I.--PRECIPITATED FROM A HYDROCHLORIC ACID SOLUTION BY HYDRIC
SULPHIDE--PRECIPITATE YELLOW OR ORANGE.[700]
Arsenic--Antimony--Cadmium.
[700] Fresenius has pointed out that sulphur may mask small quantities
of arsenic, antimony, tin, &c., and he recommends that the turbid liquid
in which apparently nothing but sulphur has separated should be treated
as follows:--A test-tube is half filled with the liquid, and then a
couple of c.c. of petroleum ether or of benzene added, the tube closed
by the thumb, and the contents well shaken. The sulphur dissolves, and
is held in solution by the solvent, which latter forms a clear upper
layer. If traces of a metallic sulphide were mixed with the sulphur,
thin coloured films are seen at the junction of the two layers, and the
sulphides may also coat the tube above the level of the liquid with a
slight faintly-coloured pellicle (_Chem. News_, Jan. 4, 1895).
1. ARSENIC.
§ 707. =Metallic Arsenic=, at. wt. 75, specific gravity of solid 5·62 to
5·96, sublimes without fusion in small quantities at 110° (230° F.)
_Guy_. It occurs in commerce in whitish-grey, somewhat brittle,
crystalline masses, and is obtained by subjecting arsenical pyrites to
sublimation in earthen retorts, the arsenic being deposited in suitable
receivers on sheet iron. Metallic arsenic is probably not poisonous, but
may be changed by the animal fluids into soluble compounds, and then
exert toxic effects--volatilised metallic arsenic is easily transformed
in the presence of air into arsenious acid, and is therefore intensely
poisonous.
§ 708. =Arsenious Anhydride--Arsenious Acid--White Arsenic--Arsenic=,
As₂O₃ = 198; specific gravity of vapour, 13·85; specific gravity of
opaque variety, 3·699; specific gravity of transparent variety, 3·7385.
Composition in 100 parts, As 75·75, O 24·25; therefore one part of
metallic arsenic equals 1·32 of As₂O₃. It is entirely volatilised at a
temperature of 204·4°.
In analysis it is obtained in brilliant octahedral crystals as a
sublimate on discs of glass, or within tubes, the result of heating a
film of metallic arsenic with access of air. It is obtained in commerce
on a very large scale from the roasting of arsenical pyrites. As thus
derived, it is usually in the form of a white cake, the arsenious acid
existing in two forms--an amorphous and a crystalline--the cake being
generally opaque externally, whilst in the centre it is transparent.
According to Kruger, this change from the crystalline to the amorphous
condition is dependent upon the absorption of moisture, no alteration
taking place in dry air. Both varieties of arsenious anhydride are acid
to test-paper.
The solubility of arsenious acid is often a question involving chemical
legal matters of great moment. Unfortunately, however, no precisely
definite statement can be made on this point, the reason being that the
two varieties of arsenic occur in very different proportions in
different samples. Both the amorphous and crystalline varieties having
very unequal solubilities, every experimenter in succession has given a
different series of figures, the only agreement amid the general
discrepancy being that arsenic is very sparingly soluble in water.
The statement of Taylor may, however, be accepted as very near the
truth, viz., that an ounce of cold water dissolves from half a grain to
a grain. According to M. L. A. Buchner,[701] one part of crystalline
arsenious acid dissolves after twenty-four hours’ digestion in 355 parts
of water at 15°; and the amorphous, under the same condition, in 108 of
water. A boiling solution of the crystalline acid, left to stand for
twenty-four hours, retains one part of acid in 46 of water; a similar
solution of the amorphous retains one of arsenic in 30 parts of water,
_i.e._, 100 parts of water dissolve from 2·01 to 3·3 parts of As₂O₃.
[701] _Bull. de la Société Chem. de Paris_, t. xx. 10, 1873.
Boiling water poured on the powdered substance retains in cooling a
grain and a quarter to the ounce; in other words, 100 parts of water
retain ·10. Lastly, arsenious acid boiled in water for an hour is
dissolved in the proportion of 12 grains to the ounce, _i.e._, 100 parts
of water retain 2·5.
K. Chodomisky[702] has investigated the solubility of recrystallised
arsenious acid in dilute acids, and his results are as follows:--100
c.c. of 1·32 per cent. hydrochloric acid dissolves 1·15 grm. As₂O₃ at
18·5°. 100 c.c. of 6 per cent. hydrochloric acid dissolves 1·27 grm. at
18·5°. 100 c.c. of pure hydrochloric acid of the ordinary commercial
strength dissolves 1·45 grm. As₂O₃. 100 c.c. of dilute sulphuric acid at
18° dissolves about 0·54 grm.; at 18·5° from 0·65 to 0·72 grm.; and at
80° from 1·09 to 1·19 grm.
