TRANSCRIBER’S NOTES:
—Obvious print and punctuation errors were corrected.
—The subscript numbers, used in chemical formulae, have been rendered
as H_{2}SO_{4}.
REPORTS OF TRIALS
FOR
MURDER BY POISONING.
REPORTS OF TRIALS
FOR
MURDER BY POISONING;
BY
PRUSSIC ACID, STRYCHNIA, ANTIMONY,
ARSENIC, AND ACONITIA.
INCLUDING THE
TRIALS OF TAWELL, W. PALMER, DOVE, MADELINE SMITH,
DR. PRITCHARD, SMETHURST, AND DR. LAMSON,
WITH
CHEMICAL INTRODUCTION AND NOTES ON
THE POISONS USED.
BY
G. LATHOM BROWNE,
OF THE MIDLAND CIRCUIT, BARRISTER-AT-LAW, AUTHOR OF “NARRATIVES OF
STATE TRIALS IN THE 19TH CENTURY,”
AND
C. G. STEWART,
SENIOR ASSISTANT IN THE LABORATORY OF ST. THOMAS’S HOSPITAL;
ASSOCIATE OF THE ROYAL COLLEGE OF SCIENCE, DUBLIN;
AND OF THE SOCIETY OF PUBLIC ANALYSTS.
LONDON:
STEVENS AND SONS, 119, CHANCERY LANE,
Law Publishers and Booksellers.
1883.
LONDON:
BRADBURY, AGNEW, & CO., PRINTERS, WHITEFRIARS.
PREFACES.
THIS volume of selected reports of the most remarkable trials for
murder by poisoning, which have been held during the past half century,
with essays and notes explanatory of the nature, and operation,
and methods of detecting the various poisons supposed to have been
employed, will it is hoped prove useful to the medical, as well as
the legal profession. With this object the evidence of the medical
and chemical witnesses has been given in detail, especially in those
cases in which a conflict of scientific testimony arose, between
experts of the highest professional character and reputation. Care has
also been taken to state the scientific nomenclature of this class of
witness correctly, a point on which the shorthand writers, otherwise
so reliable, are naturally liable to fail, catching as they do only
the sounds of a language unknown to them, in reporting which the error
even in a single letter is often most important. My colleague, besides
furnishing the latest information obtainable with reference to the
various poisons, has offered from recent experiments, made specially
for this purpose, explanations of those points in the several trials
about which the rival experts disputed, bringing to bear on them the
latest discoveries in chemical science.
In preparing these reports, I have followed the form adopted by the
late Mr. Townsend, the Recorder of Macclesfield, in his valuable
volumes of trials—now I believe quite out of print—grouping the
witnesses under the heads of the case to which their evidence specially
applied, dividing the scientific from the moral testimony, and wherever
a conflict arose between the experts called for the prosecution and
those for the defence, giving the evidence of the latter immediately
after that of the former, so as to place the points at issue more
clearly before the reader.
It would have been impossible, within reasonable limits, to have
reported in detail the elaborate speeches of counsel (most of them
models of argument, criticism, and eloquence), or the minute and
exhaustive charges of many of the presiding judges. The abstracts
which have been given will, however, serve to perpetuate the most
important and notable parts of both. In some of the cases the immediate
application of these either to certain points in the evidence, or to
the arguments adduced on either side, has been shown by quotations in
the notes. With these exceptions, and a few notes pointing out errors
or discrepancies in the evidence, I have generally forborne to express
an opinion on the verdict, preferring to present such reports of the
evidence as may enable the student to form his own conclusions.
With the progress of chemical science the field of the poisoner
is constantly extending. New poisons are yearly discovered, each
succeeding one apparently more difficult of detection than the former.
Death lurks in many unsuspected forms, and but for the parallel march
of the science of detection, the poisoner would more often escape. A
grave danger to society, too, lies in the patent medicines, so popular
and so perilous; in the vermin killers, loaded with deadly poison,
which can be bought without let or hindrance by any one; and the use
of preparations for animals—not so deleterious to the latter, as they
are death-dealing—if either intentionally or by accident given to a
human being. Stringent as the regulations of the Poisons Act appear on
paper, the facility with which Lamson purchased aconitia, merely on the
credit of his name appearing in the Medical Directory, and the really
unrestricted sale of patent medicines and vermin-killers, mark the
practical inutility of the Act. A new Act, dealing with these points,
has been promised by the Government, but there seems little probability
of its passing this session.
G. L. B.
* * * * *
IN the compilation of these chemical notes it has been found very
difficult to be sufficiently simple and complete in explanation for
non-scientific readers, without either sacrificing many important
details, or exceeding the limited space available. I have attempted
as far as possible not only to solve the questions that arose in the
trials, but to look forward to many that might occur in future cases.
No claim is laid to originality except in a few experiments; but the
search through existing authorities has involved so much labour, that I
must plead a very limited leisure as an excuse for any incompleteness.
In such portions as touched on medicine I have been guided by the later
text-books, and by living advice. It has been thought preferable to
give references in the text, at the very passage quoted, instead of in
foot-notes.
With regard to the proposed new Poisons Act one or two considerations
should not be forgotten. There are hundreds of ways of taking life: the
poisoner’s is only one. Even in his method the number of fatal agents
he may use is almost unlimited. To make a schedule of certain poisons
that are not to be sold without restriction, seems like prohibiting
knives, while allowing stilettos—the latter are certainly less usual,
but quite as fatal. Moreover, the Act of 1868 only affects one channel
by which poisons may reach the public—viz., through the retail
chemists. It secures a record of ordinary shop purchases, and thus
facilitates the tracing of crime. But the channels of trade are still
open: hundred-weights of arsenic are obtained, where ounces could not
be purchased; and these large stocks are often carelessly kept, and
left open to servants, workmen, or even children. The result is that
the supposed restrictions on obtaining poisons are almost illusory:
these substances are sown broadcast among ignorant people, and are
placed in cupboards unlabelled among articles of food. The following
are recent illustrations:—
“At Corkley, Wilts, the wife of a labourer used, instead of
baking-powder, a packet of arsenic, intended by her husband as
medicine for his horses. The husband and wife died.”—_Weekly
Dispatch, May 6, 1883._
“At Whitchurch, a farmer was accused of poisoning a large number of
cattle and other animals with arsenic. In 1881 he had obtained several
pounds of it from Liverpool, stating that he wanted it to destroy
vermin.”—_Evening Standard, June 2, 1883._
In the schedule of the 1868 Act, among the _less dangerous poisons_,
to be obtained without restriction beyond proper labelling, appears,
“Almonds, Essential Oil of (_unless deprived of prussic acid_).” Yet
this preparation is one of the most perilous, as has been shown by
numbers of deaths, and lately by the West Malling case (not yet ripe
enough for reporting). There are also other faults in the schedule.
