- loid yields a copious precipitate. If a strong solution be exposed to the vapor of ammonia, an immediate cloudiness is produced, followed by a granular deposit. In the residue from an aqueous mixture of a salt of gelsemine and excess of ammonia, as already stated, the alkaloid remains as a salt, the ammonia being displaced. 2. Picric acid produces in solutions of gelsemine salts a yellow, CHEMICAL rnOl-EUTIES. ('>U7 iiraorphtnis i)rccii)itate. 1-lOOtli of a grain of the alkaloid in one grain of water yields a very copions, bright yellow (le|)osit; l-lOOOtli grain, a greenish -yellow precipitate. 3. Iodine in a solution of potassluin iodide throws down from solutions of salts of gelseniine a brown, amorphous precipitate which is only sparingly soluble in acetic acid. The precipitate still appears in a drop of a l-10,000tli solution of the alkaloid. 4. Bromine in bromohydric acid causes a yellowish, amorphous precipitate, which still manifests itself in a l-5000th solution of the alkaloid. 5. Auric chloride produces a yellow precipitate, which dissolves with difficulty in acetic acid. A few drops of a 1-lOOOth solution of a salt of the alkaloid yield a very marked precipitate, which quickly dissolves on heating the mixture and separates in the gran- ular form as it cools. According to A. Gerrard, the ])recipitate has the composition 2Ci2Hi,N02; HCl,2AuCl3. 6. P/afinic chloride occasions in tolerably strons solutions of gelsemine salts a light yelloAV precipitate, which becomes partly granular and is readily soluble on heating the mixture. Its com- position is 2Ci2Hi,N02;HCl,PtCl^ (Gerrard). 7. Mercuric chloride throws down from strong; solutions of the salts of the alkaloid a white precipitate, which is only sparingly soluble in hydrochloric acid. Comparatively large granules may sometimes be obtained from the precipitate. 8. Potassium dichromate produces in a 1-lOOth solution of a gelsemine salt a copious, yellow precipitate, Avhich becomes somewhat granular. Solutions but little more dilute fail to yield a precipitate. Sulphuric acid causes the precipitate to assume a deep bluish-green color, and on stirring the mixture the characteristic purple coloration of the alkaloid is developed. If excess of the dichromate reagent be avoided and the liquid evaporated spontaneously, the residue from even the l-10,000th of a grain of gelsemine will, when treated with sulphuric acid, yield a series of purple colorations followed by a bluish-o;reen hue. Similar color results may be obtained with sulphuric acid by employing potassium ferrieyanide as the precipitant. This reagent, however, produces precipitates from only concentrated solutions of gelsemine salts. It need hardly be stated that none of the foregoing liquid reac- 698 GELSEMINE, AND GELSEMIC ACID. tions is in itself characteristic of gelsemine. But if the precipitates produced by any of the reagents be treated with concentrated sul- phuric acid and potassium dichromate, or other color-developing agent, the peculiar purple coloration of gelsemine will be developed. It must be remembered, however, that the color reaction of some of these precipitates, especially when excess of the precipitant is present, is not so delicate as that of the free alkaloid or its pure salts. Recovery from Organic Mixtures. Suspected Solutions and Contents of the STOMAcn. — The mixture, diluted with water if necessary, is slightly acidulated with acetic or hydrochloric acid, and digested at a moderate heat on a water-bath for an hour or longer. The cooled liquid is strained through muslin, the solids washed with alcohol, and the united fluids concentrated to one or two fluid-ounces (30 to 60 c.c), or even less if only a small portion of solid matter is present. The liquid is now filtered, and any solids on the filter washed with a mixture of equal parts of alcohol and water. It is again concentrated, taking care to expel the alcohol, allowed to cool, and, if solid matter sepa- rates, again filtered. The analysis now divides itself into two parts. a. Gelsemic acid. — The liquid, having still an acid reaction, is agitated with about twice its volume of pure ether, which will take up any gelsemic acid present and become more or less fluorescent. After decanting the ether, the aqueous liquid is washed once or twice with small portions of fresh ether, which is collected with that first employed. The aqueous liquid is reserved for examina- tion for the alkaloid. The ether thus employed is allowed to evaporate spontaneously, small portions at a time, in a thin glass capsule. The gelsemic acid may now be found, especially in the margin of the deposit, in the form of groups or single needles, readily seen by a low power of the microscope. Any crystals thus obtained may be collected, and, if not in too minute quantity, washed with a few drops of absolute alcohol, then examined by the appropriate tests for the acid. If much foreign matter is still present, the entire residue may be treated with a little water containing a drop of ammonia, and the liquid, if necessary, filtered. After examining the alkaline liquid in regard to its fluorescence, it is slightly acidulated with acetic acid and extracted with ether, which is allowed to evaporate spontane- RECOVERY FROM TIIK TISSUES. 699 ously. A portion of tlic ether residue may he examined hy the nitric acid and ammonia test for tlie organic acnd. Another portion may be dissolved in a small dro]) of sulphuric acid, and then a minute drop of ammonia carefully added, when any gelsemic acid present will separate as very delicate needles. Both these tests may react with the gelsemic acid even in the presence of considerable foreiern matter b. Gelsemine.— The acid aqueous liquid from which the gelsemic acid was extracted by ether is gently warmed until the dissolved ether has been expelled. It is then rendered slightly alkaline by ammonia or sodium carbonate, and any gelsemine present extracted by ether or chloroform in the usual manner. Should the ether or chloroform residue be too impure for the satisfactory application of the tests, it is treated with a small quan- tity of water slightly acidulated with hydrochloric acid, and the filtered solution, rendered alkaline, again extracted with ether. Portions of the final residue should be examined by the sulphuric acid and potassium dichromate and the nitric acid tests for the alkaloid. It may be remarked that the reactions of these tests are more readily interfered with by the presence of foreign matter than those of the corresponding tests for gelsemic acid. After the above general method, we have in, several instances obtained very satisfactory evidence of the presence of both gelsemic acid and gelsemine in the stomach-contents of animals poisoned by small doses of gelsemium preparations. So, also, in the case already cited, in which three teaspoonfuls of the fluid extract proved fatal to a woman, very satisfactory evidence of the presence of the organic acid, and of the alkaloid in minute quantity, was obtained from the contents of the stomach four and a half months after death. From the Tissues.— In gelsemium poisoning both gelsemic acid and gelsemine are absorbed, and enter the circulation in appar- ently the relative proportions in which they are present in the plant. The absorbed poison may be recovered from the liver by treating the finely-divided or crushed tissue wnth several times its weight of water slightly acidulated with hydrochloric acid, and gently warm- ing the mixture on a water-bath for some hours, occasionally adding w^ater to replace that evaporated. The cooled liquid is strained and the solids well washed with water. The clear liquid is concentrated at a moderate heat to a small volume, and, when cooled, filtered. 700 GELSEMINE, AND GELSEMIC ACID. Any gelsemic acid present is now extracted from the still acid solution by ether in the manner already indicated ; after which, the dissolved ether being expelled, the aqueous liquid is rendered slightly alkaline and the alkaloid extracted in a similar manner. A cat which had been under the influence of the drug for fifteen hours was given two drachms of the fluid extract. The animal was immediately paralyzed, and was dead fifteen minutes later. The liver, on being examined after the above method, furnished groups of crystals of gelsemic acid, and very satisfactory evidence of the presence of gelsemine. Like satisfactory results were ob- tained from the liver of a rabbit killed by the drug. Feom the Blood. — A few ounces of the blood are mixed with about five volumes of a mixture of equal parts of alcohol and water, a few drops of acetic or hydrochloric acid added, and the whole agi- tated in a bottle until a homogeneous mixture is formed. This is moderately heated in the closed bottle for some time in a water-bath, the mixture being frequently agitated. The cooled liquid is strained, and the solids washed with diluted alcohol and pressed. It is then concentrated at a moderate heat, filtered, and the filtrate evaporated to a thin syrup ; this is extracted with water and the filtered liquid concentrated to a small volume. From the liquid thus prepared the gelsemic acid and gelsemine are extracted by ether in the usual manner. A fluid-ounce of blood taken from the cat mentioned above was examined after this method. The ether extract from the acid aqueous liquid presented a well-marked fluorescence, and on evaporation left tufts of crystalline needles of gelsemic acid ; and a portion of the residue gave a deep red coloration with nitric acid and ammonia; whilst another portion, when treated with sulphuric acid and ammo- nia, gave a good deposit of crystalline needles. So, also, the ether extract from the alkaline liquid furnished very satisfactory evidence of the presence of gelsemine. APPENDIX. BLOOD. * COMPOSITION— DETECTION-DISCRIMINATION. I. General Nature and Properties of Blood. Physical Characters.— In its natural condition, the blood is a somewhat viscid, opaque liquid, of a characteristic red color, which is bright scarlet in arterial and of a purplish or brownish hue in venous blood. On exposure to the air the blood of the veins acquires the florid hue of that of the arteries. The blood -has a feebly alka- line reaction, a saline taste, and, while still warm, a faint odor, which differs somewhat in the blood of different animals. Its average specific gravity in man is about 1055, ranging from 1045 to 1075, and being slightly lower in women than in men, and still lower in children. The specific gravity of the blood of domestic animals is about the same as that of man. Composition. — When examined under the microscope, the blood is found to consist of a transparent, colorless, or very faintly yellow liquid, known as the liquor sanguinis, or plasma, in which is sus- pended a great number of very minute solid bodies known as the blood-corpuscles. The liquor sanguinis consists chiefly of water holding in solution albumen, fibrin, extractive matters, and certain inorganic salts, of which the principal are sodium chloride and carbonate. The corpuscles are of two kinds : the colored, consisting largely of the red coloring sub- stance, variously termed hcemoglobin, hcematoglobidin, and hcenudocrys- tallin, which confers upon the blood its red color ; and the colorless 701 702 BLOOD. or white corpuscles, these being destitute of color and present only in small proportion to the former. These several components exist in about the following proportions in 1000 parts of human blood : water, 790 ; albumen, 65 ; fibrin, 3 ; extractive matters and salts, 17 ; corpuscles (dry), 125 parts. In their moist state, it is estimated that the corpuscles form about one- half the volume of the blood. The specifi^c gravity of the red cor- puscles, according to C Schmidt, is about 1088, and that of the fluid in which they float about 1028. When seen singly, the red corpuscles have a pale reddish-yellow hue. Coagulation. — Soon after being drawn from the body, the blood undergoes spontaneous coagulation, whereby it finally separates into two distinct portions, namely, the crassamentum, or clot, consisting of the fidrin with the corpuscles entangled in its meshes ; and the serum, holding in solution the albumen and saline matters. Tliis process usually begins in normal human blood, when exposed to the air, in from two to three minutes, and in about eight minutes the mass forms a jelly. It is, however, subject to considerable variation, and also varies in the blood of different animals. According to Hewson, coagulation may take place within a few seconds, whilst it may be delayed for an hour or longer. (Op. cit., 72.) As is well known, the process is much influenced by vari- ous conditions and agents. Thus, an increased temperature hastens, while a diminished temperature delays, coagulation. So, also, the addition of water up to four-tenths the volume of blood hastens, and a larger proportion retards, the process (Hasebrock, 1883). In like manner a minute quantity of sodium chloride hastens, and a large quantity prevents, coagulation. Corpuscles. — The existence of the blood-corpuscles was first announced by Malpighi, in 1661, he having observed them in the blood of the hedgehog. They were first seen in human blood by Leeuwenhoek, in 1664, and he observed that the red color of tiie blood resided in the corpuscles, and, as in man, they were circular in outline in the blood of the rabbit, ox, and sheep, but oval in birds, fish, and the frog. ( Wattes Diet. Chem., i. 604.) Swammer- dam was the first to observe the blood-corpuscles of the frog. The earlier observers believed the corpuscles to be globular in form, but Senac, in 1749, announced that they were all more or less flattened. Number. — According to Vierordt, and also Welcker, one cubic GENERAL NATURE AND PROPERTIES. 703 railHmetre (about l-25th incli linear) oi" iiortnal Iminan Mood con- tains about 5,000,000 rod (u)rpus(!lc,s. According to these estimates, which have been confirmed by more recent observers, a single grain of human blood contains about 325,000,000 corpuscles. The weight of a single corpuscle may be stated approximately at l-800,000,000th of a grain, or, according to Harting, at 1-13,1 14,000th of a niilli- granune. The number of red corpuscles is something less in the blood of women than in that of men, and also in arterial than in venous blood, and it even varies in different parts of tiie same circula- tion. It also varies in the blood of different animals, even of the same class. Thus, in the rabbit there are about 3,500,000 corpuscles and in the goat about 18,000,000 per cubic millimetre. In general, birds have usually more than mammalia, and cold-blooded far less than warm-blooded animals. Forms of the Corpuscles. — The red corpuscles of the blood of all vertebrate animals present one or other of two forms, being either circular in outline or more or less oval. In all mammalia, ex- cept in embryo, the corpuscles are destitute of a nucleus, while in all oviparous animals they contain a nucleus. Hence the former class was designated by Prof. Gulliver, who first pointed out the dis- tinction, the Apyrenctimatous ; and the latter group, including Birds, Reptiles, and Fishes, the Pyrencematous Vertebrates. 1. Non-nucleated Corpuscles. — In man and all mammalia, except the camel tribe, the red corpuscles are circular, flattened, biconcave disks, which have been aptly compared to double concave lenses with rounded edges. As seen under the microscope, the free cor- puscles almost invariably present the flat sur- face to view. Fig. 13. The thickness of the corpuscle at its edge is usually between one- blood-coepuscles.