[702] _Chem. Centrbl._, 1889, 569.
§ 709. =Arsine--Arseniuretted Hydrogen=, H₃As.--Mol. weight, 78; vol.
weight, 39; specific gravity, 2·702; weight of a litre, 3·4944 grammes;
percentage composition, 95·69 As, 4·31 H; volumetric composition, 2 vol.
H₃As = half vol. As + 3 vol. H. A colourless inflammable gas, of a
fœtid alliaceous odour, coercible into a limpid colourless liquid at a
temperature of from -30° to -40°. The products of the combustion of
arseniuretted hydrogen are water and arsenious acid; thus, 2H₃As + 6O =
3H₂O + As₂O₃. If supplied with air in insufficient quantity, if the
flame itself be cooled by (for example) a cold porcelain plate, or if
the gas pass through a tube any portion of which is heated to redness,
the gas is decomposed and the metal separated. Such a decomposition may
be compared to the deposit of carbon from ordinary flames, when made to
play upon a cooled surface. It may also be decomposed by the electric
spark,[703] _e.g._, if the gas is passed slowly through a narrow tube
0·7 to 0·8 mm. internal diameter, provided with wires 0·5 to 0·6 mm.
apart, and a small induction coil used connected with two large Bunsen’s
cells, then, under these conditions, arsenic as a metal is deposited in
the neighbourhood of the sparks. For the decomposition to be complete,
the gas should not be delivered at a greater speed than from 10 to 15
c.c. per minute. The gas burns with a blue-white flame, which is very
characteristic, and was first observed by Wackenroder. It cannot,
however, be properly seen by using the ordinary apparatus of Marsh, for
the flame is always coloured from the glass; but if the gas is made to
stream through a platinum jet, and then ignited, the characters
mentioned are very noteworthy.
[703] N. Klobrikow, _Zeit. Anal. Chem._, xxix. 129-133.
Oxygen or air, and arsine, make an explosive mixture. Chlorine
decomposes the gas with great energy, combining with the hydrogen, and
setting free arsenic as a brown cloud; any excess of chlorine combines
with the arsenic as a chloride. Sulphur, submitted to arseniuretted
hydrogen, forms sulphuretted hydrogen, whilst first arsenic and then
sulphide of arsenic separate. Phosphorus acts in a similar way.
Arseniuretted and sulphuretted hydrogen may be evolved at ordinary
temperatures without decomposition; at the boiling-point of mercury
(350°) they are decomposed, sulphide of arsenic and hydrogen being
formed; thus, 3H₂S + 2AsH₃ = As₂S₃ + 6H₂, a reaction which is of some
importance from a practical point of view. Many metals have also the
property of decomposing the gas at high temperatures, and setting
hydrogen free. Metallic oxides, again, in like manner combine with
arsenic, and set water free, _e.g._, 3CuO + 2H₃As = Cu₃As₂ + 3H₂O.
Arsine acts on solutions of the noble metals like phosphuretted
hydrogen, precipitating the metal and setting free arsenious acid; for
example, nitrate of silver is decomposed thus--
12AgNO₃ + 2H₃As + 3H₂O = As₂O₃ + 12HNO₃ + 12Ag.
Vitali[704] thinks the reaction is in two stages, thus:--
[704] _L’Orosi_, 1892, 397-411.
(1) 2AsH₃ + 12AgNO₃ = 2(Ag₃As3AgNO₃) + 6HNO₃.
(2) 2(Ag₃As,3AgNO₃) + 6H₂O = 6HNO₃ + 6Ag₂ + 2H₃AsO₃.
This reaction admits of valuable practical application to the estimation
of arsenic; for the precipitated silver is perfectly arsenic-free; the
excess of nitrate of silver is easily got rid of by a chloride of sodium
solution, and the absorption and decomposition of the gas are complete.
In cases of poisoning by arsine, the blood, when examined by the
spectroscope (a process the analyst should never omit where it is
possible), is of a peculiar inky colour, and the bands between D and C
are melted together, and have almost vanished. Such blood, exposed to
oxygen remains unaltered.