Remembering, then, that legislation on the sale of poisons is utterly
unable to _prevent_ poisoning, that all it can do is to make the means
a little difficult, and the detection more easy, how can we approve
the proposal at this moment made, to tack on a few, very tentative
clauses to an unsuccessful Act, and four more names to a very defective
schedule? Why insert chloride of antimony, and omit nitrate of silver,
sulphate of copper, and chloride of tin? The essence of a “poison” is
_quantity_; and no Act which does not specify the maximum quantity
that may be sold, can be effective. Beyond this, why should it be more
criminal to _sell_ a dangerous substance to a poisoner than to _give_
it to him, or by culpable negligence to allow him to take possession of
it? If such neglect were made punishable, if people who left arsenic,
&c., about in cupboards without precaution, had to suffer for the
consequences, we should hear less of such “accidents.”
I am deeply indebted to Dr. Bernays, Professor of Chemistry at St.
Thomas’s Hospital, for kind advice and facilities of consultation and
experiment; to Doctors Harley, Ord, Acland, and to my namesake, Mr.
Charles Stewart, F.L.S., for many valuable suggestions; and especially
to Mr. E. G. Clayton, F.C.S., who contributed the main part of the
chapter on Aconitia, and helped me materially in other portions of the
chemical notes.
The main authorities drawn upon have been:—
Taylor’s Medical Jurisprudence, 1873.
Taylor on Poisons.
Woodman and Tidy’s Handy-Book of Forensic Medicine and Toxicology,
1877.
Blyth’s Manual of Practical Chemistry, 1879.
Guy and Ferrier’s Forensic Medicine, 1881.
Allen’s Commercial Organic Analysis, 1879.
Royle’s Materia Medica, edited by Dr. J. Harley, 1876.
Christison on Poisons, 1829.
Fresenius’ Qual. and Quant. Analysis.
Watt’s Dictionary of Chemistry.
Chemical Society’s Journal.
Chemical News, Lancet, &c.
Farquharson’s Therapeutics.
Mohr’s Toxicologie, trans. by Gautier, 1876.
Casper’s Handbook of Forensic Medicine, trans. by Balfour, 1861-5.
Beilstein’s Organische Chemie, 1882.
Year Book of Pharmacy.
British and other Pharmacopœias.
Squire’s Companion.
In conclusion, it has been obviously impossible in the limited space to
explain elementary facts or principles. These may be ascertained from
any of the standard textbooks.
C. G. S.
CONTENTS.
PAGE PREFACES v
ADDENDA: DIFFERENCES BETWEEN STRYCHNIA AND MORPHIA xv
” PROCESS FOR OBTAINING PURE CHLORINE xvi
CHAPTER I.
CHEMICAL INTRODUCTION.
Summary of symptoms exhibited by various poisons: (1) Sudden
death—(2) Insensibility—(3) Vomiting—(4) Action on the eye—(5)
Convulsions—(6) Chronic poisoning. Alkaloids, chemically
and physiologically—Processes for their detection—Necessity
for keeping the extracts separate—Dragendorff’s process—Dr.
Guy’s sublimation process—Effects on animals—Doubtful value
of this test—Preparation and effects of reagents: (1)
Mayer’s—(2) Potassium tri-iodide—(3) Sonnenschein’s test—(4)
Bismuth—(5) Phosphotungstic acid—(6) Picric acid—(7) Animal
charcoal—(8) Platinic chloride—(9) Tannin or Tannic acid—(10)
Phospho-antimonic acid—(11) Silico-tungstic acid—(12) Auric,
palladium and mercuric chlorides—Ptomaines or cadaveric
alkaloids; difficulties raised by their discovery—Principles to
be observed in analysing 1
CHAPTER II.
TRIALS FOR POISONING BY PRUSSIC ACID 16
(1) John Tawell (_Slough Case_), March, 1850.
(2) George Ball (_Lewes Case_), July, 1860.
(3) Peter Walker (_Egglesham Case_), Dec., 1857.
CHAPTER III.
HYDROCYANIC OR PRUSSIC ACID.
Nature of—Strength of different preparations of, English
and foreign—Where found—Tests, preliminary: (1) Odour—(2)
Silver—(3) Prussian blue—(4) Sulphur—(5) Guaiacum—(6)
Uranium—(7) Picric acid—(8) Cupric sulphate—(9) Cobalt
chloride—(10) Mercuric oxide—(11) Peroxide of hydrogen—(12)
Mercurous nitrate. Test apparatus—Salts of hydrocyanic acid:
(1) Potassium cyanide—(2) Mercuric cyanide—(3) Cyanides of
the heavy metals—(4) Double cyanides—(5) Sulphocyanides—Oil
of bitter almonds—Antidotes—Fatal dose—Symptoms—Post-mortem
appearances—Drops and minims—Period after death at which
hydrocyanic acid can be discovered—Formic acid to be tested
for—Processes 55
CHAPTER IV.
TRIALS FOR POISONING BY STRYCHNIA 84
(1) William Palmer (_Rugeley Case_), May, 1856.
(2) William Dove (_Leeds Case_), July, 1856.