— i. Mam- - 11 T n 1 T 1 malian : a, front view ; 6, on third and one-fourth the diameter of the disk. edge. 2. Oviparous; front In the camel tribe, the corpuscles have ^'""■' '^°'"'''s °"'=^^"^- an oval or elliptical outline, and the sides are slightly convex. The corpuscles of this tribe, however, conform to those of mammalia in general, in being destitute of a nucleus, and in smallness of size. In size the red corpuscles of the mammalia differ more or less in the different members of the class; and they also vary somewhat in the blood of the same animal. But, as we shall see hereafter, verv 704 BLOOD. close uniformity exists in much the greater proportion of the red corpuscles of the same animal. With only few exceptions, the average diameter of the red corpuscles of mammalian animals varies from l-3000th to l-6000th of an inch, or through a range of l-6000th of an inch. The largest corpuscles of this kind are those of the elephant, having a mean diameter of about l-2750th of an inch, and the smallest are found in the musk-deer, these measuring about l-12,325th of an inch, the extreme range being, therefore, about l-3500th of an inch ; that is, the diameter of the largest mam- malian blood-corpuscles known is about l-3500th of an inch greater than that of the smallest known. In regai'd to the structure of the red corpuscles, histologists have held very different views. By many of the older writers they were regarded as composed of a distinct cell-wall or membrane, filled with a fluid containing the red coloring matter of the blood. But according to more recent observers they consist of a colorless, highly elastic, porous or cavernous mass, or " stroma," albuminous in sub- stance, and the interstices of which are filled by the coloring matter of the corpuscle. 2. Nucleated Corpuscles. — In the blood of all birds, reptiles, and fishes the red corpuscles contain a distinct nucleus, which is generally oval in form, but sometimes nearly or altogether circular. The nucleus is dark in color, rough in contour, and usually occupies the central portion of the corpuscle, but sometimes it is eccentric. In the blood of birds the nucleus is relatively much more elongated than the corpuscle itself; in reptiles and fishes it has usually the figure of the corpuscle. The corpuscles in all these classes, except in a small family of fishes (the Cyclostomata), are more or less oval in form, the ellipticity being greatest in the blood of birds, in which the long diameter of the disk may be, according to Gulliver, twice its short diameter. This difference is somewhat less in the blood of reptiles and least in that of fishes, in which the corpuscles pass by gradations to the circular form. In size the corpuscles of these classes are considerably larger than in the mammalia, the largest being found in the blood of reptiles, especially batrachians. In the blood of the AmpMumia tridactylum the corpuscles can be seen by the unaided eye, their length being about l-350th of an inch. GENERAL NATURE AND PROPERTIES. 705 The flattened sides of the nucleated corpuscles are generally niDre or less convex, and the thickness of the disks is about one- third their short diameter. In the Cyclostomata, the lowest order of fishes, the corpuscles are circular in form, flattened, and have their sides slightly concave; hence they differ from those of man and the regular mammalia only in the presence of a nucleus and in larger size (l-2100th of an inch). In the Amphioxus lanceolatm, a member of this order and the very lowest of vertebrates, there is an entire absence of the red corpuscles, the circulating fluid containing only colorless disks. Action of Water and Reagents on Red Corpuscles. — The red corpuscles of the blood of all animals are more. or less affected by most liquids and certain gases. 1. Circular Corpuscles. — Water, if added only in very minute quantity to the blood of man or any of the regular mammalia, causes the corpuscles to become thicker and somewhat cUrainished in diameter, the concave sides becoming first flat, then convex, the thickening, according to Frey, beginning in the margins. After a time, or if more water be added, the corpuscles still increase in thickness, become less in diameter, pale in color, and finally entirely decolorized and spherical in form, the diameter being reduced in human blood-corpuscles to about l-4200th of an inch or less. In this state they are so transparent as to be nearly or altogether invisi- ble to the microscope. The addition of a potassium iodide solution tinged with iodine will render the outlines more distinct, and may render them quite visible after they have disappeared from view. If the blood be treated at once with a comparatively large quan- tity of water, the corpuscles are instantly deprived of color, and be- come globular and nearly or wholly inv^isible, or they may undergo entire disintegration. ISTot only is the effect of water thus determined somewhat by the relative quantity employed, but its action differs somewhat, it is said, on the blood of different animals. That the corpuscles, by the action of water, are rendered spherical and less in diameter was first observed by Hewson. If the corpuscles when thus distended be treated with a neutral liquid of greater density, as a solution of common salt, they regain more or less their original forms. It has long been known that some of the corpuscles in the same 45 706 BLOOD. sample of blood resist the action of water very much more th^n others, the former retaining their color and form long after the latter have entirely disappeared. In neutral liquids of the same density as the liquor sanguinis, the corpuscles undergo little or no change. In liquids more dense than the serum, they become shrivelled, and crenated or jagged in outline. The caustic alkalies quickly dissolve the corpuscles, ammonia acting more energetically than the fixed alkalies. 2. Oval Corpuscles. — The effect of vKder upon corpuscles of oval form is much the same as that upon the circular disks. The sides become more convex, the long diameter shortens and the short diameter lengthens, and they become lighter in color. As the action continues, they assume a nearly or altogether spherical form, with a diameter intermediate between the long and short diameters of the original corpuscle, and finally become colorless and exceedingly transparent, or invisible. Thus, under the action of water, the cor- puscles of oviparous animals may closely resemble in outline those of mammalia under like conditions ; but the presence of the nuclei and their larger size readily distinguish the former from the latter. Water has little action upon the nuclei, other than to cause them to become more spherical ; they may frequently be seen even when the outlines of the corpuscles have become invisible. If the swollen corpuscles be treated with a more dense liquid, they regain their original forms. Acetic acid causes the corpuscles to thicken and become transparent, but it does not readily act upon the nuclei. White Corpuscles. — The white or color^less corpuscles, known also as leucocytes, were first described by Hewson. These have the singular property of amoeboid or spontaneous movement, and of absorbing within themselves, when brought in contact, finely -divided coloring matters. Their average proportion in normal human blood is one to about 350 of the red corpuscles ; but their number is subject to great variation, depending upon age, sex, and various conditions. The colorless corpuscles are globular or spheroidal in form, more or less granular, and contain one or more nuclei, which may be either round, oval, or irregular in outline, and sometimes more or less superimposed one upon the other. The colorless corpuscles have a higher refractive power, greater firmness, and are specifically lighter, than the red corpuscles. The nuclei are not generally visible GENKRAI. NATURE AND PROPERTIES. 707 until tlio corpiiselo is treated with acetic acid or other reagent, which dissolves or renders the granules of the disk more transparent. In size the white corpuscles are pretty uniform throughout the entire Vertebrata, ranging in diameter from about l-2500th to l-3000th of an inch, and being, according to Prof. Gulliver, as large in the musk-deer as in ordinary mammals. As is well known, the proportion of the white to the red corpuscles is sometimes very greatly increased in disease [leucocythccmia], in which the former may almost equal in number the latter. Water causes the colorless corpuscles to 'become smoother in appearance and more transparent, brings to view the nuclei, and finally causes the mass to disintegrate. Histologists are now generally agreed that the white corpuscles of the blood are identical in general character with the ordinary corpuscles of lymph, chyle, saliva, mucus, and pus. Identification of Blood. When in its fresh condition, the physical characters of blood are usually quite sufficient to distinguish it from all other liquids. But as presented for identification in medico-legal investigations, it is generally in the dried state, in the form of stains, more or less minute, which may be recent or old and may have been washed. Under these circumstances the presence of one or more of the constituents of blood may be established either by their chemical properties, by their optical effects, or by their microscopic appearances, or by these methods combined. In medico-legal practice, when any account is given of a suspected stain, the primary question usually presents itself under one or other of the following forms : 1st. Is the suspected stain blood ? 2d. Is it the blood of an oviparous animal? 3d. Is it, or may it be, that of a specific mammal, or may it be human blood ? In many in- stances, however, no explanation of this kind is given or obtained, and the medical jurist has to determine whether the stain is really blood, and, if so, its true character, so far as he can. Physical Character of Blood-stains.— The color and general ap- pearance of a blood-stain will de])end much upon its thickness, age, the nature of the material upon which deposited, and also the condition of the atmosphere to which exposed. The characteristic red color of a fresh stain will after a time change to reddish-brown 708 BLOOD. or brown. This change may take place even within a few hours. When upon a fabric, dried blood imparts to it more or less stiffness. The side of the fabric upon which the stain was received should be noted, and also its exact location on the article upon which found. For the examination of minute stains, a low power of the micro- scope, especially with the binocular instrument, with condensed reflected light, may be employed with great advantage. If blood, the stain will present a bright shining appearance and a highly characteristic red color. In this manner coagula may be found even in exceedingly minute stains. Stains upon dark-colored substances may sometimes, it is said, be best detected by artificial light. Water dissolves the hcemoglobin, or red coloring matter, of dried blood, together with the albumen and salts, leaving the fibrin as a nearly colorless film. The red color of the solution, even when containing the coloring matter of only one part of blood in 1000 parts of liquid, may be well marked, especially ou lookiug down the tube in which it is contained ; a reddish hue may even be observed in a l-5000th solution of blood. A portion of the stained fabric, or the matter scraped from a spot, is treated in a very small test-tube with a little pure water, when, if the stain is recent or comparatively so, the liquid will quickly assume a red color, which at first appears as a red coloration around the stain ; but when the stain is older, some hours may be required for its solution, and the liquid may acquire only a brown- ish hue. The age of a stain cannot always be determined by its solubility in water, since one some months old may dissolve more readily than another only a few weeks old. If the stain has been heated, the coloring matter will generally be insoluble in water ; but it may be rendered soluble by the addition of a little alkali. Very old stains usually entirely resist the action of pure water. Any stains removed from a substance for examination should be corre- spondingly marked. Any solution thus obtained may now be examined by the chem- ical tests, or by means of the spectroscope, for blood. II. Chemical Tests for Blood. 1. Heat. — If an aqueous solution of blood be heated to near the boiling point, its red color is quickly discharged, with the formation of a dirty-brownish precipitate or turbidity, due to the coagulation CHEMICAL PROPERTIES. 709 of the albumen; tlie upper portion of the liquid usually presents a faint yellow hue. A 1-1 000th solution of blood will yield only a marked turbidity of a lii!;ht color. U' a drop of sodium hydrate solution be now added, the precipi- tate or turbidity immediately disappears, and the liquid acquires a more or less red color by reflected and a greenish hue by transmitted light, being dichroic. The precipitate may be reproduced by adding a drop of nitric acid. If a few drops of the acid be allowed to flow down the side of the tube and quietly subside to the bottom, a white zone will appear at the surface of contact of the two liquids, even if only 1-lOOOth of blood be present. The immediate discharge of the red color of solutions of blood, with the formation of a coagulum, when heated, distinguishes it from the red extracts of roots, fruits, flowers, and dyes, which are unchanged by heat. 2. Ammonia. — When diluted and added in limited quantity, ammonia has little or no action upon the red color of solutions of blood; if added in large quantity, the solution will assume a brown- ish hue. A minute quantity of ammonia really heightens the color of a blood solution. Under the action of this reao-ent the red color of vegetable extracts, cochineal, and certain mineral substances is either changed to green, violet, crimson, or blue, or entirely dis- charged, depending upon the nature of the coloring matter. 3. G^iaiacum Test. — On treatino; a solution of the colorino- matter of blood with an alcoholic tincture of gudiacum and an ethereal solu- tion of hydrogen peroxide, a deep blue coloration is produced, due to the oxidation of the guaiacura resin. The alcoholic solution should be freshly prepared from inner portions of the resin. The ethereal solution of peroxide of hydrogen, known in the shops as ozonie ether, may be prepared by suspending some pure barium dioxide in water, adding an equivalent quantity of dilute sulphuric acid, and extract- ing the liberated hydrogen peroxide by ether. A portion of the ether extract, if fit for use, will strike a beautiful blue or violet coloration on the addition of a fragment of chromic acid. In applying this test, a drop of the blood solution, placed over a white surface or in a porcelain dish, is first treated with a drop of the guaiacum tincture, and then a drop of the ether reagent added, when, even if only a trace of the coloring matter of blood be present, a blue color will immediately or very quickly appear. A drop of a 710 BLOOD. 