§ 710. =Arsine in the Arts, &c.=--In the bronzing of brass, in the
desilverising of lead by zinc, and subsequent treatment of the silver
zinc with hydrochloric acid, in the tinning of sheet iron, and similar
processes, either from the use of acids containing arsenic as an
impurity, or from the application of arsenic itself, arsine is evolved.
§ 711. =Effects on Animals and Man of Breathing Arsine.=--The most
general effect on mammals is to produce jaundice, bloody urine, and
bile. In the course of numerous experiments on dogs, Stadelmann[705]
found that by making them breathe a dose of arsine, which would not be
immediately fatal, icterus was always produced under these
circumstances, and could be always detected by the appearance of the
tissues. The bile is remarkably thickened, and the theory is, that in
such cases the jaundice is purely mechanical, the gall-duct being
occluded by the inspissated bile. Rabbits experimented upon similarly
showed increased biliary secretion, but no jaundice; while it was proved
that cats are not so sensitive to arsine as either rabbits or dogs.
There are not wanting instances of arsine having been breathed by
man--the discoverer of the gas, Gehlen, was in fact the first victim on
record. In order to discover a flaw in his apparatus he smelt strongly
at the joints, and died in eight days from the effects of the
inhalation.
[705] _Die Arsenwasserstoff-Vergiftung, Archiv f. exper. Path. u.
Pharm._, Leipzig, 1882.
Nine persons, workmen in a factory, were poisoned by arsine being
evolved during the treatment by hydrochloric acid of silver-lead
containing arsenic. Three of the nine died; their symptoms were briefly
as follows:--
(1) H. K., 22 years old; his duty was to pour hydrochloric acid on the
metal. Towards mid-day, after this operation, he complained of nausea,
giddiness, and _malaise_. In the afternoon he felt an uncommon weight of
the limbs, and an oppression in breathing. His fellow-workmen thought
that he looked yellow. On going home he lay down and passed into a
narcotic sleep. Next morning he went to his work as usual, but was not
capable of doing anything; he passed bloody urine several times
throughout the day, and fell into a deep sleep, from which he could
scarcely be roused. On the third day after the accident, a physician
called in found him in a deep sleep, with well-developed jaundice, the
temperature moderately high, pulse 100. On the fifth day the jaundice
diminished, but it was several months before he could resume his work.
(2) J. T., aged 19, suffered from similar symptoms after five and a half
hours’ exposure to the gas. He went home, vomited, was jaundiced, and
suffered from bloody urine; in six days became convalescent, but could
not go to work for many months.
(3) C. E. was very little exposed, but was unwell for a few days.
(4) L. M., 37 years old, was exposed two days to the gas; he vomited,
had bloody urine, passed into a narcotic sleep, and died in three days
from the date of the first exposure.
(5) J. S., aged 40, was exposed for two days to the gas; the symptoms
were similar to No. 4, there was suppression of urine, the catheter
drawing blood only, and death in eight days.
(6) M. E., 36 years old; death in three days with similar symptoms.
(7), (8), and (9) suffered like Nos. 1 and 2, and recovered after
several months.
The chief _post-mortem_ appearance was a dirty green colour of the
mucous membrane of the intestines, and congestion of the kidneys.
Arsenic was detected in all parts of the body.[706]
[706] Trost, _Vergiftung durch Arsenwasserstoff bei der technischen
Gewinnung des Silbers, Vierteljahrsschrift f. gericht. Med._, xviii.
Bd., 2 Heft, S. 6, 1873.
Two cases are detailed by Dr. Valette in Tardieu’s _Étude_.[707] A
mistake occurred in a laboratory, by which a solution of arsenic
(instead of sulphuric acid) was poured on zinc to develop hydrogen. Of
the two sufferers, the one recovered after an illness of about a week or
ten days, the other died at the end of twenty-eight days. The main
symptoms were yellowness of skin, vomiting, bloody urine, great
depression, slight diarrhœa, headache, and in the fatal case a
morbiliform eruption. In a case recorded in the _British Medical
Journal_, November 4, 1876, there were none of the usual symptoms of
gastric irritation, but loss of memory of recent acts, drowsiness, and
giddiness.
[707] Ambroise Tardieu, _Étude Médico-légale sur l’Empoisonnement_, Obs.
xxv. p. 449.
§ 712. =The Sulphides of Arsenic.=--Of the sulphides of arsenic, two
only, realgar and orpiment, are of any practical importance. _Realgar_,
As₂S₂ = 214; specific gravity, 3·356; composition in 100 parts, As
70·01, S 29·91; average composition of commercial product, As 75, S 25.