(3) Silas Barlow (_Vauxhall Case_), November, 1876.
CHAPTER V.
STRYCHNIA AND BRUCIA.
Contained in St. Ignatius’s bean—False Angostura bark—_Nux
Vomica_, &c.—Properties of strychnia—Facility of detection.
_Tests_: (1) Microscope—(2) Taste—(3) Color test; ditto in
other alkaloids, in bile, and in resinous and saccharine
matters—(4) Physiological test (Marshall Hall)—(5) Bichromate
of potash—(6) Picric acid—(7) Sulphuric acid and sodium
nitrite—(8) Mercuric chloride. Preparations of strychnia:
_Vermin killers_—Battle’s, Gibson’s, Miller’s, Marsden’s,
Barber’s, Hunter’s, Keating’s—_Brucia_—_Igasuria_—_Igasuric
acid_. _Doses of strychnia_: medicinal, fatal, recovery—_Nux
vomica_. _Fatal period_ for strychnia—_Symptoms_ in man,
commencement of symptoms, if given in powder, in solution,
in pills. _Explanation of symptoms_: by hysteria, tetanus,
epilepsy, gritty granules on spinal cord—Angina pectoris.
_Post-mortem_ appearances—Treatment—Antidotes—Dr. Taylor’s
evidence—Ptomaine—Did Cook die from morphia?—_Granular
preparations_ at St. Thomas’s Hospital 276
CHAPTER VI.
TRIALS FOR POISONING BY ARSENIC 294
(1) Madeline Smith (_Glasgow Case_), June, 1857.
(2) Ann Merritt (_Clapton Case_), March, 1850.
CHAPTER VII.
ARSENIC.
The element (arsenicum)—The oxide (white
arsenic)—Arsenicum—Arsenicum trioxide. Forms of: (1)
Crystalline—(2) Amorphous—Solubility. Uses and occurrences: (1)
Steeping, wheat—(2) Preservation of skins—(3) Antiseptics—(4)
Glass making—(5) Fur in boilers—(6) Candles—(7) Preservation
of wood—(8) Sheep washes—(9) Scheele’s green and emerald
green as pigments in sweets (case of Franklin and Randall),
wall papers, toys, &c.—(10) Medicinal—(11) For horses—(12)
Tooth-stopping—(13) Aniline dyes—(14) Fireworks—(15) Rat
and fly poisons (case of Maria Gage)—(16) For cleansing
metals—(17) Arsenic eaters—(18) Cosmetics—(19) For bronzing
metals—(20) Beer brewed from glucose—(21) American paper
collars—(22) Speculum metal—(23) Inhalation for asthma and
bronchitis—(24) Mineral waters. Sulphides of Arsenic: (1)
Orpiment (case of M. A. Burdock)—(2) Realgar. Arsenic acid—The
arsenates—Arsenic trichloride—Arseniuretted hydrogen—Methods
of extraction—Tests—Modifications of old processes
suggested—Marsh’s test, distinction of results in arsenic
and antimony—Reinsch’s test—Doses—Antidotes—Physiological
effects—Remarks—Did L’Angelier commit suicide? 373
CHAPTER VIII.
TRIALS FOR POISONING BY ANTIMONY 397
(1) Dr. Pritchard (_Glasgow Case_), July, 1865.
(2) Dr. Smethurst (_Richmond Case_), August, 1859.
(3) Thos. Winslow (_Liverpool Case_), August, 1860.
CHAPTER IX.
ANTIMONY.
Properties of the metal—Alloys—Compounds—Chlorides,
sulphides, oxides, hydride. Tartar emetic—solubility,
composition, uses and occurrence—commercial, veterinary,
medicinal. Doses and preparations—fatal dose, fatal period.
Physiological effects—Antidotes—Separations and tests—(1)
Reinsch’s—Presence of antimony; purity of the copper employed,
how to be secured; different stains resulting from presence
of arsenic, antimony, mercury, bismuth, tin, silver, gold,
platinum, palladium, sulphur compounds—(2) Dr. Maclagan’s test
in Pritchard’s trial—(3) Marsh’s test—Remarks on Pritchard’s
trial—On Smethurst’s trial—Dr. Taylor and Mr. Herapath—Arsenic
in bismuth—Antimony in grey powder 490
CHAPTER X.
TRIALS FOR POISONING BY ACONITIA OR ACONITINE 514
(1) McConkey—Dublin.
(2) G. H. Lamson (_Wimbledon Case_), December, 1881.
CHAPTER XI.
ACONITE, AND ACONITIA, OR ACONITINE.
Plants: Aconitum napellus—A. ferox. Alkaloids:
aconitia—Pseudaconitia—other bases—Decompositions—Proportions
in the plants. Commercial aconitia—German aconitia—English
aconitia. Separation—Tests, chemical and physiological.
History—Preparations, official and non-official. Physiological
effects—Causes of death—Post-mortem appearances—Treatment and
antidotes—Remarks 568
INDEX 583
ADDENDA.
A.
THE following is my own experience of the differences between strychnia
and morphia.—C. G. S.