1-lOOOth solution of blood will thus immediately yield a decided blue coloration ; and a l-5000th solution a quite distinct reaction. The test may be applied directly to the stain, if on a white fabric, by moistening it with a drop of water, and then adding the guaiacum and ethereal solutions. Even the minutest shred of a blood-stained fabric may show this coloration. When the stain is on colored material, it may be, as advised by Dr. Taylor, thoroughly soaked with a drop of water, and the liquid absorbed by slips of white bibulous paper; these, while still moist or after they have dried, are submitted to the action of the reagents. This test will react even with very old stains, provided they are first well moistened with water ; and even when the stains have been washed, evidence of their nature may be obtained. In one of our experiments, a piece of muslin 1-lOth of an inch square, containing a moderate blood-stain of ten years' standing, was macerated with a few drops of water for ten hours ; the liquid, which had acquired only a faint reddish hue, was then decanted and evaporated spontaneously, when it left a smooth, ring-like deposit of a faintly reddish-yellow color. This, under the action of the test, immediately assumed a deep blue color. So, also, a minute portion of a single thread of the soaked material immediately acquired a deep blue color on the application of the reagents. For the extraction of the coloring matter of very old blood- stains, M. Blondlot strongly advises [Annates d'Hygihne, 1868, i. 130) the use of ammoniated alcohol (1 : 20). This we have found a very good mixture for the purpose. A little potassium hydrate (free from nitrite) may also be used for the extraction, the liquid being neutralized with acetic acid before adding the guaiacum tincture. D. Vitali has observed that guaiacum, when precipitated from its alcoholic solution by water in the presence of haemoglobin, carries down with it the whole of the latter, even, he states, when forming only l-100,000,000th of the liquid. The precipitate is then col- lected and tested by the ether solution. (Jour. Chem. Soc. Abst, 1880, 926.) On collecting the precipitate, however, according to our experience, it sometimes acquires a faint blue color even in the absence of blood and before the ether reagent is added, due to slow oxidation. For the recovery of the blood coloring matter when under great dilution in water, the urine, and other liquids, it may be precipi- CHEMICAIi PR0PERTIE8. 711 tated, as advised by Sclnvarz, hy zinc acetate. The solution is treated witii a little of the salt, and tlu; mixture allowed to stand several hours, or until the precipitate has eoinj)lctely subsided ; the latter is then collected on a filter, washed, and tested by the guai- acuni and ether reagents. In this manner we have obtained very satisfactory evidence of the presence of blood when forming only 1 -50,000th of the solution. Fallacies. — As the bluing of the guaiacum resin in this test is simply due to oxidation, a like result is produced by various other substances, organic and mineral, especially certain salts of iron, even in very minute quantity. But all these substances, according to Dr. Taylor, who has critically examined this test (Guy's Hosp. RepoHs, 1868, 431), effect the bluing loiihout the aid of the hydrogen solution ; whereas blood does not; moreover, they have not the color of blood. According to this author, there is no red coloring matter known, other than that of blood, that will yield these results under the action of the test. If the reagent solutions be applied in a state of mixture, as is sometimes advised, the results are open to serious objections. In the examination of a suspected stain, the result of the guaiacum solution alone should first be determined; and after the addition of the ether reagent the blue coloration should appear very promptly, otherwise the result would be very doubtful. 4. Hcemin Crystals. — When heated with acetic acid and a little common salt, the haemoglobin of the blood undergoes decomposition, with the formation, as one of its products, of hcematin, which, uniting with hydrochloric acid produced from the sodium chloride, forms hccmatin hydrochloride, or hcemin. This compound readily crystallizes, forming what are known as Teichraann' s crystals, he having first described them, in 1853; its composition, according to Hoppe-Seyler, is C^3H7()N8Fe20io,2HCl. For its preparation, the blood should be in the dried state, and only the most concentrated glacial acetic acid employed. When the blood is in solution, a drop of the liquid is evaporated to dryness on a thin glass slide or in a watch-glass, the residue scraped together and pulverized, a trace of finely-powdered salt added, and then a drop or two of the acid. The heat of a very small flame of a spirit-lamp is now applied to the mixture, first around and slightly beyond the edges of the dispersed liquid, until it has collected on the centre of the slide in the form of a globule. This is then heated 712 BLOOD. until bubbles of gas appear and the liquid acquires a reddish-brown color, when the heat is gradually withdrawn until only a minute por- tion of liquid remains, this being allowed to evaporate by the heat of the slide. The residue thus obtained usually consists of brownish-red lines or stains, more or less curved or circular in form. Under the micro- scope the hsemin will appear as minute crystals, of a yellowish, reddish, or brown color, more or less transparent, and frequently arranged in the form of stellate groups, Plate XV., fig. 5. When from only a minute quantity of blood, the crystals are single, and usually range in size from 1-1 200th to 1-1 800th of an inch in length, and from l-6000th to 1-1 2000th of an inch in width. Under this test, 1-1 00th of a grain of blood will yield a residue in which the crystals may readily be recognized under a power of 75 diameters. From l-500th of a grain the crystals are usually so minute as to require a high power for their identification, Plate XV., fig. 6. With care, crystals may be obtained from even the 1-lOOOth of a grain of blood. Sometimes the hsemin, even under a high power, is in the form of opaque, irregular granules. When this is the case, the residue is again treated with a trace of salt and heated with acetic acid. Unless the blood-stain be very old or had been washed, the addition of the salt is not essential, as the quantity normally present in blood is sufficient for the purpose. It is always best, however, to add a minute quantity of salt, as its crystals interfere but little with the recognition of those of hsemin, and they may readily be removed by a drop of water. Hsemin crystals are insoluble in water, alcohol, and acetic and hydrochloric acids, sparingly soluble in ammonia, but freely so in the fixed alkalies. Under the action of the guaiacum test, they im- mediately assume a deep blue color. The crystals may be mounted in Canada balsam and thus preserved indefinitely. When the stains are very old or have been washed, and also when they are recent, a small portion of the stained fabric or of the dried clot may be heated in a very small test-tube with a few drops of the acetic acid and a little salt to about the boiling temperature, until the liquid acquires a reddish or brown color. The liquid is then transferred by a capillary pipette to a watch-glass and evaporated as above directed. In this manner a very satisfactory crystalline CIIEMICAI. PROPERTIES. 713 residue was obtained from 1-lOtli of an inch squan; ol" a fabric con- taining a blood-stain ten years old. So lonii; as any of the coloring:; matter or hfoinatin remains unde- composed, crystals may be obtained by this test. But it must be borne in mind, as pointed out by Struve, that a blood-stain may have undergone such change as no longer to respond to this test, its color being due to the products of decomposition. Hence a failure to obtain crystals should not be regarded as proof of the absence of blood. Moreover, it is sometimes quite difficult to obtain crystals from minute quantities of blood, even when recent. And, again, the presence of certain substances, especially free acids, except acetic acid, may interfere with their formation. Various methods have been advised for the precipitation of the coloring matter of the blood when under great dilution for the application of this test. That by acetate of zinc has already been mentioned when considering the guaiacum test. Another is to treat the solution with a little ammonia, then tannic acid, and finally excess of acetic acid, and allow the mixture to stand twelve or twenty-four hours. The dark brownish precipitate is collected, washed, and subjected to the action of the test, a portion being exam- ined by the guaiacum method. Satisfactory results may be obtained by this, as also by the zinc method, from solutions containing only l-50,000th of blood. Fallacies. — The forms and appearances of hsemin crystals are so peculiar and striking that they could not be confounded, at least by any one familiar with their characters, with any other substance. Their production is characteristic of blood, there being no other substance known from which they can be obtained. It has been asserted that the crystals from the blood of different animals differ somewhat in appearance ; but this is an error, since they are essentially the same in form and character as produced from the blood of all vertebrate animals. Of the various other chemical methods that have been proposed for the detection of blood there need only be mentioned that of M. Sonnenschein (1873). This consists in treating a solution of the stain with a solution of sodium molybdate or tungstate strongly acidulated with acetic or phosphoric acid, whereby a precipitate is produced which under a gentle heat collects into a pulverulent, brownish mass. This, 714 BLOOD. when collected and gently heated with a few drops of aqua ammonise, dissolves to a solution which appears of a dark red color by reflected, and greenish by transmitted, light. This dichroism will still appear when obtained from a blood solution so dilute as to have only a faint red color. The precipitate is reproduced on addition of excess of acetic acid, and may then be examined by the guaiacum test. III. — Optical Properties of Blood. History. — When light that has passed through a solution of blood is received upon a prism, the spectrum produced presents character- istic black bands, the corresponding portions of the light having been absorbed by the coloring matter of the blood. This fact was first observed by Hoppe-Seyler, in 1862, and he proposed it as a means of detecting the presence of blood in medico-legal investiga- tions. A few years later, 1864, Prof. Stokes found that two distinct spectra might be obtained from the blood, depending upon the state of oxidation of its coloring matter, the one corresponding to arterial blood and the other to deoxidized or venous blood. Further re- searches have shown that under the action of chemical reagents a number of characteristic spectra may thus be obtained from hae- moglobin, and its products and compounds. Application. — For the appli- cation of this method in con- nection with the microscope, the instrument known as the Sorby- Browning spectroscope eye-piece, or micro-spectroscope, is admira- bly adapted. Fig. 14. This in- strument permits two spectra to be examined at the same time, and thus the spectrum of the suspected substance may be com- pared side by side with that of a known sample of blood. Any microscope, provided the eye-piece fits, will answer this purpose; but it is somewhat more convenient Sorby's spectroscope eye-piece. OPTICAL PROPERTIES. 715 to employ :i hinociilar instrument. Only low |)ovvcrs, such as the one and a half or two-thirds inch, are required for the examination. It is well to cut ofl'all extraneous light from the front of the objective by placing over it a capped tube having a small perforation in the centre of the cap. The solution to be examined may be placed, as advised by Mr. Sorby, in small cells about half an inch deep, made from barometer tubing, and cemented to a glass plate. These cells permit the ex- amination of a long column with only a small amount of fluid, and are convenient for the addition of reagents. But the examination may be made with a small drop of the solution placed simply on a glass slide. Either ordinary or artificial light may be employed : the latter is usually to be preferred. The focus of the microscope having been adjusted to the sur- face of the blood solution, and the slit of the spectroscope so nar- rowed as to allow only sufficient light to pass, the appearances pre- sented will depend somewhat on the age of the blood, the strength of the solution, and also, in part, the length of the column of fluid examined. 1. Oxy-JHcemoglobin. — When the blood is fresh and the solution not too strong, more or less of the blue end of the spectrum is ab- sorbed, and two characteristic bands appear in the green portion of the spectrum. Of these bands, the one towards the red end of the spectrum nearly or altogether touches Fraunhofer's line D, is darker in appearance, sharper in outline, and narrower than the other, wdiich is placed near the line E, Chromo-lithograph, Spectrum 2. In stronger solutions these bands unite, and may occupy the entire space between D and E. In a deep cell, such as above described, a solution containing 1-oOOth of its weight of blood gives the spectrum in great perfection ; in a 1-lOOOth solution the bands are still well marked, though some- what narrowed. Under much dilution, the band next Fraunhofer's line E diminishes in intensity more rapidly than its fellow. The delicacy of this test is such, in fact, that with proper manipulation, as first announced by Mr. Sorby, a faint spectrum may be obtained from even a single blood-corpuscle. These results are wholly due to the oxy- haemoglobin of the blood, of which it forms only about one-eighth by weight. The differences observed in the spectra of solutions of oxy-hsemoglobin 716 BLOOD. of varying degrees of dilution have been described and figured by W. Preyer. [Die Blutkrystalle, Jena, 1871.) 2. Hcemoglobin. — If a solution of fresh blood be treated with a little ammonia, the two bands become somewhat narrowed and sharper in outline. On now adding a little citric or tartaric acid, avoiding excess, and then stirring in the solution a minute crystal of ferrous sulphate, preventing free access of air, the liquid acquires a purple color, and exhibits under the spectroscope a single broad band, extending over and beyond what was the space between the two former bands. Spectrum 3. This is the spectrum of Iwemoglohin, known also as reduced hcemo- globin, and may be seen in blood-stains or solutions that have be- come more or less brown. This reduction may also be effected by ammonium sulphide, without the other reagents. On agitating the reduced mixture with air, the two bands of oxy-hsemoglobin reappear. If in this experiment the citric or tartaric acid be added first, and then the ammonia and iron salt, the mixture assumes a brown color and presents the spectrum of reduced hcematin. 3. Methcemoglobin. — In blood that has been exposed to the nir for some time and become more or less brown, there is gradually formed a substance named by Hoppe-Seyler methcemoglobin. Tlie exact nature of this substance is not yet fully understood. Accord- ing to Hoppe-Seyler, it is an oxide of haemoglobin containing less oxygen, and this more firmly combined, than is present in oxy- hsemoglobin. {Physiol. Chem., 1881, 391.) This compound may be produced at once by treating a solution of blood with potassium permanganate solution. The spectrum of methcemoglobin presents a deep band in the red, and usually two bands more or less faint in the green, Spectrum 4. In the conversion into this substance, the band in the red, at first only very feeble, gradually increases in intensity, whilst the bands in the green gradually become more feeble and are finally lost. Mr. Sorby found that while it usually required some weeks to effect this change in a pure country atmosphere, it might take place within a few hours in the impure air of a city. We have seen the change only moderately marked in a stain three weeks old. If a little ammonium sulphide be added to the methsemoglobin solution, the band in the red disappears and the broad band of haemoglobin appears in the green. This may now be oxidized, by OPTICAL PROPERTIES. 