Realgar is found native in ruby-red crystals, and is also prepared
artificially by heating together 9 parts of arsenic and 4 of sulphur, or
198 parts of arsenious anhydride with 112 parts of sulphur, 2As₂O₃ + 7S
= 2As₂S₂ + 3SO₂. It is insoluble in water and in hydrochloric acid, but
is readily dissolved by potassic disulphide, by nitric acid, and by
aqua regia. It is decomposed by caustic potash, leaving undissolved a
brown sediment (As₁₂S), which contains 96·5 per cent. of arsenic. The
dissolved portion is readily converted into arsine by aluminium.
§ 713. =Orpiment, or Arsenic Trisulphide.=--As₂S₃ = 246; specific
gravity, 3·48; composition in 100 parts, As 60·98, S 39·02; found native
in crystals, presents itself in the laboratory usually as a brilliant
yellow amorphous powder, on passing sulphuretted hydrogen through an
acid solution of arsenious acid or an arsenite. It is very insoluble in
water (about one in a million, _Fresenius_), scarcely soluble in boiling
concentrated hydrochloric acid, and insoluble generally in dilute acids.
Red fuming nitric acid dissolves it, converting it into arsenic and
sulphuric acids; ammonia and other alkaline sulphides, the alkalies
themselves, alkaline carbonates, bisulphide of potassium, and aqua
regia, all dissolve it readily. In the arts it is used as King’s yellow
(see p. 532). Tanners also formerly employed a mixture of 90 parts of
orpiment and 10 of quicklime, under the name of _Rusma_, as a
depilatory; but the alkaline sulphides from gas-works are replacing this
to a great extent.
§ 714. =Haloid Arsenical Compounds.--The Chloride of Arsenic=, AsCl₃ =
181·5; specific gravity liquid, 0° 2·205; boiling-point 134° (273·2°F.),
is a heavy, colourless, oily liquid, which has been used as an
escharotic in cancerous affections (principally by quacks). In one
process of detecting and estimating arsenic, the properties of this
substance are utilised (see p. 575). It is immediately decomposed by
water into arsenious and hydrochloric acids.
=The Iodide of Arsenic= (AsI₃) is used occasionally in skin diseases,
but is of little interest to the analyst; it is commonly seen in the
form of brick-red brilliant flakes.
§ 715. =Arsenic in the Arts.=--The metal is used in various alloys; for
example, speculum metal is made of tin, copper, and a little arsenic;
white copper is an alloy of copper and arsenic; shot is composed of 1000
parts of lead mixed with 3 of arsenic; the common Britannia metal used
for tea-pots, spoons, &c., often contains arsenic; and brass is bronzed
with a thin film of arsenic. It was formerly much employed in the
manufacture of glass, but is being gradually superseded. It is also now
used to some extent in the reduction of indigo blue, and in that of
nitro-benzole in the manufacture of aniline.
In cases of suspected poisoning, therefore, and the finding of arsenic
in the stomach, or elsewhere, it may be set up as a defence that the
arsenic was derived from shot used in the cleansing of bottles, from the
bottles themselves, or from metal vessels, such as tea-pots, &c.
The arsenic in all these alloys being extremely insoluble, any solution
to a poisonous extent is in the highest degree improbable. It may,
however, be necessary to treat the vessels with the fluid or fluids
which have been supposed to exert this prejudicial action, and test
them for arsenic. The treatment should, of course, be of a severe and
exhaustive character, and the fluids should be allowed to stand cold in
the vessels for twenty-four hours; then the effect of a gentle heat
should be studied, and, lastly, that of boiling temperatures. The
analysis of the alloy itself, or of the glass, it would seldom be of
value to undertake, for the crushed and finely divided substance is in a
condition very different from that of the article when entire, and
inferences drawn from such analytical data would be fallacious.
Arsenious anhydride is also used for the preservation of wood, and is
thrown occasionally into the holds of vessels in large quantities to
prevent vegetable decomposition. In India, again, a solution of arsenic
is applied to the walls as a wash, in order to prevent the attacks of
insects.
§ 716. =Pharmaceutical, Non-officinal, and other Preparations of
Arsenic.=--(1) =Pharmaceutical Preparations.=--The Liquor arsenicalis
(Fowler’s solution), or solution of arsenic of the pharmacopœia, is
composed of:--
Carbonate of Potash, 87 grains (5·64 grms.)