┌—─—─—─—─—─—──────────—─—─—─┬—─—─—─—─—─—────────—─┬—─—─—─—───────—─—─┐
│ │ MORPHIA. │ STRYCHNIA. │
├—─—─—─—─—─—──────────—─—─—─┼—─—─—─—─—─—────────—─┼—─—─—─—─—───────—─┤
│Concent. H_{2}SO_{4}—cold. │If pure, nothing at │If pure, nothing. │
│ │ first. │Some yellow─brown.│
│ ” ” warmed.│Violet, not strong. │ Do. │
│ To this warmed solution │ │ │
│add:— │ │ │
├—─—─—─—─—─—─—─—──────────—─┼—─—─—─—─—─—────────—─┼—─—─—─—───────—─—─┤
│ MnO_{2}. │Red, changing slowly │_Deep blue purple_│
│ │ to brown, then │ —tored purple— │
│ │ orange. On dilution,│cherryred—finally │
│ │ yellow─brown. │(changes slow). On│
│ │ │ dilution, rich │
│ │ │ orange red. │
├—─—─—─—─—─—─—──────────—─—─┼—─—────────—─—─—─—─—─┼—─—─—─—───────—─—─┤
│ K_{6}Cfy_{2}. │Violet, changing to │Same changes, but │
│ │ orange; not strong. │ more rapid and │
│ │ On dilution, at once│ less distinct. On│
│ │ destroyed to │ dilution, at once│
│ │ greenish─yellow │ destroyed to │
│ │ solution, turning │ greenish─yellow │
│ │blue. │ solution. │
├—─—─—─—─—─—──────────—─—─—─┼—─—─—─—─—─—────────—─┼—─—─—───────—─—─—─┤
│ K_{2}Cr_{2}O_{7}. │Red─brown, │Same as with │
│ │ orange─brown, │ MnO_{2}, but more│
│ │ _green_. │ evanescent and │
│ │ On dilution, │ rapid in change. │
│ │ _green_. │ On dilution, at │
│ │ │ once removed to │
│ │ │ yellowish─brown. │
├—─—─—─—─—─—─—─—──────────—─┼—─—─—─—────────—─—─—─┼—─—─—───────—─—─—─┤
│ HNO_{3} concent. │_Intense brownish─ │_In the cold, │
│ │ red_, changing │ nothing if pure._│
│ │ to brown— bleached │ On warming, │
│ │ by SnCl_{2}. │ orange─yellow │
│ │ │ —then SnCl_{2} │
│ │ │ _brown_ changing│
│ │ │ with excess to │
│ │ │ yellow. │
└—─—─—─—─—─—──────────—─—─—─┴—─—─—─—────────—─—─—─┴—─—─—─—───────—─—─┘
B.
The chlorine used in the separation of arsenic (p. 385) must be _pure_.
The best process for making it is to heat _pure_ potass. dichromate
with _pure_ hydrochloric acid. The latter may be obtained by heating
the “pure” acid of commerce in a retort until a portion of the
distillate gives no indication of arsenic by the tests. The remainder
in the retort is then arsenic-free.
* * * * *
ERRATUM.
Page 397, line 11, _for_ “Waislow,” _read_, “Winslow.”
TRIALS FOR POISONING.
CHAPTER I.
CHEMICAL INTRODUCTION.
Summary of symptoms exhibited by various poisons: (1) Sudden
death—(2) Insensibility—(3) Vomiting—(4) Action on the eye—(5)
Convulsions—(6) Chronic poisoning. Alkaloids, chemically and
physiologically—Processes for their detection—Necessity for keeping
the extracts separate—Dragendorff’s process—Dr. Guy’s sublimation
process—Effects on animals—Doubtful value of this test—Preparation
and effects of reagents: (1) Mayer’s—(2) Potassium tri-iodide—(3)
Sonnenschein’s test—(4) Bismuth—(5) Phosphotungstic acid—(6) Picric
acid—(7) Animal charcoal—(8) Platinic chloride—(9) Tannin or tannic
acid—(10) Phospho-antimonic acid—(11) Silico-tungstic acid—(11)
Auric, palladium and mercuric chlorides—Ptomaines or cadaveric
alkaloids; difficulties raised by their discovery—Principles to be
observed in analysing.
BEFORE proceeding to a separate examination of the poisons used in
the following trials, it will be advisable to take a general view
of poisons, specially noticing those that we have selected as the
most important legally. They do not admit, perhaps, of accurate
classification, but inasmuch as the manner of death and symptoms are
usually the most available indication as to the nature of the poison
that has acted, the following arrangement will be serviceable. The
heads indicate the most prominent symptom:
I. SUDDEN DEATH.—Large quantities of any poison might be rapid
in fatal result, but the sudden poisons proper are:—concentrated
sulphuric, nitric, and hydrochloric acids; poisonous gases and vapours,
such as carbonic acid and sulphuretted hydrogen (_see_ Casper’s
Forensic Medicine, Case CCXLI.), carbonic oxide, arseniuretted and
antimoniuretted hydrogen, and certain rare organic compounds, as
kakodyl, &c.; strychnia sometimes, oxalic acid in large doses,
chloroform under certain circumstances. But beyond all others, the
quickest of poisons is _hydrocyanic or prussic acid_.
II. INSENSIBILITY, generally following nervous excitement. Morphia
and opium; henbane (_Hyoscyamus_); stramonium; belladonna; nicotine
(_tobacco_); darnel (_lolium temulentum_); hemlock (_Conium
maculatum_); water hemlock (_Œnanthe crocata_); fool’s parsley (_Æthusa
cynapium_), [Dr. J. Harley shows that this is not so poisonous
as believed: _see_ St. Thomas’s Hospital Reports, x. 25]; Indian
hemp (_Cannabis indica_); Woody Nightshade (_Solanum dulcamara_);
Solanum nigrum; the berries of Potato (_Solanum tuberosum_); Lobelia
inflata: Foxglove (_Digitalis_); cocculus indicus; certain fungi
(notably _Amanita muscaria_); chloroform; chloral; butylchloral
—“croton chloral”): amylene; methylene dichloride; sulphuretted
hydrogen; carbonic oxide; and many other substances usually classed as
_narcotics_.
III. VOMITING.—Irritant poisons, such as acids, alkalies, alkaline
salts in considerable doses (even common salt has proved fatal: _see_
Christison[1]); most soluble compounds of the heavy metals (especially
antimony, arsenic, zinc, and copper); certain vegetal alkaloids (from
colchicum, laburnum, yew, savin, ipecacuanha, capsicum, pepper,
ergot, many species of Ranunculaceæ, the Hellebores, and some fungi);
cantharides, turpentine, and essential oils, &c. Pain in the digestive
organs, purging, and general inflammation are commonly present. Most of
the medicinal purgatives will produce sickness and vomiting if given in
overdoses; of course unwholesome food or disease may frequently be the
cause.