717 exposure to the air, to oxy-hffimo^lobin. jMcthaemoglobin has recently been obtained in the crystalline state by Hiifncr and Otto. (Zeiis. f. Phys. C/iem., vii. 1883, G5.) 4. Hcemat'm. — When blood is exposed to the action of the air for long periods, the haemoglobin undergoes complete decomposi- tion, giving rise, with other products, to hccmatln, which is more stable in its nature than haemoglobin, and may resist decomposition for many years. A stain in which this change has taken place is no longer soluble in water, but may be dissolved by diluted acids. Tliis conversion is effected immediately on treatino; fresh blood with an acid. Hence, if a solution of blood, either fresh or old, be treated with a little acetic or citric acid, the spectrum of add hcema- tin will appear, in which there is an absorption band in the red and another in the green. Spectrum 5. Sometimes, according to the strength of the solution, the band in the green is absent, whilst at other times two faint bands may be seen in the green. It need hardly be stated that when lisemalin has once been formed, it is no longer possible to obtain the spectra of haemoglobin and its oxides. 5. Alkaline Hcematin. — If to the solution of acid haematin slight excess of ammonia be added, the spectrum of alkaline hcematin, having a single broad band in the red, will manifest itself. Spectrum 6. With stronger solutions, according to Preyer, the band extends beyond the line D. 6. Reduced Hcematin. — On adding a little ferrous sulphate to the last-mentioned solution, it will exhibit the spectrum of reduced hcematin, Spectrum 7, as figured by Preyer. This spectrum closely resembles that of a somewhat dilute solution of oxy-haemoglobin, only that the two bands are slightly moved towards the blue end of the spectrum. This substance has been named by Hoppe-Seyler hcemochromogen. The three haematin spectra usually exhibit themselves more strongly marked than the spectrum of haemoglobin under like con- ditions. These spectra may be obtained from blood-stains after the lapse of many years. 7. Carbonic oxide Hcemoglohin. — In fatal asphyxia from car- bonic oxide gas, as is well known, the blood acquires a peculiar rose-red color, which it may retain for long periods. In poisoning by this substance, the carbonic oxide unites with the haemoglobin of the blood to form carbonic oxide hcemoglohin, the gas taking the place. 718 BLOOD. volume for volume, of oxygen in the formation, by the latter, of oxy-hsemoglobin. This compound is not decomposed by the oxygen of the air, and it more strongly resists the action of reducing agents and putrefaction than do the oxides of hsemoglobin. Accepting Prof. Hiifner's formula for hsemoglobin, the molecular composition of the carbonic oxide compound, according to the re- searches of my assistant, Dr. J. Marshall, while in Prof. Hiifner's laboratory, is CgjgHioss^ieiFeSsOigg-CO, its molecular weight being 14,157. {Zeits. fur Phys. Chem., Jan. 1883, 81.) The spectrum of carbonic oxide hsemoglobin, shown in Spectrum 8 (after Preyer), is very similar to that of oxyhsemoglobin, only that the two bands are of equal intensity and about equal in width. Its strong resistance to reducing agents readily distinguishes it from the spectrum of oxy-hsemoglobin. Thus, when the solution is treated with a drop or two of ammonium sulphide, the two bands remain unchanged; whereas with oxyhsemoglobin they are immediately re- placed by the single band of hsemoglobin. Indeed, Prof. Vogel has proposed this property as a test for the presence of carbonic oxide in the atmosphere, by exposing to the air a single drop of fresh blood, and then adding to the liquid the ammonium salt, when, if the air contains only 0.3 per cent, of the gas, the reduction will be prevented. {Chem. News, 1877, i. 184.) Examination of Suspected Stains. — In the practical appli- cation of the spectroscopic method to a suspected stain, the proce- dure will depend somewhat upon the amount of material at com- mand and the age of the stain. When the stain is fresh, it requires only a small amount of blood to furnish the various spectra above described. When on a fabric and at least of moderate size, a portion of the stained material is macerated with a little water in a small tube or watch-glass, and any red solution obtained, after subsidence of sus- pended matters, transferred to a deep cell and examined. If the liquid exhibits the spectrum of oxy-hsemoglobin, a little ammonia may be added, then a minute crystal of citric acid, avoiding excess, and finally a little ferrous sulphate, when, as the latter dissolves, the spectrum of hsemoglobin will appear. Or, the solution which showed the two bands of oxy-hsemoglobin may be treated with a little citric acid, when the bands will disap- pear, and the bands of acid hsematin may or may not appear ; on EXAMINATION OF SUSPECTED STAINS. 719 the subsequent addition of ammonia and then fVrrous sulphate, the spectrum of reduced hsematin will be developed. From dilute solu- tions this spectrum is more readily obtained than that of reduced hcBnioj^lobin. A blood-stain only 1-lOth of an inch square, if readily soluble, will suffice to show these spectra in a very marked degree. If the solution has only a faint red hue, a very narrow and deep cell should be employed. When the stain is on colored material, an equal portion of the unstained fabric should be examined in a simi- lar manner. If the stain is sufficiently thick to permit the separation of solid particles, these should be dissolved in a drop or two of water and examined. Should the solution first obtained exhibit the spectrum of met- haemoglobin, it may be further examined in the manner already indicated. A blood-stain in which this change has taken place may be only partially soluble in water, a portion of the coloring matter having been further changed into hsematin, which is insoluble in water. If the stain is old or has been washed, it may be wholly insoluble in pure water. Under these circumstances it is treated with a few drops of water containing a little citric or acetic acid, and digested at the ordinary temperature for several hours, if necessary. Any brownish or yellowish liquid thus obtained is examined for the spectra of haematin in its acid, alkaline, and reduced states. In very dilute solutions, as already indicated, the spectrum of reduced haematin may sometimes be obtained when there is a failure to obtain that of either acid or alkaline htematin. From a stain seven- teen years old, in wdiich the coloring matter was wholly changed into haematin, Dr. Letheby {London Hosp. Rep., iii. 41) obtained from a portion of the fabric not exceeding one-fourth inch in diam- eter only faint traces of the spectrum of acid hiematin, but under the action of ammonia and then of ferrous sulphate he obtained as well-marked spectra as from comparatively recent blood. If the blood-stain has been heated or washed with hot water, dilute acids will generally fail to act upon it, but it may be dissolved in water containing a little ammonia, especially if the mixture be heated. The solution is then treated with a little citric acid and ferrous sulphate and examined for reduced hsematin. For this reduction it is somewhat better to substitute for the citric acid the double tartrate of potassium and sodium, and for the iron salt the 720 BLOOD. double ferrous and ammonium sulphate ; or, the ammoniacal solution may be treated at once with ferrous tartrate. When the stain is only in very minute quantity, it should be carefully examined for any dried clot, which, if found, is placed on a glass slide, moistened with a very minute drop of diluted glycerine (1 : 5), and any solution obtained examined directly by the spectro- scope. In this manner we have found, as stated by Dr. J. G. Richardson [Med. Times, Nov. 1875, 78), that a clot not exceeding 1-1 00th of an inch in diameter will yield a very satisfactory spectrum. Dr. Richardson advises to place the minute clot moistened with the glycerine on a thin glass cover, and then invert this over the concaved centre of a slide : it may then, after examination by the spectroscope, be examined under a higher power for the presence of blood-corpuscles, and finally by the guaiacum test. If no clot is found, a shred of the stained fabric may be moistened with diluted glycerine and examined in a similar manner. The solvent action of moderately diluted glycerine upon somewhat old blood-stains is markedly less than that of pure water. Fallacies. — There are certain other coloring substances that ex- hibit spectra more or less similar in appearances to those of blood. In his extended examination of various coloring principles, Mr. Sorby found the spectrum of alkanet root in alum to bear the closest resemblance in this respect, it having two bands in the green ; but the band towards the red is the broader of the two, whereas the I'e verse is the case in the blood spectrum. So, also, cochineal presents two bands in the green, but these are about equal in intensity and width. Moreover, neither of these substances resists the action of ammonia, nor will they yield the other spectra of blood. It has also been asserted that the coloring matter of the feathers of the banana-eater {Turacus albocristatus) of the East Indies exhibits a spectrum very similar, both in position and appearance of the bands, to that of fresh blood ; but it is said to be unaffected by sodium sulphide, which quickly changes the character of the blood spectrum. Prof. Reichardt has asserted (Arch. d. Pharm., 1875) that the spectrum of purpurin sulphuric acid might be confounded with that of alkaline hsematin. According to Dr. Ch. Gauge, of Jena, how- ever, this substance yields its spectrum only from warm solutions, and the band lies between D and E, whilst that from blood is MICROSCOPIC DETECTION AND DISCRIMINATION. 721 between D luul C; moreover, although the spectrum of potassium purpurin sulj)hatc hears great siinihirity to tliat of hieinoglohin, yet it roinaiiis unchanged on exposure to the air, whereas hicmoglobin is oxidized to oxy-lia)moglobin. Hence these fallacious substances differ from blood in most in- stances in the position and character of the spectral bands, and in aU cases in the effect of reagents upon their solutions. At present there is no substance known that in all these respects is similar to the coloring matter of blood. The methods thus far considered simply serve to answer the question whether or not a suspected stain or substance is blood, the results, when positive, being common to the blood of man and all animals having red blood. Any further determination as to whether it is, or may be, the blood of man, or the kind of animal from which it was derived, can, so far as at present known, be made only by means of the microscope in determining the character of the blood- corpuscles. It is true that many years since (1829) M. Barruel pro- posed to treat the blood with concentrated sulphuric acid, when, as he claimed, a peculiar odor would be evolved resembling that of the cutaneous exhalation of man or the animal from which the blood was derived. But numerous observers have long since shown that no reliance whatever could be placed in this method, even when ap- plied to fresh blood and in comparatively large quantity. So, more recently, Adolph Neumann proposed to evaporate the blood solution to dryness at about 15.5° C. (60° F.), when the residue would, under the microscope, present appearances or " pictures," whereby the blood of man could be distinguished from that of animals and these from one another. Numerous colored illustrations of the appearances thus presented by different bloods are given by this observer. [Die Er- kennung des Blutes bei gerichtlichen Untersuchungen, Leipsic, 1869.) On examining this method, however, we find no constancy in the appearances of the same blood, and even different portions of the same residue may exhibit widely different appearances. IV. Microscopic Determination and Discrimination of Blood. Oviparous Blood. — Injudicial investigations, as already stated, it is sometimes very important to determine, at least, whether the 46 722 BLOOD. blood is that of an oviparous animal or that of a mammal. We have already seen that the blood- corpuscles of all oviparous animals, including birds, rejDtiles, and fishes, are oval in form, except in a small family of the last-named class, in which they are circular ; whereas in the blood of all mammals, except the camel tribe, they are circular in outline. Moreover, in the former group of animals, without exception, the corpuscles have each a nucleus, whilst in the latter and in man they are destitute of a nucleus. Hence this question is one of ready solution in fresh blood ; but when the blood is in the form of dried stains the distinction may be difficult, or even impossible, especially if the stains are old. When in the dried state, a small clot, or a thread of the stained fabric, is treated on a glass slide with a drop of diluted glycerine (1: 10), then covered with a thin glass, and examined under a power of about 400 diameters. Sooner or later, according to the age of the blood, unless very old, the mass will disintegrate and the corpuscles may be seen of their distinctive characters. For this purpose it is generally more satisfactory to employ a clot, even if only very minute, than a stained fibre. If the clot is so old and dry as not to disintegrate under the action of the diluted glycerine, the moistened mass is gently crushed and then examined. It is sometimes better, in order to prevent the distribution of the liquid, to place the crushed clot on the thin glass cover, and then, after addition of the glycerine, invert this over a shallow glass cell attached to a glass slide. On examining a crushed mass of this kind under the microscope, the nuclei, if oviparous blood, and the outlines of the corpuscles of normal form, may sometimes be distinctly seen in the thinner por- tions and margins of the particles before any disintegration of the mass itself has taken place. We have thus seen the nuclei and outlines most distinctly marked in thin portions of oviparous bloods that had been loosely preserved in paper for over ten years. At times only the nuclei are to be seen, the outlines of the corpuscles themselves being wholly invisible. After a time the corpuscles become more or less detached from the entangled mass, and then their nature may be readily determined. It must be remembered that if the blood be treated with excess of a liquid specifically lighter than itself, the oval corpuscles may become nearly or altogether spherical in outline ; but under these MICROSCOPIC DETECrriON AND DISCRIMINATION. 723 circumstances the nuclei will still be seen, they being generally much more strongly marked than the outlines of the corpuscles themselves. When the outlines are not well marked or are invisible, they may often i)e rendered distinct by the addition of a little iodine solution. Carmine and aniline may also be employed for this purpose. Much may often l)e done in rendering the outlines visible by simply changing the light from the mirror of the microscope. The following method for this differentiation, advised by Dr. R. M. Bertolet {Amer. Jour. Med. *Se/., Jan. 1872, 128), may sometimes be used with great advantage. The dried blood is treated with a small drop of pure glycerine slightly acidulated with acetic acid, whereby the nuclei, when present, are rendered more distinct. On now adding a little fresh tincture of guaiacum, and then a drop of "ozonic ether," the nuclei will appear sharply defined and of a dark blue color, while the surrounding portions of the corpuscles will have a delicate violet hue or may remain uncolored. With recent blood and that of moderate age this method yields well-marked results; but with older stains the guaiacum reagents produce little or no effect, since the coloring matter is then unacted upon by pure glycerine. Mammalian Blood. — When the foregoing examination has shown, or it is admitted, that the blood is that of a mammal, the question may then arise. In how far can the blood of man and the blood of other mammals be distinguished from each other? Our ability to answer this question will obviously depend upon, (1) how far the red corpuscles of the different mammals differ from one another in average size ; and (2) our ability to appreciate or measure such differences. Reversing the order of these propositions, we may consider, — 1. Limit of Determinln'o Differences. a. By the unaided Eye. — With an ordinary rule divided into 1-lOOths of an inch the unaided eye will measure the distance between two points, or the centres of two fine linas, with considerable accuracy to within one-half division, and in some cases even less, — that is, to within l-200th of an inch, or less. By transmitted light, fine lines ruled on glass, with their centres l-200th of an inch apart, are, with the interspaces, readily distinguished by the naked eye. Very minute differences in the size of objects may thus be detected. 724 BLOOD. Thus, if two discoidal diatoms (arachnoidiscus) measuring respec- tively l-139th and l-166th of an inch in diameter be placed side by side on a glass slide, they are readily discriminated in size by transmitted light, although their diameters differ by only l-854th of an inch. It is true that the difference of the areas in this instance aids the eye in the distinction, this difference being, however, only l-82,317th of a square inch. In like manner, as we have found by experiment, many persons can readily distinguish, by the unaided eye, the long from the short diameter of a single oval blood-corpuscle of the Proteus, measuring l-450th by l-850th of an inch, the difference of the diameters being l-956th of an inch. b. By the Microscope. — Our ability thus to discriminate minute differences will obviously be increased in proportion as the size of the object is apparently increased. As is well known, it is not the object itself that is seen in the eye-piece of a compound microscope, but the image of the object placed upon the stage. Thus, under an amplification of ten diameters, the 1-1 000th of an inch of an object becomes apparently 1-lOOth of an inch ; and under a power of one hundred, the diameter of an object is increased one-hundredfold, the l-10,000th of an inch now being represented by 1-lOOth of an inch. So, in like manner, under one thousand diameters, the 1-lOOth of an inch of the image corresponds to only l-100,000th of an inch of the object, and now the latter can be measured to within the 1-1 00,000th of an inch with the same degree of accuracy that an ordinary object can be measured to 1— 100th of an inch by the unaided eye. The effect of amplification is strikingly shown in Fig. 15, in which the inner circle or disk represents the ap- ^^" parent size of an object 1-lOOOth of an inch in diameter under a power of 10 diameters ; the second, the same under a power of 100 ; and the outer, the original when amplified 1000 times. If three blood-corpuscles, measuring respec- tively l-3000th, l-3500th, and l-4000th of an inch in diameter, be examined under a power of 400 diameters, they will appear, in round num- bers, 13-lOOths, 11-lOOths, and 10-lOOths of an inch in diameter; under 1000 diameters, 38-lOOths, 28-lOOths, and 25-lOOths of an MICROSCOPIC DETECmON AND DISCRIMINATION. 725 inch; and under a power of 2/300, they will measure 83-lOOtlis, 71-lOOths, and 62-lOOtlis of an inch respectively. Under the last-named power, there would be an (ij)j)(!rcn( diflerence of 1-lOOth of an inch in the diameters of two corpuscles measuring respectively l-3200th and l-3240th of an inch in diameter. In the amplification of blood-corpuscles, however, there is a limit beyond which any increase of apparent size is attended with more or less loss of sharpness of outline, which is essential for exact measure- ment. Exactly where this limit lies will depend much on the excel- lency of the optical parts of the instrument employed. Measurement by the Mici^oscope. Stage Micrometer. — Among the appliances necessary for micro- metric measurement is a stage micrometer of known value. This usually consists, according to English measurement, of a series of fine lines ruled upon glass at a distance from each other of 1-lOOth of an inch, one of the divisions being subdivided into tenths, or thousandths of an inch. Other fractions of an inch are sometimes added to the scale. As these subdivisions of 1-lOOOth inch, as found in scales, are by no means always exactly equal, the scale before being used should be carefully examined in this respect, under a high power. If it is found that the spaces are unequal in value, it should then be de- termined whether, at least, any one of the subdivisions represents exactly the one-tenth of the 1-lOOth inch division, and this, if found, should be employed as the standard. We have seen scales in which the discrepancy between certain spaces amounted to l-35th of a subdivision (l-35,000th of an inch). Eye-piece Micrometer. — Employing the stage micrometer as the standard, measurements may be made by means either of a cobweb micrometer, the eye-piece micrometer, or the camera lucida. Of these methods, and others that might be mentioned, only that by means of Jackson's eye-piece micrometer will be considered. This consists of short lines ruled on a slip of glass, every fifth line being longer, and the tenth still longer than the others, to facilitate counting. The slip is placed in a brass frame, and so arranged that its position may be somewhat changed by a fine screw at one end of the frame. Thus mounted, it is placed through slits in the eye-piece just above the diaphragm. If its lines, when thus 726 BLOOD. Fig. 16.* placed, are not sharply defined, the eye-lens of the eye-piece is un- screwed until perfect definition is obtained. The value of the divisions of the eye- piece micrometer will of course, other con- ditions being equal, vary with the power of the objective employed. To determine their value for any given objective or combination, it is only necessary to place one of the di- visions of the stage micrometer in focus on the stage of the instrument, and then observe how many divisions of the eye-piece microm- eter are covered by it, bringing the lines of the two scales into coincidence by means of the screw in the end of the eye-piece microm- eter. For example, if the 1-1 000th of an inch of the stage scale when examined under, say a 1-1 2th inch objective, should cover eighteen divisions of the eye-piece micrometer, then obviously each division of the latter would have a value of l-18,000th of an inch. If now the draw-tube of the instrument be with- drawn more or less, the 1-1 000th of an inch may be made to cover exactly twenty spaces of the eye-piece scale, when each division of the latter will represent just l-20,000th of an inch. Fig. 16. But it must be borne in mind that this will be true only so long as the then present conditions are observed. Hence we should now accurately note (1) the position of the draw-tube, which should be graduated ; (2) the position of the eye-lens, in case it has been unscrewed to obtain definition of the lines of the scale ; and (3) the position of the screw- collar of the objective for adjustment of thick- * Although this drawing is not strictly accurate, and the scales are neces- sarily greatly out of proportion, yet it will serve to illustrate the general prin- ciple of micrometry. MICROSCOPIC DETECTION AND DISCRIMINATION. 727 iiess of cover, the stage-scale being covered by gla.ss of the thickness most likely to be used afterward in the measurement of objects. So, also, the position of the fine-adjiistment of the microscope should be noted, and this should be practically the same in future measure- ments. Under objectives of still higher power the value of each division of the eye-piece scale may be reduced to l-40,000th or l-50,000th of an inch, or even less. The last-named value would require an amplification of about three thousand diameters. The amplification of any given objective will, of course, depend much upon the stand and the eye-piece with which it is employed. Application. — Having established the value of the divisions of the eye-piece scale for a given combination, the object to be measured is brought into focus and then the number of divisions of the scale it covers read off, just as in measuring an object with an ordinary rule. Thus, if under a micrometry of l-20,000th of an inch a blood- corpuscle covered just five divisions of the scale, its diameter would ^^ To.'oiToj °^* ToTOJ ^^ ^° n^c\\ ; whereas if it covered eight divisions its diameter would be -gu-.-fo-jj-, or -25V0, of an inch. In these read- ings one of the long lines of the micrometer scale should be made, by means of the fine screw at the end of the scale, just coincident with the margin of the corpuscle, and the number of divisions read from this line. Since the micrometer scale is amplified by the power of the eye-lens of the eye-piece, each division may again be divided by the eye into fractional parts. After many experiments on this point, we find that a practised eye, especially if accustomed to read- ing minute scales into tenths, will read these subdivisions with very considerable uniformity to the tenths of a division. Hence, if the whole division had a value of l-20,000th of an inch, one-tenth of the division would represent only l-200,000th of an inch. In confirmation of the close coincidents that may be obtained in readings of this kind may be cited the results of three independent observers in measuring the 1-lOOOth inch divisions of a stage scale, the question being, If the ninth division of the scale measures twenty divisions of the eye-piece micrometer, what is the relative value, under the same power, of the other divisions? The results were as follows : 728 BLOOD. Obseevebs. Divisions or Scaie. 1. ' 2. 3. 4. 5. 6. 7. 8. 9. 10. w M ....... . H 19.7 19.7 19.7 20+ 20 20.1 19.6 19.6 19.6 20 20 20 20 20— 19.9 20— 20 19.9 19.8 19.8 19.8 19.6 19.7 19.7 20 20 20 19.6 19.5 19.6 As will be observed, the readings, which were made upon dif- ferent instruments, did not differ at most to exceed the l-200,000th of an inch. In support of this uniformity might also be cited two inde- pendent series of measurements of twenty designated blood-corpuscles varying in size, under a micrometry of l-20,000th of an inch, from 6.6 to 5.0 divisions (l-3030th to l-4000th of an inch), in which the results for each corpuscle were identical except in four instances, and in each of these the discrepancy was only 0.1 division. In order to ascertain to what extent the results might vary under different powers within a certain range, and by different methods of measurement, seven human blood-corpuscles, gradually varying in size from about the largest to the smallest found in this blood, were selected. These were measured under powers ranging from 1150 to about 3500 diameters, with widely difierent values of the microm- eter; and also by the cobweb micrometer, and by the camera. The averages of the seven corpuscles under these various measurements ranged from l-3224th to (by the camera) l-3275th of an inch, the mean of the averages being l-3236th of an inch. A subsequent and independent measurement of the same corpuscles by Dr. J. G. Rich- ardson with a cobweb micrometer gave an average of l-3266th of an inch, the difference between this and the former final average being something less than l-350,000th of an inch. 2. Average Size of Mammaliak Coepuscles. Repeated experiments of our own have shown, as stated by sev- eral.observers, that, as a general result, the blood-corpuscles on dry- ing in very thin layers on a glass slide undergo no appreciable change in diameter. When they have once attached themselves by their flattened sides to the glass, they remain unchanged for at least many years. Distribution for Measurement. — It requires some little experience MICROSCOPIC DETECTION AND DISCRIMINATION. 729 properly to distribute the corpuscles for measurement ; and various metliods liiive hoeii advised for this purpose. A very j^ood method is to moisten a small conical roll of soft paper having a free end with the blood, and then draw this over the slide. The best method yet proposed, however, according to our experience, is that of Prof. Christopher Johnston, of Baltimore. This consists in applying a little of the blood to the well-ground end of a slide, and then drawing the latter, slightly inclined, over the face of another slide or over a thin glass cover. In this way the corpuscles may be very evenly distributed, with rarely any change of their form and very few l)eing in actual contact. If the preparation is for permanent mounting, the blood should be spread upon a thin glass cover. If on examining the slide with the microscope any notable number of the corpuscles should be of irregular form or have crenated edges, the slide should be rejected for standard measure- ment. Sometimes these irregularities will be observed only in por- tions of the deposit. But even when no such change in form is apparent, the corpuscles sometimes diminish to a marked extent in diameter before becoming dry, especially in a moist atmosphere. In no case should the measurement of a corpuscle of irregular form be accepted : so soon as it has changed in this respect it is, of course, no longer normal. Uniformity in Size. — Some years since, Prof. Schmidt announced that at least from 95 to 98 per cent, of the corpuscles of the same animal were equal in size ; and this statement is frequently repeated at the present day. To what extent they appear of the same size, however, will depend much upon the power under which they are examined. On the other hand, it is sometimes loosely asserted that the corpuscles of man vary from l-2000th to 1 -4000th of an inch in diameter, imjilying, apparently at least, that there is but little uniformity in this respect. In regard to the extent of this uniformity in the corpuscles of human blood, the following series of observations may be cited. (1) On a well-spread slide of human blood five hundred corpus- cles were measured in the order presented by a mechanical stage, under a power of 2300 diameters and a micrometry of l-40,000th of an inch, every corpuscle of normal form being included. The averages of this series hj fifties and then by hundreds, in the order measured, ranged as follows : 730 BLOOD. Averages. Maximum. Minimum. Difference. By fifties . . " hundreds . l-3213th inch. l-3222d " l-3292d inch. 1-32 74th " 1-1 33,880th inch. l-202,862d " Of the five hundred corpuscles : 385, or 77.0 per cent., measured from l-3077th to l-3389th of an inch. 42, " 8.4 " " " l-3389th " l-3636th " " 20, " 4.0 " " " l-3636th " l-4000th " " 49, " 9.8 " " " l-3077th " l-2898th " " 4, " 0.8 " " " l-2898th " l-2817th " " The mean average of the five hundred corpuscles was l-3255th of an inch. Only one corpuscle in the series measured over l-2857th of an inch, and only two less than l-3846th of an inch, in diameter. Two hundred and seventy of the corpuscles, or 64 per cent., fell in size within a range of l-50,000th of an inch. (2) A second like series, from a different sample of human blood, examined under a power of 1150 diameters and a micrometry of l-20,000th of an inch, gave the following results : Averages. Maximum. Minimum. DifferencG. By fifties . . " hundreds . l-3215th inch. l-3228th " l-3275th inch. l-3265th " l-175,485th inch. l-284,850th " Of these five hundred corpuscles : 361, or 72.2 per cent., ranged from l-3077th to l-3389th of an inch. 56, " 11.2 " " " l-3389th " l-3636th " " 12, " 2.4 " " " l-3636th " l-4000th " " 65, " 13.0 " " " l-30r7th " l-2898th " " 6, " 1.2 " " " l-2898th " l-2817th " " The mean average of the five hundred corpuscles was l-3242d of an inch. Only one of the corpuscles measured over l-2857th and only one less than l-3846th of an inch in diameter. Three hundred of the corpuscles, or 60 per cent., fell within a range of l-50,000th of an inch. (3) A third sample of similar blood, mounted by Prof. C. Johns- ton and being thirteen months old, examined under a micrometry of l-40,000th of an inch, gave as follows : MICROSCOPIC DETECTION AND DISCRIMINATION. 