IV. ACTION ON THE EYE.—Opium and morphia, calabar bean, aconite (?),
and strychnia, _contract_ the pupil: belladonna, henbane, tobacco,
stramonium, digitalis and hemlock, _dilate_ the pupil. The effect is
often temporary, and sometimes is reversed after a time. It is a
valuable indication in after-experiments on animals.
V. CONVULSIONS.—Strychnia, brucia, and some fungi: but this symptom
is by no means confined to these, and may even result as tetanus, from
disease or irritants (_see_ Trial of Palmer). Morphia, in rare cases,
has also caused it.
VI. CHRONIC POISONING, prostration and wasting. Antimony, mercury,
and lead in small repeated doses. With the two latter, but more
especially with lead, there is a _blue line at the edge of the gums_;
constipation and colic, paralysis and trembling of the limbs. As lead
frequently occurs as an impurity in food, and also may be absorbed by
those working with it, these symptoms may be often accidental. Mercury
also is given, less than of old, it is true, but still systematically
by some, as a regular course in syphilis, &c.: also to children in
teething powders. Antimony has been almost abandoned in medicine, from
its depressant effect. In these cases, motive, amount, and necessity
of dose, and right to administer, must be considered before wilful
poisoning can be proved. The analysis, therefore, must be strictly
_quantitative_, which is fortunately tolerably easy.
The above summary is by no means perfect, since there are minor
differences in each class, which may sometimes rise into such
prominence as to confuse the classification. But in medical evidence
on the individual poisons of which we treat, those physiologically
resembling them in action are always most heard of at the trial, and
questions are asked whether this or that may not produce the same
symptoms; and hence it is well to direct attention to the analogues of
our types.
The primary idea of an _alkaloid_ is derived from its resemblance to
an _alkali_. Alkaloids are often called also “Organic Bases.” Their
names terminate in—_ia_ or _ine_.[2] They are more or less alkaline
to test paper, and combine with acids to form salts which are neutral
in reaction and often crystallizable. Only a few of the alkaloids
are liquid and easily volatile, but almost all can be volatilized
by careful heating at definite temperatures, giving in many cases
a sublimate of characteristic appearance under the microscope,
either of crystals, globules, or a mere film. In a free state, the
alkaloids are very slightly soluble in water, but soluble in alcohol,
and generally in ether and chloroform. Some are soluble in benzine,
others in amylic alcohol, petroleum spirit, acetic ether, &c. On a
judicious use of these various solvents depend the different processes
of isolation, among which Dragendorff’s is the most complete, but so
complicated that it is rarely used in its entirety. Fortunately there
is generally a clue more or less definite to the probable poison
administered, enabling a shorter and quicker method to be adopted. For
further details as to these processes see Blyth’s Manual of Practical
Chemistry. The sulphates, chlorides, and acetates of the alkaloids
are generally soluble in water; if ammonia or potash be added to the
solution, a precipitate (usually crystalline) of the free alkaloid
occurs if the solution be of moderate strength.
Chemically, the alkaloids are derived from ammonia (NH_{3}) by
substituting various organic groups or “compound radicles” (compounds
of carbon and hydrogen), for the hydrogen of the ammonia. They are
therefore “compound ammonias,” or “amines.” Nitrogen, carbon, and
hydrogen, are always present in natural alkaloids, the non-volatile
ones, including the greater number, also contain oxygen.
Physiologically, alkaloids as a class have a powerful action on
the human and animal frame. The medicinal properties of plants are
generally due to these substances, though many are still undiscovered
or imperfectly known. They exist in the plant combined with vegetal
acids, some of which are characteristic, as aconitic acid in aconite,
meconic in opium, igasuric (?) in nux vomica, &c. The very small
quantity which may sometimes be fatal (a fraction of a grain of the
pure alkaloid), the indefiniteness of many of their chemical reactions,
and the facility with which they decompose if too high a heat, or too
strong reagents, be employed in their extraction, render the detection
often a difficult, and sometimes an impossible matter. Fortunately,
however, fresh tests and better processes develop from every case, and
other indications, from symptoms and collateral circumstances, rarely
fail to bring home the guilt even to the most ingenious and scientific
of poisoners.
For extracting the alkaloids from animal matters the following process
has been used by the author. Mince finely, digest with rectified spirit
and enough acetic acid to _just acidify_, warm to blood-heat for 15
minutes, filter: this is the first extract. Warm the insoluble matters
with more alcohol and filter again: this is the second extract. Repeat
the extraction a third time. _Keep the three extracts separate._ Each
should be evaporated at as low a temperature as possible, not exceeding
50° C., and preferably in a vacuum at the ordinary temperature, if this
can be done fairly quickly. The syrupy residues must be treated with
water and a drop of acetic acid, passed through wet filters to separate
fat, rendered just alkaline with ammonia, and shaken with a moderate
quantity of a mixture of equal volumes of ether and chloroform (Allen).
By a stoppered funnel or burette the ethereal layer is separated,
the shaking with ether and chloroform and the separation repeated a
second and a third time, the ethereal extracts mixed, transferred to
a large porcelain dish, and evaporated, first in a current of air,
then in a vacuum or spontaneously. As the solvents evaporate, water
generally appears: this hinders any crystallization. Therefore the
residue must be rendered _dry_, then dissolved in a little _anhydrous_
chloroform (dried by standing over fused calcium chloride), and again
evaporated in air in a large watch glass. The residue will generally be
crystalline under the microscope if any alkaloid be present. Dissolve
again in chloroform, transfer to a graduated burette, make up to a
convenient volume (say 10 cubic centimetres), and transfer a measured
fraction to a number of watch glasses, reserving about one-fourth for
any subsequent _quantitative_ test that may be necessary. Allow the
liquid in the watch glasses to spontaneously evaporate. To the first
add a little water and a very minute quantity of dilute hydrochloric
acid, and cautiously taste a portion. A tingling of the lips and
subsequent numbness indicate _aconite_; intense bitterness points
to _strychnia_; if there be no taste at all it is unlikely that any
alkaloid is present. There are some alkaloids of a peppery taste; these
are irritants, and are not common as poisons. Bitterness is the most
frequent characteristic.