731 AVXBAOES. Maximum. Miaimum. DllTereDce. By fifties . . '• huiKlrods . l-3225th inch. l-3236th " l-3332d inch, l-330Cth " l-in0,427th inch. l-152,83lBt " Of the five hundred corpuscles : 406, or 81.2 per cent., ranged from l-3077th to l-33S9th of an inch. 59, " 11.8 " " " l-33S9th " l-3636th " " 9, " 1.8 " " " l-3636th " l-4000th " " 22, « 4.4 " " " l-3077th " l-2898th " *' 4, " 0.8 " " " l-289Sth " l-2758th " " The mean average of the five hundred corpuscles was l-3266th of an inch. Again only one corpuscle was found over l-2857th and oiu le.ss than l-3846tli of an inch in diameter. Three hundred and nine of the corpuscles, or 61.8 per cent., fell within a range of l-50,000th of an inch. Twenty-one of this series, or 4.2 per cent., measured over l-3000th, and nine, or 1.8 per cent., less than l-3636th of an inch. The mean average of tlie three foreo-oing; series of measurements is l-3254th of an inch. Of some twenty other less extended series of measurements of human blood, the mean average was slightly greater than that just stated. So long ago as 1718,- Jurin estimated the human corpuscles to be l-3240th of an inch in diameter. [Heuo- soji's Works, note by Gulliver, 216.) We have repeatedly seen slides of human blood in which no corpuscles were found of less diameter than about l-3600th of an inch. On the other hand, not unfrequently the corpuscles on dif- ferent slides of the same blood, or even in certain portions of the same slide, are uniformly smaller in size' than usually found in the given blood. This diminution in size in human blood may be so general that very many of the corpuscles measure from l-3600th to l-4000th of an inch, or even less, in diameter. This contraction, as already stated, is likely to occur when the blood absorbs moisture before drying. There is strong reason to believe that the corpuscles as they circulate in the healthy blood are even more uniform in size than our measurements would seem to indicate. Although the blood-disks may thus under certain conditions diminish in size, they never increase, while under examination, above their normal diameters. Thus, then, whilst the blood of man might. 732 BLOOD. on account of contraction in diameter of the corpuscles, be con- founded with that of an animal having markedly smaller corpuscles, the reverse could never take place. The importance of this fact in certain medico-legal inquiries is quite apparent. Notwithstanding the possible diminution in the size of the cor- puscles, the general coincidence in the measurements of the same kind of blood by different observers and under different conditions is in the main very close. This close coincidence in the case of human blood under different circumstances we have already seen ; and equally concordant results might be cited of the measurements of the blood of various animals. For measurements of this kind, when the ordinary eye-piece micrometer is employed, a micrometry of l-20,000th of an inch is quite as satisfactory as a higher power. In Disease. — It has long been known that in certain diseases there is more or less change in the proportion of the blood-con- stituents; but according to more recent observers the corpuscles themselves may sometimes be altered in size. In leucocyihcemia, as already stated, the white corpuscles are very greatly increased in number, whilst the colored disks are somewhat diminished in num- ber, but there is little or no change in the mean diameter of the corpuscles. In chronic ancemia, according to Hayem, as cited by Dr. Gamgee [Physiological Chemistry, i. 148), the red corpuscles are always dimin- ished both in number and in size, their average diameter, it is said, being sometimes so low as l-3900th of an inch ; whilst, according to Dr. Eichhorst, in progressive pernicious ancemia the corpuscles are somewhat increased in size, their mean diameter being about l-3000th of an inch. From an extended series of experiments on different animals, M. Manassein concluded that the corpuscles were diminished in size in septicsemic poisoning, by a high temperature, and by carbonic acid gas; whilst they were enlarged under the action of oxygen and agents lowering the temperature of the body, as alcohol and quinine, and in acute anaemia. {Centralblatt f. Med. Wiss., 1871, 689.) In the following table of the average size of the normal blood- corpuscles of different animals, our own measurements were made in some instances while the blood was still fluid, but generally only after the corpuscles had dried in very thin layers. The average in AVERAGE SIZE OF RED CORPUSCLES. 73;J each case, expressed in vulgar fractions of tin En<;lish inch, is the mean of two or more series of nieasiirenients, and in some instances of the blootl of different intlividuals of the species. The powers employed were usually 1150 and 2300 diameters. To our own measurements we have added the corresponding results, with some additional, of Prof. Gulliver, from his very extended measurements as published in the Proceedings of the Zoological Society of London, June 15, 1875 ; and also in Hewson's Works, p. 237 et seq. Average Size of the Red Blood- Corpuscles. Man 1-3250 Monkey 1-3382 Opossum 1-3145 Guinea-pig .... 1-3223 Kangaroo .... 1-3410 Musk-rat .... 1-3282 Dog 1-3561 Rabbit 1-3653 Rat 1-3652 Mouse 1-3743 Pig 1-4268 Ox 1-4219 Horse 1-4243 Cat 1-4372 Elk 1-4384 Buffalo 1-4351 Wolf (prairie) ... 1-3422 Bear (black) ... 1-3656 Hyena 1-3644 Squirrel (red) . . . i 1-4140 Raccoon j 1-4084 Elephant .... 1-2738 Leopard ! 1-4390 Hippopotamus . . ' 1-3560 Wormley. Gulliver. 1-3200 1-3412 1-3557 1-3538 1-3440 1-3550 1-3532 1-3607 1-3754 1-3814 1-4230 1-4267 1-4600 1-4404 1-3938 1-4586 1-3600 1-3693 1-3735 1-4000 1-3950 1-2745 1-4319 1-3429 Rhinoceros .... Tapir Lion Ocelot Mule Ass Ground-squirrel . . Bat Sheep Ibex Goat Sloth Platypus (duck-billed) Whale ^. j Capybara . . . . I Seal ! Woodchuck . . . . Musk-deer . . . . Beaver Porcupine . . . . f long diam. . ^ I short " f long diam. short " Wonnley.| Gulliver. 1-3649 1-4175 1-4143 1-3885 1-3760 1-3620 1-4200 1-3966 1-4912 1-6445 1-6189 1-3164 Llama Camel 1-3201 1-6408 1-3331 1-5280 1-3765 1-4000 1-4322 1-4220 1-4000 1-4175 1-5300 1-6366 1-2865 1-3000 1-3099 1-3190 1-3281 1-3484 1-12325 1-3325 1-3369 1-3361 1-6229 1-3123 1-5876 Birds. Wormley. GuUiver. ' 1 Length. Breadth. Length. Breadth. 1-2080 1-1894 1-1955 1-1892 1-3483 1-3444 1-3504 1-3804 1-2102 1-2045 1-19.37 1-1973 1-1836 1-2347 1-2005 1-3466 1-3598 1-3424 1-3643 1-3839 1-3470 1 1-3369 Turkey Duck Quail . . . 1 . . . 1 1-2140 ' 1-3500 1-1763 1-4076 Owl . . . 1 . . . 1 1 734 BLOOD. Wormley. Length. Breadth. Length. Breadth. Tortoise (land) Turtle (green) Boa-constrictor Viper . . . Lizard . . . 1-1250 i-1245 1-2200 1-2538 1-1252 1-1231 1-1440 1-1274 1-1555 1-2216 1-1882 1-2400 1-1800 1-2743 Batrachians. "Wormley. Gulliver. Length. Breadth. Length. Breadth. 1-1089 1-1801 1-1 108 1-1821 Toad 1-1043 1-848 1-400 1-363 1-2000 1-1280 1-727 i 1-615 Triton . Amphiuma tridactyluni i-358 1-622 Fishes. Gulliver. Length. Breadth. Tront 1-1524 1-2099 1-2460 1-2S24 Perch Pike 1-2000 1-3555 1-1745 1-2842 Circular. 1-2134 Eel 1-6400 On comparing the foregoing results of Prof. Gulliver and our own, it is seen that the greatest difference is in the blood of the opossum (Didelphys Vtrginiana), in which the difference between the averages is 1-27,1 52d of an inch. Not only in respect to size, according to our own measurements, are the corpuscles of the opossum closely allied to those of man, but they also present that peculiar bright appearance, or "stamp of individuality," as Prof. Johnston expresses it (Mieroscopy of the Blood, Transactions International Medical Congress, 1876, 479), observed in human corpuscles. This same peculiarity is also strongly marked in the blood-corpuscles of the kangaroo. The next greatest difference, in the above measurements, occurs in the blood of the guinea-pig, in which it is l-36,200th of an inch. However, the species of animal examined by Prof. Gulliver was MICROSCOPIC DISCRIMINATION. 735 the Cav'ia cohaya, whilst that which we examined was the (Javia apcretained. These readily revealed tiie presence of blood-corpuscles ranging in diameter from l-3030th to l-3600th of an inch, the average being l-3242d of an inch. Before execution the prisoner admitted that he had hastily washed the stain with water from a small stream near which the murder was committed. In another case, it was claimed that some spots upon a hat were made by the blood of a turkey, and was so testified by two associates of the accused. The blood, however, was clearly that of a mammal, and was quite consistent with that of the human subject. In both these instances the examination was made within a few days after the stain was received. In a case tried a few years since, the clothes of the accused pre- sented a great number of stains, some of which were quite large, which he claimed were due to the slaughter of sheep, his statement in regard to killing sheep being confirmed by several witnesses. A closer examination of the clotlfes, however, indicated a somewhat marked difference between certain of the stains, -and independent examinations by three different observers showed that while some of the stains contained blood-corpuscles quite consistent with those of the sheep, others contained corpuscles wholly inconsistent with those of that animal, but quite consistent with human blood. Fallacies. — In the examination of suspected stains the examiner should bear in mind the possible presence of vegetable spores, which in appearance and size may closely resemble blood-corpuscles. Two instances of this kind have come within our own personal knowledge. In one of these, minute circular bodies were found in very great numbers in a suspected pail partly filled with water, and, as many of the bodies had a diameter of about l-3300th of an inch, they were pronounced human blood-corpuscles. A subsequent and independent examination, however, proved them to be simply the sporules of a confervoid algae. In a more recent case, similar spores, found in a suspected de- posit upon a rock, were at first mistaken for blood-corpuscles; but a subsequent examination convinced the observer tiiat he was in error. 740 BLOOD. Gorup-Besanez cites a similar case iPhys. Chem., 1867, 350), where an earth which from its red color appeared strongly saturated with blood was found on microscopic examination by Prof. Erdmann to contain circular bodies which at first might readily be mistaken for blood-corpuscles, but which were really the spores of the algse Por- phyridium cruentum. The general character and appearance of spores of this kind, when more carefully examined, will in most instances readily dis- tinguish them from blood-corpuscles ; they usually vary much more in size than the corpuscles of any single blood : in respect to size, however, they may be pretty uniform. Under the action of water they generally remain unchanged in appearance ; whereas blood- corpuscles become transparent and, at least for the most part, dis- appear from view. It need hardly be stated that vegetable spores have not the chemical and optical properties of blood-corpuscles. Location of Stains. — jSTot only should all stains of this kind be accurately located upon the article on which they are found, but it is sometimes of very great importance to determine upon which side of the fabric they were received. For determinations of this kind the binocular microscope, with a low power, will sometimes be found very useful. The following very remarkable case {State of Ohio v. Amelia Richardson, 1876), in which this question was involved, may be briefly cited. Two pistol-shots were heard shortly after midnight, at an interval of several minutes or more. A few minutes after the second shot an officer entered the room from which the report proceeded. He found a man lying on the floor on the left side of the bed, dead, with a pistol-ball wound in his head and blood oozing from the wound upon the carpet. The wife of the dead man was bleeding from an incised wound in the throat, and was also wounded, appar- ently by a ball, in the loose flesh upon her side, upon which there were two apertures near each other. The woman stated that while asleep her husband attempted to cut her throat with a razor, which she wrested from him. He then shot her in the side, after which she obtained the pistol and shot him in self-defence. In confirmation of her statement she pointed to blood-stains on the upper portion of the sheet on the right side of the bed, which side she claimed she occupied when she received the wound in her throat. IX TXSECTS. 741 On carefully examining these stains, they were readily found to consist of blood. But on one side of the sheet the stains were much more marked than on the other, and they contained many small clots; whilst on the least stained side there were but few clots, and these were very minute ; further, i)ortions of the stains at their edges, on the most strongly marked side of the sheet, did not fully extend through the fabric. These apjaearances, with other facts, seemed clearly to indicate that the blood was received on the side of the sheet on which the stains were most marked. This proved to be the under side of the lower sheet as found on the bed. At the trial of the case, the State held that the woman first shot her husband upon the left side of the bed, aud that his body then fell or was put upon the floor, and that the sheet which was thus stained was then reversed so as to bring the stains upon her side of the bed. Several surgeons testified that in their opinion the wound on the throat of the woman was self-inflicted, and that when the ball was received upon her side the skin was folded and distended. There was strong reason to believe she had an accomplice, who escaped from the house as the officer entered. The woman was found guilty of murder in the second degree. Blood in Insects. — The singular observation has been made by M. Curtmann that when blood-sucking insects are killed stains may result in which human blood-corpuscles are plainly recognizable. Human blood, he states, is more rapidly digested by bugs than by mosquitoes, since it is not detected in the former after twelve hours, while in the latter it may be found even later than twenty-four hours after the ins^estion of the blood. PLATE I. Fig. 1. 3-^0 grain Potassium Oxide, as nitrate or chhride, -\- Platinic Chloride, X 225 diameters. " 2. y^Q- grain Potassium Oxide, as nitrate, + lartaric Acid, X 100 diameters. " ^- 2TT g'^^i" Potassium Oxide, as chloride, + Sodium Tartrate, X 80 diameters. " 4. 