2. Moisten the contents of the second watch glass with a little water
and a trace of acetic acid, and apply through an incision in the
skin of the back of a young frog. He should be kept as comfortable
as possible and the symptoms observed. Strychnia readily produces
tetanus in this animal; other poisons also have peculiar effects. Some
observers have used mice, rabbits, or cats; in the Palmer trial it was
observed that dogs were not employed because they were inconvenient
and might bite! On the whole this so-called physiological test has
been overrated, as it is hardly to be expected that an animal with its
back cut and otherwise injured will not exhibit some symptoms; and
all who have kept wild animals in confinement will know how soon they
become, first almost convulsive from excitement, then finally sink into
stupor and die. If necessary, any judge may grant a special licence to
the experts in a trial to make experiments on animals, otherwise such
cruelty is rendered penal by the Vivisection Act.[3]
3. To the third watch glass, after the contents have been dissolved
as before, a drop of a solution of iodine in potassium iodide is
added. Nearly all alkaloids give a brown precipitate. If none occur, a
negative conclusion may be expected.
4. Test the fourth watch glass in one corner for strychnia by
concentrated sulphuric acid and peroxide of manganese; in another
corner for morphia by iodic acid and starch; in a third corner for
brucia (and morphia) by strong nitric acid. (See the special paragraphs
on these reactions, pp. 280, 285.)
5. If there is still no indication, and no information has
been obtained from other sources, it may be necessary to employ
Dragendorff’s process on the remainder. But if the poison has been
discovered, the solution reserved in the burette should be evaporated,
dissolved in water and a little dilute acid, avoiding heat, and
titrated by Mayer’s reagent to ascertain the quantity.[4]
The second and third extractions of the organs must now be considered.
Most of the text-books recommend that _all the extracts should be
mixed_. The objection to this is, that since the alkaloid is usually
present in very small amount, the first extraction will remove nearly
all of it, while the second and third will mainly contain other
matters, and therefore will be only adding to the impurities, and
consequently to the difficulty of isolation. If it be worth while, the
second and third extracts may be treated _separately_ as above, and
should any further quantity of alkaloid be found, it may be determined
quantitatively, and the amount added to that already obtained.
It has been proposed to precipitate the original spirituous extract by
neutral or basic acetate of lead, which throws down many impurities,
but leaves the alkaloids in solution. After filtration, the liquid
is treated with a current of sulphuretted hydrogen to remove lead;
again filtered, evaporated (as speedily as can be done without
overheating) to a moderate bulk, and treated with a little ammonia
and with ether-chloroform as before. If the sulphuretted hydrogen be
left exposed to the air for some time, it oxidizes to sulphuric acid,
which, during and after evaporation, tends to destroy the alkaloid.
Hence I have found it advisable to remove the H_{2}S quickly by a
current of carbonic acid and warming—previous to evaporation. But
this process is not good for alkaloids, as sulphur compounds are often
formed, which interfere with subsequent operations.
The foregoing process may fail to extract _morphia_, _curarine_, and
_solanine_, as these, being very little soluble in ether-chloroform,
may remain behind in the aqueous liquid. This, therefore, should be
afterwards treated in one of the following ways:—
1. Heat some redistilled amylic alcohol nearly to boiling (it boils
at 120° C.), add an equal volume to the aqueous (alkaline) solution;
shake vigorously, separate while still hot, and shake again with a
fresh, but rather smaller, quantity of the hot solvent. The united
amylic alcohol solutions will contain all the morphia, but can only be
distilled in vacuo, since at 120° C. the stability of the morphia would
be endangered. It is better to extract the morphia from the amylic
solution by shaking with successive small portions of weak acetic acid,
separating each time, till the acidity remains unneutralized. The
alkaloid will now be in the acid solution. Nearly neutralize this with
ammonia, evaporate at a gentle heat, and apply the special tests.
2. Instead of the above, the aqueous alkaline solution may be agitated
with a mixture of equal volumes of ether and _pure_ acetic ether (the
latter having been previously purified from free acid by standing over
powdered carbonate of lime). Although this mixture does not extract the
morphia so readily as amylic alcohol, it has this advantage that, after
separation from the aqueous layer, it can be evaporated at a moderate
temperature, when the morphia, if in sufficient quantity, will be left
in the crystalline state, and can be tested as usual.
If sufficient material be at hand, of course both processes may be
used.[5]
Selmi (Gazz. Chim. Ital. vi., 32) has given a process for alkaloidal
extraction of which I have no experience.
When the alkaloid is obtained in a sufficiently pure form and in
sufficient quantity, the sublimation process of Dr. Guy, as improved
by Blyth, may be used. For the entire original method, see Blyth’s
Practical Chemistry, page 285.
Dr. Guy’s “subliming cell” is a ring of glass tubing about ⅛-inch long
and ⅓ to ½-inch diameter, ground true and smooth at top and bottom,
resting on a circle of thin microscope glass, and covered with another
similar circle. The alkaloid, thoroughly dry, is placed on the lower
disc (a drop of the solution may be evaporated on it), the whole fitted
together, and floated on mercury, or better, fusible metal, contained
in a small glass beaker nearly full, supported on wire gauze over a
small flame. A thermometer held by a clamp dips in the liquid metal.
With a hand lens of as high power as possible, the melting point, and
also the point when the first sublimate occurs on the upper glass, may
be observed. As soon as the sublimate has become sufficiently distinct,
the upper disc is removed, replaced by another, and examined under
¼-inch power of the microscope. The heat is slowly raised till charring
occurs, and anything characteristic noted.
_Morphia_ gives a clouding, consisting of minute dots, at 150° C.; from
188° to 200° C., distinct crystals are obtained; then it commences to
brown, melt, and carbonize.