2-^-o grain Potassium Oxide, as nitrate, + Picric Acid, X 40 diameters. " 5. yi^ grain Ammonia, as ammonium chloride, -|- Picric Acid, X 40 diameters. " ^- TS" g^^i"! Sodium Oxide, + Picric Acid, X 40 diameters. Il.l.l /;,/ nn PLATE 11. Fig. 1. -^-T-g-jf grain Sodium 0:ki'D'b, -\- Potassium Metantimoniafe, X 1^0 diameters. " 2. ^ grain Sodium Oxide, -\- Tartaric Acid, X 40 diameters. " ^- nrW grain Sodium Oxide, as chloride, -|- Platinic Chloride, X 40 diameters. " ^- T¥T7 gJ'^i'i Sulphuric Acid, -)- Barium Chloride, X 100 diameters. " 5. Htdbofluosilicic Acid, -|- Barium Chloride, X 100 diameters. " ^- TOT grain Sulphuric Acid, -\- Strontium Nitrate, X 75 diameters. Fi^f.5. Fiil-O- PLATE III. Fig. 1. Y017 grain Hydrochloric Acid, + Lead Acetate, X 40 diameters. " 2. YWTT grain Oxalic Acid, on spontaneous evaporation, X 80 diameters. " 3. -Y^ grain Oxalic Acid, + Calcium Chloride, X 225 diameters. " ^' T0T5" gi"ain Oxalic Acid, -(- Barium Chloride, X 80 diameters. " ^- T¥Tr grain Oxalic Acid, + Strontium Nitrate, X 125 diameters. " ^- 7¥Tr gi'ain Oxalic Acid, -(- Lead Acetate, X 80 diameters. 111. /;; /; "f nn n,.y /;;/.// PLATE IV. Fig. 1. Yo^^ grain Hydrocyanic Acid vapor, -f Silver Nitrate, X 225 diameters. " ■^- 1 0^0 gi'aiii Hydrocyanic Acid vapor, + Silver Nitrate. X 1-5 diameters. " ^' 1 0^0 E^^^^ Phosphoric Acid, -j- Ammonium Magnesium Sul- phate, X 80 diameters. " 4. Tartar Emetic, from hot supersaturated solution, X 40 diameters. " 5. Arsenious Oxide, sublimed, X 125 diameters. " 6. YoTT grain Arsenious Oxide, -j- Ammonium Silver Nitrate, X 75 diameters. //<•/ / /;,/..- /of ', 'v./..-y. flf/.O'. PLATE V. YlQ. 1. Y^ grain Arsenic Oxide, -\- Ammonium Magnesium Sulphate, X 75 diameters. " 2. Corrosive Sublimate, sublimed, X 40 diameters. <' 3. __i^ grain Lead, -|- diluted Sulphuric Acid, X 80 diameters. «« 4. _^ grain Lead, -f diluted Hydrochloric Add, X 80 diameters. " 5. 2-^L^ grain Lead, + Potassium Iodide, X 80 diameters. « 6. y^^ grain Zinc, -(- Occa^^z'c J.ctc^, X 80 diameters. \hu\ / /// o um PLATE VI. 48 Fig. 1. YUT gi'^ii Nicotine, -f- Platinic Chloride, X 40 diameters. 2. yi-g- grain Nicotine, -|- Corrosive Sublimate, X 40 diameters. 3. YoVo gi'^iii Nicotine, + Picric Acid, X 40 diameters. 4. Conine, pure, -f- vapor of Hydrochloric Acid, X 40 diameters. 5. yig- grain Conine, -\- Picric Acid, X 40 diameters. 6. Ywo g^'^iii Morphine, -[- Potassium Hydrate, X 40 diameters. n.n.vi //>/ / f'n, y h.l /'w /■'/'/./' PLATE VIL Fig. 1. Yyg- grain Morphine, -{- Potassium Iodide, X 40 diameters. 2. y-J-Q- grain Morphine, -j- Potassium Chromate, X 80 diameters. 3. -j-^-jy grain Morphine, -|- Platinic Cliloride, X 80 diameters. 4. YCTj- grain Meconic Acid, -|- Barium Chloride, X 80 diameters. 5. Y^ grain Meconic Acid, -\- Hydrochloric Acid, X 75 diameters. 6. Yuu g^^iii Meconic Acid, -|- Potassium Ferricyanide, X 40 diam- eters. 1 1,1 1. All //// / ■/// MM /;./.. //>/.// n PLATE VIIL Fig. 1. YTo grain Meconic Acid, + Calcium Chloride^ X 75 diameters. " ^' TWO gi"ain Narcotine, -|- Potassium Hydrate, X 40 diameters. " ^- OTT oJ"ain Narcotine, -)- Potassium Acetate, X 80 diameters. " ^- TW gi"ain Codeine, -j- Iodine in Potassium, Iodide, X 40 diameters. " 5. ywq grain Codeine Iodide, from alcoholic solution, X 75 diameters. " ^- T¥¥ grain Codeine, -(- Potassium, Sulphocyanide, X 40 diameters. I.ll. ///// ////./-' nn Fuio Firf.6. PLATE IX. Fig. 1. Yoir grain Codeine, -\- Potassium Dichromafe, X 40 diameters. " 2. Y^ grain Codeine, -(- Potassium Iodide, X 40 diameters. « 3. y^i^-g- grain Narceine, -|- Iodine in Potassium Iodide, X 40 diam- eters. « 4, .g.1^ grain Narceine, -|- Potassium Dichromate, X 40 diameters. " 5. gi^. grain Opianyl, -|- Iodine in Potassium Iodide, X 40 diameters. « 6. ,^Q grain Opianyl, -|- Bromine in Bromohydric Acid,y^ 40 diam- eters. n.H.ix /'./ 5^ I J I ^ i ■v//../. Fiif.o'. n PLATE X. YiQ. 1. j^ grain STRYCHNINE, -f- Potassium Hydrate or Ammonia, X 40 diameters. " 2- TW gJ'a^'3 Strychnine, -|- Potassium Sulphocyanide, X 40 diam- eters. " 3. -gig. grain Strychnine, -j- Potassium Dichromate, X 40 diameters. " 4. 2~5Vn- grain Strychnine, -f- Potassium Dichromate, X 80 diameters, grain Strychnine, -|- Auric Chloride, X 40 diameters. 1000 6. --^^-^ grain Strychnine, + Platinic Chloride, X 40 diameters. /;. I'irl.O. nn PLATE XI. Fig. 1. YWW^ grain Strychnine, -[- Picric Acid, X 80 diameters. " 2. Ywo grai'^ Strychnine, + Corrosive Sublimate, X 40 diameters. " 3. ^_ grain Strychnine, + Potassium Ferricyanide, X 40 diam- eters. " 4. -yqw^ erain Strychnine, -(- Iodine in Potassium Iodide, X 80 diameters. " ^- Too' grain Brucine, -(- Potassium Hydrate or Ammonia, X 40 diameters. " 6. yi^ grain Brucine, -{- Potassium Sulphocyanide, X 40 diameters. ll.i.-XI /■/// / /;>/../. /;./.// PLATE XII. Fi(j. 1 . -^_i_g. grain Brucine, -\- Potassium Bichromate, X 80 diameters. " 2. y-oVs- grain Brucine, -|- Platinic Chloride, X 40 diameters. '< 3. _-i^ grain Brucine, -j- Potassium Ferricyanide, X 40 diameters. " 4. 1^ grain Atropine, + Potassium Hydrate or Ammonia, X 75 diameters. <■'■ 5. 1^ grain Atropine, -)- Bromine in Bromohydric Acid, X 75 diam- eters. « 6. y^-^^-Q grain Atropine, -\- Bromine in Bromohydric Acid, X 125 diameters. 1,.t.-XII f'.r / /v//. :/ J'i>r./r nn PLATE XIII. Fig. 1. Yw^ grain Atropine, + Picric Acid, X 80 diameters. " 2. yItj grain Atropine, -f- Aw-ic Chloride, X 80 diameters. " ^- TFO" S^^^'^ Veratrine, -|- J.M?nc CJdoride, X 40 diameters. '< 4. _i^ grain Veratrine, -)- Bromine in Bromoliydric Acid, X 80 diameters. " 5. SoLANiNE, from alcoholic solution, X 80 diameters. " 6. Y^ grain Solanine, as sulphate, on spontaneous evaporation, X 80 diameters. 1.1. XIII ru/.-'. I'n, ////.// nn PLATE XIV. 49 Fig. 1. YTo- grain Morphine,-]- Iodine in Potassium Iodide, X 40 diam- eters. " ^- 10^0 6 g'"ai" Morphine, -\- Potassium lodohydrargyrate, X 40 diam- eters. " 3. Jervine, from ethereal solution, X 40 diameters. " ^- Too" gi'^i" Jervine, -|- Sulplmric Add, X 75 diameters. " ^- TTU" gi'ain Jervine, -j- Nitric Acid, X 75 diameters. " 6. Jervine, from blood of cat, X 75 diameters. n.iirxiv. I'ni I- /"/ />./, //'/ FhjF) /■'/'/. //■ Mrs.T.G.Wormle)'.ad nat.iiel.el &culp. PLATE XV. Fig. 1. GrBLSEMiNE Hydrochloride, X 40 diameters. " 2. GrELSEMic AciD, from ethereal solution, X 40 diameters. " 3. Gelsemic Acid, sublimed, X 75 diameters. " 4. yJ=Q^ ejrain GtELSEMIC Acid, -f Sulphuric Acid, then Ammonia, X 75 diameters. " 5. H^MATiN Hydrochloride, X 400 diameters. " 6. H^MATiN Hydrochloride, from 3-J-g^ grain blood, X 750 diameters. n.iir.w n.f. I. Fill,. Fhf. d PLATE XVL Apparent size of Red Blood Corpuscles under an amplification of 1150 diameters. ' The actual diameters of the corpuscles delineated are expressed in vulgar fractions of an inch, and as the numerator is always one, this is omitted in the illustration, thus: 3250 ^^gVo ^^ ^^ inch. Fig. 1. Blood-Corpuscles of Man, X 1150 diameters; average g-^Vo ^'^^^• ' Dog, X ' Mouse, X ' Ox, X ■ Sheep, X ' Goat, X u 1 u 356 1 a 1 a 3743 4119 iBTO" u 1 u llilrWl V M7S m 3400 j "^ r (^^«T( ^ , r^ ^^ 1 V -^ ^' ^' f 3«00 j 1 l^^^ { 3450 )H r--\ r~\ 1 ■ / ■ ' 3550 3600 j — [ r ( 30/5 ) J ^^k ^-^ ■^v , -\(3000) ^H B bl 3900 j( 3300 j ''^~ ^ /'/'/• ' MoilM Jni /. /.' ( 3825 ) 4300 i I +li>^ <^ (^Q ("4000, (^:^ (p) ? 4075 ) ( 4150 ) 4.501 (^ - J'lff .7 ■Shrr/r Fifl ^> (T'liit ^r -~\ /-\© ( ^^H ^F 5000) (5050) Q^ f- (^ P,© ' 1 ^""^ ^--^ /^'"^ © 1 ^ /^ © € ) ^^^ M w ^^1 ^^^^. '^~N [4400 iifl B ^ ^^^B ^ (6250^ ^^^^-^ ^_^ ^B f .Q' @ © @^@l 1 /■ — s @ ^ @ J ^ ^ @ @ ^ ^L ll 3 © '8^^ Mrs J Macchdl it. ,,imit^,\,^^ grain, /late xi., tig. 4. t#range-bro\vn »l amorp. ppt. a-imit offr/ooij grnin. lAeddish-brown ;i amorp. ppt. psrownish amorp. ppt. >™>t TooW grain. rjleddish-brown I amorp. ppt. 'imit TiJi^ou grain. p^rangc-brown amorp. ]>pt. i-irait -^'^ grain. eSrown amorp. ppt. ^timit ijjjjj grain. 13. Bromine in Bromohydric Acid. Vollow amorp. ppt. f-imit ygJoo grain. Vcllow amorp. ppt. Limit ,0000 grain. Yellow amorp. p|)t. Limit n:^r, grain. Yoliow amorp. ppt. Limit TooVoo gr^'n. Yellow amorp. ppt. Limit Tjjffn grain. Yellow amorp. ppt. Limit yjjJo^ grain. Yellow cryst. jipt. Limit 2^55 grain. Plate ix., tig. 0. Yellow amorp. ppt. Limit r^^oxj-i) grain. Brown or 3-ellow amorp. ppt. Limit ^lyjgj grain. Yellow amorp. ppt. Limit 25juij grain. Yellow cryst. ppt. Limit ^oJgj grain. Plate xii., Jigs. 5. 0. Yellow amorp. ppt. Limit TooVon gniin. Plate xiii., fig. 4. Bright yellow ppt. Yellow or orange- yellow amorp. ppt. Limit 5^ grain. Yellow amorp. ppt. Limit 55^17 grain. SOLUIilLtJY. Watkk, in III! proportinn.-!. Km Kit, freely soluble. Ciii.oRoKORM, freely soluble. Watkk, in 100 parts. Etiikh, freely soluble. Ciii.ouoFonM, freely soluble. Watkr, in 4160 part.s. ErnK.ii, in 7725 parts. Ciii/)ROForcM, in 6550 part.=. Water, in 25,000 parts. Ethkr, in 209 parts. CHr.ouoFOKM, in nearly all proportions. Water, in 128 parts. Ether, in 54.8 parts. Chloroform, in 21.5 parts. Water, in 1G60 parts. Ether, in 4066 parts. CHi.OROFuRJf, in 7950 part.'. Watkr, in 515 parts. Ether, in '[?>(S parts. Cnr-OROFORJi, in nearly all proportions. Water, in 8333 parts. • Ether, in 1400 parts. Chloroform, in 8 parts. Water, in 900 parts. P^THKR, in 440 parts. Chloroform, very freely soluble. Water, in 1783 parts. Ether, in 777 parts. Chloroform, in nearly all proportions. Water, in 414 parts. Ether, freely soluble. CHLOROFOTtM, in nearly all proportions. Water, in 7860? parts. Ether, in 108? ]>arts. Chloroform, freely soluble. Water, nearly insoluble. Ether, sparingly soluble. Chloroform, freely soluble. Water, in 1750 parts. Ether, in 9000 parts. Chloroform, in 50,000 parts. Water in 644 parts. Ether, freely soluble. CoLOROFORM, freely soluble. TABULAR VIKW OF THF BEHAVIOR OK CERTAIN ALKALOIDS WITH REAGENTS. " "', lQ«\?'^*^™in, ,oJo( groin. Llmli rf, j io5f!"n""r 'pr"to''^"n""2' i^'-*" INDEX. Absorpt'ion, effects of, 55. Acotftte of lead, fatal quantity, 367. General chemical nature, 368. Period when fatal, 366. Poisoning by, 364. Post-mortem appearances, 308. Quantitative analysis, 381. Recovery from organic mixtures, 378. Solubility, 3G9. Special chemical properties, 369-378. Symptoms produced by, 364. Treatment of poisoning by, 367. Acid, arsenic, 322. Arsenious, 241. Comenic, 497. Gelsemic, 691. Hydrochloric, poisoning by, 138- Hydrocyanic, poisoning by, 168. Igasuric, 537. Meconic, 495. Nitric, poisoning by, 119. Oxalic, poisoning by, 150. Phosphoric, 207. Pyromeconic, 497. Strychnic, 537. Sulphuric, poisoning by, 98. Acids, mineral, nature and effects of, 97. Aconite, fatal quantity, 618. Period when fatal, 617. Poisoning by, 615. Post-mortem appearances, 623. Symptoms produced by, 615. Treatment of poisoning by, 621. Aconitine, chemical properties of, 624. Fallacies of tests for, 628. History, 613. Physiological test for, 628. Aconitine, poisoning by, 615. Preparation, 613. Recovery from the blood, 630. Separation from organic mixtures, 629. Solubility, 625. Aconitum ferox, 613. Napellus, 613. Ji:sculin, 683. .\lkalies, distinguishing f)roperties, 61- 73. Fatal quantity, 65. General chemical nature of, 61. Pathological effects of, 67. Period when fatal, 64. Symptoms produced bj', 62. Treatment of poisoning by, 66. Vegetable, 417. Alkaloids, fixed, general nature of 418. Graham and Hofmann's method for recovering, 426. Liquid, 417. Recovery by dialysis. 427. By method of Draij;endorff, 429. By method of Stas, 418. Rodgers and Girdwood's method for recovering, 423. Uslar and Erdmann's method for re- covering, 424. .Vmerican hellebore, 657. .\mmonia, carbonate of, 64. Density of solutions of, 89. Effects of vapor, 64. Fatal quantity, 65. General chemical nature, 89. Period when fatal, 64. Quantitative analysis, 96. 775 776 AMM — ATR Ammonia, separation from organic mixtures, 95. Special chemical properties, 90-95. Symptoms produced by, 63. Analyses, precautions in regard to, 48. Analysis, substances requiring, 47. Analyst, qualifications requisite, 58. Aniline, source of fallacy, 570. Antimonuretted hydrogen, 227. Antimony, history of, 217. Quantitative analysis, 238. Eecovery from the tissues, 236. Eecovery from the urine, 237. Separation from complex mixtures, 233. Apparatus, chemical, 58. Appeamnces, post-mortem, 44. Aqua ammonise, chemical properties of, 89. Poisoning by, 63. Aqua fortis, 119. Arsenic, compounds of, 241. Eating of, 36. Metallic, history, 239. Physiological effects, 240. Special chemical properties, 240. White, 241. Arsenic acid, ammonio-copper sulphate test, 325. Physiological effects of, 322. Quantitative analysis, 328. Eeinsch's test for, 326. Special chemical properties, 323. Sulphuretted hydrogen test, 323. Arsenic oxide and acid, general chem- ical nature, 322. Arsenious acid, 241. Arsenious oxide, 241. Antidotes for, 247. Antiseptic properties of, 251. Bettendorff's test, 295. Danger and Piandin's method, 307. Detection after long periods, 312. In the stomach, 299. In vomited matters, 298. Distribution of absorbed, 310. Duflos and Hirsch's method, 308. Arsenious oxide, external application of, 245. Failure to detect, 312. Fallacies of Eeinsch's test, 275. Of sulphur test, 269. Fatal quantity, 246. Fresenius and Babo's method, 301. General chemical nature, 252. Iodide of potassium test, 296. Lime-water test, 296. Marsh's test, 279. Bloxam's modification, 293. Delicacy of, 283, 287, 291. Fallacies of, 285, 288, 291. Nitrate of silver test, 261. Period when fatal, 246. Post-mortem appearances, 250. Diffusion, 313. Quantitative analysis, 321. Recovery from the urine, P>09. Reduction test, 257. Reinsch's test, 271. Interferences of, 278. Separation from organic mixtures, 297. From the tissues, 300. Gautier's method, 306. Solubility in alcohol, 256. In chloroform, 256. In water, 2-53. Solutions of, 260. Sublimation test for, 256. Sulphate of copper test, 263. Sulphuretted hydrogen test, 264. Symptoms produced by, 242. Taste of, 242. Time of symptoms, 244. Treatment for, 247. Vaporization of, 252. Varieties of, 242. Asagrsea officinalis, 653. Atropa belladonna, 631. Atropia, 631. Atropine, chemical properties of, 640. External application of, 638. History, 631. Physiological test, 645. Poisoning by, 633. ATR — COM 777 Atropine, post-mortem appeiiriinces, (•.39. Preparation, 031. Recovery from the blood, 047. Separation from complex inixture.«. 645. Solubility, 640. Subcutaneous injection of, 037. Treatment for poisoning by, 038. Belladonna, poisoning by, 033. Post-mortem appearances, 039. Symptoms produced bj", 633. Treatment of poisoning by, 038. Bettendorff's test for arsenic, 295. Biiioxalate of potassium, poisoning bv, 72. Bismuth nitrate, 310. Bittersweet, 673. Blood, physical characters, 701. Composition of, 701. Eed corpuscles, 702. Action of water on, 705. "White corpuscles, 706. Blood-stains, 707. Chemical tests for, 708. Heat, 708. Ammonia, 709. Guaiacum test, 709. Hfemin crystals, 711. Optical properties, 714. Micro-spectroscope, 714. Blood-spectra, 715. Examination of stains, 718. Fallacies, 720. Microscopic detection and discrimi- nation, 721. Oviparous blood, 721. Mammalian blood, 723. Limit of determining differences, 723. Measurement by the microscope, 725. Average size of mammalian cor- puscles, 728. Table of, 733. Limit of discrimination, 735. Examination of dried blood, 737. Blood, liquids employed for examina- tion of, 737. Fallacies, 739. Location of .