_Strychnia_ gives a minute sublimate of fine needles at 169° C., and
melts at about 221° C.
_Brucia_ melts at 151° C., browns easily, but gives no true sublimate.
_Aconitine_ or aconitia melts at 183° to 184° C.
_Pseudaconitine_ melts at 104° to 105° C., and easily decomposes,
giving off water.
_Commercial aconitine_ usually melts below 100° C., and gives an
amorphous sublimate above 150° C.
The reactions of the other alkaloids will be found in Blyth’s Practical
Chemistry.
In order to avoid repetition, the mode of preparing the general
reagents for alkaloids will be given here.
1. _Mayers Reagent_, potassio-iodide of mercury, already described (p.
7; Liebig’s Annalen, 133, 286), gives white precipitates with almost
all alkaloids. The latter can be recovered from the precipitate by
treating it with a solution of zinc chloride mixed with caustic soda.
(Mayer.)
2. _Potassium tri-iodide_, a solution of iodine in potassium iodide,
gives a brown or reddish precipitate.[6]
3. _Sonnenschein’s test_, Phosphomolybdic acid, is prepared as follows.
To a warm solution of molybdate of ammonia acidified with nitric
acid, phosphate of soda is added as long as any yellow precipitate is
obtained. The precipitate is washed with water containing a little
nitric acid, and heated with sodium carbonate solution till dissolved.
Evaporate to dryness, heat to expel ammonia, add a little nitric
acid and heat again. One part of the residue is then dissolved in a
mixture of one part of nitric acid of 1·4 sp. gr., and nine parts of
water. With this reagent _strychnia_ gives a pale, other _alkaloids_
a bright yellow flocculent precipitate, in very dilute solutions. The
precipitates are soluble in ammonia, with the production of a greenish
blue colour in the cases of aconitia and morphia. From the alkaline
liquid the _alkaloid_ can be dissolved out by at once shaking with
ether-chloroform or hot amylic alcohol as already described. Instead of
using ammonia, the precipitate may be agitated with barium carbonate,
which has less tendency to decompose the base on its liberation.
4. A solution of _bismuth iodide_ in iodide of potassium is recommended
by Dragendorff (Zeitschr. f. Chimie, 1866, 478). 80 grammes of
commercial bismuth subnitrate are dissolved in 200 cubic centimetres
of nitric acid of sp. gr. 1·18: 272 grammes of potassium iodide
dissolved in a little water are added, the potassium nitrate allowed
to crystallize out, and the whole diluted to one litre. This solution
precipitates most alkaloids. The precipitate can be treated with sodium
carbonate and the liberated alkaloid extracted by ether-chloroform, &c.
For the equivalents, see Maugini, Gazz. Chim. Ital. 12, 155.
5. Scheibler has proposed _Phosphotungstic acid_ as a precipitant.
Sodium tungstate is digested with half its weight of phosphoric
acid, sp. gr. 1·13: on standing, phosphotungstic acid crystallizes.
Its solution is said to give a distinct precipitate with 1/200000
of a grain of strychnia and 1/100000 of quina, and with similar
amounts of other alkaloids. From this precipitate the alkaloid is
obtained by treating with sufficient milk of lime and shaking with
ether-chloroform, &c., as before. He recommends the previous removal
of impurities by lead acetate and sulphuretted hydrogen as already
described (p. 7) (Fresenius, Zeitschr. f. anal. Chemie, 12, 315).
6. _Picric acid_, a saturated aqueous solution, gives precipitates in
_neutral_ solutions of morphia and atropia. In solutions acidified with
sulphuric acid it gives the following:—morphia, and pseudomorphia, no
precipitate; aconitia, a precipitate only in concentrated solutions;
other alkaloids of opium, a thick precipitate.[7]
7. _Animal charcoal_, previously purified by hydrochloric acid and
thorough washing with water, when digested with neutral or alkaline
solutions of alkaloids, not too dilute, absorbs them from the liquid.
The charcoal, washed twice or thrice with small quantities of water,
is dried at a moderate temperature, and boiled with strong alcohol,
which extracts the alkaloid. This process has been used for separating
picrotoxin from beer, but has the inconvenience that the alkaloid is
liable to gradual oxidation within the pores of the charcoal, and that
the separation is never complete. It is this property that has caused
charcoal to be recommended as an antidote in poisoning.
8. All alkaloids form with _platinic chloride_ double salts of more or
less sparing solubility. These precipitates, washed, dried and weighed,
and then burnt, leave metallic platinum, the amount of which yields
a clue to the composition of the base. But aconitine and narcotine
are only thrown down from concentrated solutions, and a few are not
precipitated at all. Hence this test is of only occasional value in
toxicological work. The same may be said of _auric chloride_.
9. _Tannin_ or tannic acid, a moderately strong solution in water,
throws down most alkaloids. Coffee and tea, and other tannin-containing
infusions, have, therefore, been used as antidotes with dubious
success. As a test it is not distinctive.
10. _Phospho-antimonic acid_ (Schultze), prepared by mixing antimony
pentachloride with ordinary sodium phosphate and decanting the clear
liquid, gives whitish amorphous precipitates with alkaloids.
11. _Silico-tungstic acid_ is prepared by boiling commercial tungstate
of soda with fresh gelatinous silica. Filter and allow to crystallize.
This gives precipitates with very dilute solutions of alkaloids, but it
is also precipitated by ammonium chloride (Godefroy, Arch. d. Pharm.,
Nov. 1879). Zaubenheimer recommends it as a most delicate test: the
precipitate may be decomposed by soda or potash, and the base extracted
by ether-chloroform.
12. Auric chloride, palladious chloride, and mercuric chloride have
been proposed, but are not of much use. Potassium chromate and
sulphocyanide, and sodium nitroprusside give somewhat insoluble
precipitates, generally crystalline and of characteristic appearance
under the microscope. These tests should be strong, and must be used in
small quantity.
PTOMAINES OR CADAVERIC ALKALOIDS.—Much attention has been attracted
lately by the possible interference to toxicological detections owing
to the undoubted existence of natural alkaloids in the dead body
unpoisoned. Some of these, called by Selmi “Ptomaines” ([Greek: ptôma],
a corpse), somewhat simulate strychnia, &c., in their chemical and
physiological characters. The observation is not new, as years ago, in
the Privy Council’s reports, Thudichum called attention to alkaloids
separated by Sonnenschein’s process (phosphomolybdic acid) from the
brain, urine, and from decomposed bodies. Various substances of the
kind have also been found by other investigators. To these “cadaveric
alkaloids” have been attributed the “sausage poisoning,” so frequent
in Germany (for cases, see Casper’s Handbook, vol. 3), poisoning by
various foods, such as tinned meats, cheese, &c. Some are irritants,
others narcotics: different periods and circumstances of putrefaction
producing different compounds.
In an Italian criminal prosecution, F. Ciotto, who made the
investigation of the corpse, gave it as his opinion that strychnia was
probably present. Selmi, for the defence, pointed out differences from
strychnia, and considered the compound to be a ptomaine. [Arch. Pharm.
(3), 19, 187.] This will show the importance of the subject.
Casali (Gazetta, 1881, 312) regards ptomaines as not true alkaloids,
but as “acid or basic amidated compounds.” It is only the basic ones
that will interfere with testing. Panum and Bergmann have isolated a
substance called “_sepsin_,” generated by putrefaction, poisonous,
acting like a ferment but not destroyed by boiling, soluble in water,
but insoluble in alcohol, and thereby distinguished from alkaloids.
Sonnenschein and Zuelzer found a product of putrefaction which
produced tetanic symptoms, besides one resembling atropine. But these
substances, or similar ones, can be produced _without_ putrefaction, as
Paterno and Spica have shown that fresh blood and fresh albumen (white
of egg) yielded, with phosphomolybdic acid, potassio-mercuric iodide,
and other alkaloidal reagents, precipitates like those of the vegetal
alkaloids. Selmi has even supposed that death from various diseases may
be due to the formation of these compounds. The same author obtained
from a dead body one month after death a considerable amount of a
_crystallizable_ ptomaine, giving reactions like those of alkaloidal
poisons, and having poisonous effects on frogs.
Brouardel and Bouting (Compt. Rend. 92, 1056) propose the reducing
action of ptomaines as a distinction between them and vegetal
alkaloids. The solution in weak acid is added to a dilute mixture of
ferric chloride and potassium ferricyanide: the latter, if a ptomaine
be present, is reduced to ferrocyanide, and Prussian blue is thereby
precipitated. But Spica (Gazetta, 11, 486) has shown that strychnia,
brucia, morphia, and some others produce this reaction readily, and
Beckurts (Arch. Pharm. 3, 20, 104) adds aconitine and others as
producing it slowly. Hence the distinction is delusive. See also
Husemann (Arch. Pharm. 3, 16, 169; also 3, 20, 270), Tauret (Compt.
Rend. 92, 1163).
The discovery of these bodies has certainly raised a new difficulty for
toxicologists, and suggested a new and plausible defence, as it must be
confessed that at present there is no general method of distinguishing
between “cadaveric” and vegetal alkaloids. Yet this mainly affects
the “physiological” tests—on frogs and other small animals—for
there is no ptomaine yet discovered which gives _all_ the reactions
of strychnia, morphia, &c. If a chemist be asked, “Could any other
substance produce these reactions?” he can only answer, “I do not know
of any”; he cannot aver the impossibility. Then the circumstantial
evidence must decide.
In conclusion, the following principles should be noted:—
1. The quantity of poison found is generally only a small fraction
of the quantity taken. The vomit and evacuations are frequently
lost, and much may be decomposed by vital actions in the body, or by
putrefaction. That which has caused death is probably thereby either
decomposed or so combined as to be rendered undetectible: that which is
found is merely the surplus beyond the fatal dose. This would account
for the frequent non-discovery in the tissues when a small amount has
been given, or much time has elapsed. To metallic poisons this does not
apply, as, unless eliminated, they can always be found. See further
under Strychnia.
2. The symptoms will differ according to the dose, the form (solid
or solution, pure or admixed), habit, or idiosyncrasy, the state of
health, &c.
3. In the post-mortem examination, appearances common to dead bodies
generally are often mistaken for the effects of poison. See Casper’s
Handbook, vol. I., _et passim_.
4. Unhealthy or improper food or acute disease may cause suspicious
symptoms. This is the commonest solution of suspected poisoning.
5. In experiments on animals, it may be objected that they are
inconclusive as to man. This is not strictly true. But if a _recent
vomit_ proves poisonous to an animal, _with the same symptoms as in the
man_, that is almost conclusive evidence.
6. When a poison is not found by analysis, it does not follow that
it has not caused death. Unequal distribution, uncertainty of tests,
improper securing of the samples (Palmer case), decomposition or
elimination of the poison, may hinder discovery.
7. In every case, if possible, the approximate _quantity_ of the poison
should be ascertained and stated. This specially applies to substances
that _may_ have been administered medicinally.
“If poison be administered _with intent to murder_, it is not necessary
that there should be enough in the article administered to cause death,
or that it should be given in such a way as to act fatally. If any
poison be there, and the intent be proved, the crime of attempting to
administer poison is complete.” [Judge’s ruling in _Hartley_, Cent.
Crim. Court, May 12th, 1850; _Reg._ v. _Bacon_, Lincoln Summer Assizes,
1857; _Reg._ v. _Southgate_, Chelmsford Lent Assizes; _Reg._ v.
_Cluderay_, York, 1849].
For minute directions as to the conduct of toxicological
investigations, see Taylor’s Medical Jurisprudence, 1873, I., 202-209;
also Guy and Ferrier’s Forensic Medicine, 1881, p. 359, _et seq._