^tains, 740. Blood-sucking insects, 741. Bloxara's method for detecting arsenic, 293. Blue vitriol, 883. Brucia, 600. Brucine, general chemical nature, 600. History, 000. Xitric acid and tin test, 003. Physiological effects, 601. Preparation, 600. Recovery from the blood, 612. From the stomach, 611. Separation from organic mixtures, 611. Solubility, 601. Special chemical properties, 002. Sulphuric acid and nitre test, 005. Test for nitric acid, 129. Buffenbarger, Peter, case, 252. Burnett's disinfecting fluid, 402. CESIUM, 01. Carbonic oxide haemoglobin, 717. Causes modifying effects of poisons, 3-5. Cerebral poisons, 37. Cevadine, 654. Chemical analysis, importance of, 49. Failure of, 54, Decomposition of poisons, 56. Reagents, 50. Tests, value of, 50. Chemicals, arsenic in, 316. Chloride of zinc, poisoning by, 403. Classification of poisons, 37. Codeia, 523. Codeine, general chemical nature, 524. History, 523. Preparation, 523. Physiological effects, 523. Salts of, 524. Solubility, 525. Tests for, 52-5-528. Comenic acid, 497. Compound poisoning, 39. 778 CON — GEL Conia, 453. Conicine, 453. Conine, distinguished from nicutine, 463. Fallacies of tests for, 463. General chemical nature, 456. History, 453. Physiological effects of, 454. Preparation, 453. Solubility, 457. Special chemical properties, 457-463. Eecovery from the blood, 464. Salts of, 459. Separation from organic mixtures, 464. Conium maculatum, 453. Copper, chemical properties of salts of, 387. Combinations, 383. Fatal quantity, 385. History and chemical nature, 382. Period when fatal, 385. Physiological effects, 383. Post-mortem appearances, 386. Quantitative analysis, 400. Eecovery from organic mixtures, 396. From the tissues, 398. From the urine, 399. Solutions of, 387. Special chemical properties, 387. Subacetate, 383. Sulphate, 383. Symptoms produced by, 384. Treatment of poisoning by, 386. Corrosive sublimate, chemical proper- ties, 340. Ammonia test for, 343. Chloride of tin test, 347. Chronic poisoning by, 334. Composition, 331. Copper test for, 348. External application, 334. Failure to detect, 361. Fatal quantity, 335. ' General chemical nature, 339. Period when fatal, 335. Poisoning by, 331. Post-mortem appearances, 337. Corrosive sublimate, quantitative anal- ysis, 362. Eecovery from organic mixtures, 354. From the urine, 360. Eeduction test, 342. Solubility, 339. Sulphuretted hydrogen test, 345. Symptoms produced by, 331. Treatment of poisoning by, 336. Curara, properties of, 571. Curarine, 570. Danger and Flandin's method for de- tecting arsenic, 307. Datura stramonium, 647. Daturia, 647. Daturine, chemical properties, 651. History, 647. Preparation, 648. Recovery from the blood, 652. Separation from organic mixtures, 652. Davy's method for arsenic, 295. Dialysis, method of application, 427. Disease, modifying influence of, 36. Diseases simulating poisoning, 40. Duflos and Hirsch's method for de- tecting arsenic, 308. Elimination of poisons, 55. Evidences of poisoning, 38. From chemical analysis, 47. From post-mortem appearances, 43. Prom symptoms, 38. Fabrics, arsenic in, 318. Failure to detect a poison, 54. Fleitmann's test for arsenic, 294. Freet, case, 549. Fresenius and Babo's method of analy- sis, 301. Galvanized iron, poisoning by, 404. Gelsemia, 683. Gelsemic acid, 683. Chemical properties, 691. Preparation, 684. Reactions with reagents, 693. (JKI, — LKA 779 Gelsemic acid, recovery from ori^iinic mixtures, 698. From the blood, 700. From the ti.ssues, 700. Solubility, 692. (iclscmine, 683. Chemical properties, 694. In solid state, 095. In solution, 096. Fatal quantity, 688. Pathological effects, 690. Period when fatal, 687. Recovery from organic mixtures, 698. From the blood, 700. From the tissues, 699. wSolubility, 095. Symptoms produced by, G85. Treatment, 689. Gelsemium sempervirens, 683. Preparations of, 685. Glass, arsenic in, 319. Graham and Hofmann's method for recovering strychnine, 426. Habit, modifying influence of, 35. Hajmatin, 717. Haemoglobin, 716. Hellebore, American, poisoning by, 6.57. White, poisoning by, 656. Post-mortem appearances, 660. Symptoms, 657. Treatment, 660. Hemlock, detection in oi-ganic mix- tures, 464. Poisoning by, 4-54. Post-mortem appearances, 456. Symptoms produced by, 454. Treatment of poisoning by, 455. Hydrochloric acid, density of solutions of, 142. Fatal quantity, 140. General chemical nature, 141. Period when fatal, 139. Poisoning by, 138. Post-mortem appearances, 141. Quantitative analysis, 148. Hydrochloric acid, rccoverj' from or- ganic mixtures, 146. Recovery from organic fabrics, 148. Special chemical properties, 143-146. Symptoms produced by, 138. Test for meconic acid, 497. Treatment of poisoning by, 141. Hydrocyanic acid, failure to detect, 192. Fatal quantity, 173. General chemical nature, 177. History and composition, 167. Period when fatal, 172. Poisoning by, 168. Post-mortem appearances, 175. Quantitative analysis, 192. Recovery from the blood, 191. Separation from organic mixtures, 187. Special chemical properties, 178-187. Symptoms produced by, 168. Treatment of poisoning by, 174. Hydrofluosilicic acid as a reagent, 81. Hyoscine, 6-52. Idiosyncrasy, effects of, 35. Igasuric acid, 537. Indian poke, 657. Intestines, perforation of, 46. Irritant poisoning, morbid appearances in, 45. Irritant poisons, effects of, 37. Jamestown weed, poisoning by, 647. Japaconitine, 613. Jervine, chemical properties, 667. History, 653. Preparation, 655. Separation from organic mixtures, 670. From the blood, 671. Solubility, 667. Jessamine, 683. Lamson^ case, 621. Laudanum, 467. Lead acetate, chronic poisoning by, 365. 780 LEA XIC Lead acetate, fatal quantity, 367. General chemical nature, 368. Period when fatal, 366. Post-mortem appearances, 368. Solubility, 369. Special chemical properties, 369. Symptoms produced by, 364. Treatment of poisoning by, 367. Detection in the urine, 381. External application of, 366. History and chemical nature, 363. Physiological effects of, 364. Quantitative analysis, 381. Separation from organic mixtures, 378. Prom the tissues, 380. Sulphuretted hydrogen test for, 371. Lithium, chemical properties of, 61. Lloyd, iSIrs. E., case, 317. Mallet. Prof., aconite poisoning, 618. Marsh's test for arsenic, 279. Meconie acid, failure to detect, 513. General chemical nature, 496. History, 495. Iron test for, 497. Physiological effects of, 496. Preparation, 495. Pecovery from the blood, 511. From the tissues, 510. Separation from organic mixtures, 503. Solubility, 496. Special chemical properties, 497-503. Meconine, 533. Medicines, arsenic in, 316. Mercury, compounds of, 330. Detection in the urine, 360. Metallic, properties of, 330. Physiological effects, 330. Methsemoglobin, 716. Meyer, Dr., case, 620. Micro-chemistry of poisons, definition. 33, Microscope, application of, 34. Mineral acids, nature and effects of, 97. Monkshood, 613. , Morphia, 476. Morphine, external application of, 479. Pailure to detect, 513. Patal quantity, 477. General chemical nature, 480. History and preparation, 476. Nitric acid test for, 485. Period when fatal, 477. Post-mortem appearances, 480. Quantitative analysis, 514. Kecovery from the blood, 511. Prom organic mixtures, 503. Prom the tissues, 510. Prom the urine, 513. Separation from organic mixtures, 503. Solubility, 480. Special chemical properties, 483-495. Symptoms produced by, 476. Treatment of poisoning by, 480. Muriatic acid, 138. Xarceine, chemical tests for, 529-532. General chemical nature, 529. History, 529. Physiological effects, 529. Preparation, -529. Solubility, 530. Narcotic poisoning, morbid effects of, 44. Narcotic poisons, symptoms of, 37. Narcotico-irritant poisoning, 37. Narcotine, general chemical nature, 516. History, 515. Physiological effects of, 515. Preparation, 515. Solubility, 516. Special chemical properties, 517-522. Test for nitric acid, 131. Nessler's test for ammonia, 93. Nicotia, 434. Nicotiana tabacum, 434. Nicotine, general chemical nature, 439. Hi-story, 434. Period when fatal, 437. Post-mortem appearances, 438. Preparation, 434. Kecovery from the blood, 4.50. Nrc — pi< 781 Nicotine, recovery from orgunif mix- tures, 447. From the tissues, 450. Suits of, 441. Solubility, 439. Special chemical properties, 440-447. Symptoms produced by, 43o. Treatment of poisoning by, 438. Nightshade, deadly, G31. Garden, symptoms of. 072. Woody, 672. Nitrate of potassium, poisoning by, 69. Nitric acid, anhydrous, 123. Antidotes for, 121. Density of solutions of, 124. Fatal quantity, 121. Fumes of, fatal, 120. General chemical nature, 123. Pathological effects, 121. Period when fatal, 121. Poisoning by, 119. Quantitative analysis, 137. Recovery from organic fabrics, 136. From organic mixtures, 134. Special chemical properties, 124-133. Symptoms produced by, 119. Nux vomica, chemical propertie.', 541. Fatal quantity, 539. History and composition. 537. Period when fatal, 539. Physical properties, 541. Post-mortem appearances, .540. Symptoms produced by, 537. Treatment of poisoning by, 540. (Esophagus, perforation of, 46. Oil of vitriol, poisoning by, 98. Opianyl, chemical tests for, 533-536. General chemical nature, 533. History, 533. Physiological effects of, 533. Preparation, 533. Solubility, 534. Opium, effects of enema of, 469. Effects of external application, 469. Failure to detect, 513. Fatal quantity, 470. History and chemical nature, 466. Opium, period when fatal, 469. Physical and chemical properties, 475. Post-mortem appearance?, 474. Recovery after large doses of, 471. From organic mixtures, 503. Symptoms produced by, 467. Time of symptoms, 468. Treatment of poisoning by, 472. Orpiment, 241, 264. Oxalic acid, fatal quantity, 153. General chemical nature, 155. History, 1.50. Period when fatal, 152. Poisoning by, 150. Post-mortem appearances, 1-54. Quantitative analysis, 166. Eecovery from organic mixtures, 162. From the urine, 166. Solubility, 1.56. Special chemical properties, 156-162. Symptoms produced by, 150. Treatment of poisoning by, 154. Oxy-hsemoglobin, 715. Papater somniferum, 466. Phosphoric acid, general chemical na- ture, 207. Special chemical properties, 208-212. Phosphorus, failure to detect, 215. Fatal quantity, 196. General chemical nature, 199. History, 193. Hydrogen test, 205. Lipowitzs test, 207, 214. Mitscherlich^s test, 202, 213. Period when fatal, 195. Poisoning by, 193. Post-mortem appearances, 198. Quantitative analysis, 216. Recovery as oxide, 215. From organic mixtures, 212. Solubility, 200. Special chemical properties, 201-207. Symptoms produced by, 193. Treatment of poisoning by, 197. Varieties of, 200. Picraconitine, 613. 782 PIL — STR Pilocarpine, 639. Poison, definition of, 34. Failure to detect, 54. Poisons, classification of, 37. Polarized ligbt, tests for sodium, 87. Porphyroxin, 509. Post-mortem appearances, as evidence of poisoning, 44. Diffusion, 313. Examinations, 46. Potassium chlorate, 70. Nitrate, 69. Oxalate, 72. Tartrate, 72. Density of solutions of, 74. Patal quantity, 65. General chemical nature, 73. Period when fatal, 64. Picric acid test for, 80. Platinum test for, 76. Post-mortem appearances, 67. Quantitative analysis, 84. Kecovery from organic mixtures, 83. Special chemical properties, 73-75. Sulphate, poisoning by, 72. Symptoms produced by, 62. Tartaric acid test for, 78. Tartrate, poisoning by, 72. Treatment of poisoning by, 66. Prussic acid, 167. Pseudaconitine, 613. Ptomaines, 431. Pyromeconic acid, 497. EATSBAJfE, 241. Eeagents, chemical, 56. Kealgar, 241. Reinsch's test for arsenic, 271. Eodgers and Girdwood's method for recovering alkaloids, 423. Eubidium, 61. Sababilla, 653. Sodium hydrate, density of solutions of, 85. General chemical nature, 84. Poisoning by, 62. Recovery from organic mixtures, 89. Sodium hydrate, special chemical prop- erties, 85-88. Solania, 672. Solanine, chemical properties of, 675. History, 672. Preparation, 672. Post-mortem appearances, 675. Recovery from organic mixtures, 681. Solubility, 676. Symptoms produced by, 674. Treatment of poisoning by, 675. Solanum dulcamara, symptoms of, 673. Nigrum, symptoms of, 673. Tuberosum, poisoning by, 674. Sonnenschein's test for ammonia, 95. Sources of evidence of poisoning, 38. Spectrum analysis, 82. Spinal poisons, 38. Spirit of salt, 138. Stas's method for recovering alkaloids, 418. Stramonium, external application, 650. Poisoning by, 648. Post-mortem appearances, 651. Symptoms produced by, 648. Treatment for poisoning by, 650. St. Ignatius' bean, 542. Stomach, redness of, 44. Softening of, 45. Ulceration and perforation, 45. Strychnia, 542. Strychnic acid, 537. Strychnine, accumulative eft'ects of, 548. Color test for, 562. Delicacy of, 564. Fallacies of, 569. Interferences with, 566. External application of, 547. Failure to detect, 597. Fatal quantity, 550. Frog test for, 584. Galvanic test, 574. General chemical nature, 557. History, 542. Period when fatal, 549. Physiological test for, 584. RTR — VOM 783 Strychniiio j)uisoniiii^, diagnosis of, 548. Post-iiii>rtom appearances, 565. Preparation, 542. Quantitative analysis, GOO. Recovery from the blood, 598. From mix vomica, 586. From orijanie mi.\tures, 587. From the tis.^ucs, 500. From the urine, 59(i. By dialysis, 590. Salts of, 559. Solubility, 558. Special chemical properties, 559. Symptoms produced by, 543. Taste of, 559. Time of symptoms, 540. Treatment of poisoning by, 552. Strychnos Ignatii, 542. Sugar of lead, poisoning by, 364. Sulphate of potassium, 72. Sulphuric acid, density of solutions of, 106. Fatal quantity, 101. General chemical nature, 105. Period when fatal, 100. Poisoning by, 98. Post-mortem appearances, 102. Quantitative analysis, 118. Recovery from organic mixtures, 113. Separation from organic fabrics, 118. Special chemical properties, 106-112. Symptoms produced by, 98. Treatment of poisoning by, 101. Suspected poisoning, 42. Symptoms, as evidence of poisoninsj. 38. Tartar emetic, composition, 217. Fatal quantity, 220. General chemical nature, 222. Period when fatal, 219. Post-mortem appearances, 221. Quantitative analysis, 238. Recovery from organic mixtures, 233. From the tissues, 236. From the urine, 237. Tartar cniotic, .solubility, 222, Special chemical j)roportic8, 223. .Symptoms produced by, 218. Treatment, 221. Tartrate of potassium, poisoning by, 72. Tetanus, distinguished from poisoning, 548. Thorn-apple, 647. Tincture of opium, [)oisoning by, 467. Tobacco, chemical prcjporties of, 439. Detection in organic mixture.«. 447. External application of, 43G. Fatal quantity, 438. Period when fatal, 437. Poisoning by, 435. Post-mortem appearances, 438. Smoking of, 436. Symptoms produced by, 435. Treatment of poisoning by, 438. UsLAR and Erdmann's method for re- covering alkaloids, 424. Valser's method for recovery of mor- phine, 508. Vegetable alkaloids, 417. Poisons, general considerations, 417. Veratralbine, 654. Veratria, 653. Veratrine, chemical properties, 660. History, 653. Poisoning by, 656. Preparation, 654. Recovery from organic mixtures, 670. From the blood, 671. Salts of, 661. Solubility, 662. Test for sulphuric acid, 112. Veratroidia, 653. Veratrum album, 653. Post-mortem appearances, 660. Sabadilla, 653. Treatment, 660. Viride, poisoning by, 657. Verdigris, 383 Viridia, 653. Vomiting, effects of, 54. 784 WAL— ZIN Wall- Papers, arsenic in, 318. White hellebore, poisoning by, 656. White vitriol, 402. Wolfsbane, 613. Woorara, properties of, 571. Yellow jessamine, 683. Zinc, chloride of, 402. History and chemical nature, 400. Post-mortem appearances, 405. Zinc, properties of salts of, 402. Quantitative analysis, 413. Kecovery from organic mixtures, 412. Salts of, 402. Solutions of, 407. Special chemical properties, 406. Sulphate of, 402. Symptoms produced by, 402. Treatment of poisoning by, 405. Use of, for culinary purposes, 404. THE END. COLUMBIA UNIVERSITY LIBRARIES This book is due on the date indicated below, or at the expiration of a definite period after the date of borrowing, as provided by the rules of the Library or by special ar- rangement with the Librarian in charge. DATE BORROWED DATE DUE DATE BORROWED DATE DUE n ' \A: -ly-l^ C2a(1 1 40) Ml 00 0><'*-«A\ t. x. A YVvu>