Arsenious Acid, 87 „ (5·64 „ )
Compound Tincture of Lavender, 5 drachms (17·72 c.c.)
dissolved in 1 pint (567·9 c.c.) of water; every ounce, therefore,
contains 4·3 grains of arsenious acid (or 100 c.c. = ·9As₂O₃); the
strength is therefore nearly 1 per cent.
=Liquor Ammonii Arsenitis= (not officinal) is made of the same strength,
ammonium carbonate being substituted for potassic carbonate.
The _hydrochloric solution of arsenic_ is simply arsenious acid
dissolved in hydrochloric acid; its strength should be exactly the same
as that of Fowler’s solution.
A solution of _arseniate of soda_[708] contains the _anhydrous_ salt in
the proportion of 4 grains to the ounce (·9 in 100 c.c.) of water.
[708] The formula for arseniate of soda is Na₂HAsO₄7H₂O, but it
sometimes contains more water.
=Liquor Arsenii et Hydrargyri Iodidi= (Donovan’s Solution of
Arsenic).--This is not officinal, but is used to some extent in skin
diseases; it is a solution of the iodides of mercury and arsenic;
strength about 1 per cent. of each of the iodides.
=Arseniate of Iron=, Fe₃As₂O₈, is an amorphous green powder, used to
some extent in medicine. It should contain 33·6 per cent. of metallic
arsenic.
=Clemen’s Solution.=--A solution of the bromide and arseniate of
potassium; strength equal to 1 per cent. arsenious acid. Officinal in
U.S., France, and Norway.
=Pilula Asiatica= (not officinal) is composed of arsenious acid, extract
of gentian, and black pepper. There is 1/12th of a grain (5·4
milligrams) of arsenious acid in each pill.
=Dr. De Valanguis’ Solutio solventes mineralis= is composed of 30 grains
of As₂O₃ dissolved by 90 minims of HCl in 20 oz. of water; strength =
0·034 per cent. As₂O₃.
(2) =Veterinary Arsenical Medicine.=--Common veterinary preparations
containing arsenic are:--A ball for worms, containing in parts--
Calomel, 1·3 per cent.
Arsenious Acid, 1·3 „
Tin Filings, 77·9 „
Venice Turpentine,[709] 19·5 „
[709] The Venice turpentine is rarely found in ordinary commerce, what
is sold under that name consisting of black resin and oil of turpentine.
A common tonic ball:[710]--
[710] A similar preparation in common use has the addition of sulphate
of zinc.
Arsenious Acid, 5 to 10 grains (·324 to ·648 grm.)
Aniseed, ½ oz. (14·1744 grms.)
Opium, 30 grains ( 1·94 „ )
Treacle, q. s.
An arsenical ball, often given by grooms to horses for the purpose of
improving their coats, contains in 100 parts:--
Arsenious Acid, 2·5 per cent.
Pimento, 19·2 „
Extract of Gentian, 78·3 „
Another ball in use is composed of arsenic and verdigris (acetate of
copper), of each 8 grains (·518 grm.); cupric sulphate, 20 grains (1·3
grm.); q. s. of linseed meal and treacle.
(3) =Rat and Fly Poisons, &c.=--An arsenical paste sold for rats has the
following composition:--
Arsenious Acid, 5·0 per cent.
Lampblack, ·6 „
Wheat Flour, 46·3 „
Suet, 46·3 „
Oil of Aniseed, a small quantity.
Another rat poison is composed as follows:--
White Arsenic, 46·8 per cent.
Carbonate of Baryta, 46·8 „
Rose-pink,[711] 5·8 „
Oil of Aniseed, ·2 „
Oil of Rhodium, ·2 „
[711] Alum and carbonate of lead coloured with Brazil and peach woods.
Various arsenical preparations are used to kill flies; the active
principle of the brown “_papier moure_” is arsenious acid. A dark grey
powder, which used to be sold under the name of fly-powder, consisted of
metallic arsenic that had been exposed some time to the air.
=Fly-water= is a strong solution of arsenious acid of uncertain
strength, sweetened with sugar, treacle, or honey. Another fly-poison
consists of a mixture of arsenious acid, tersulphide of arsenic,
treacle, and honey.
(4) =Quack and other Nostrums.=--The analyst may meet with several quack
preparations for external use in cancer. A celebrated arsenical paste
for this purpose is composed of:--
Arsenious Acid, 8 per cent.
Cinnabar, 70 „
Dragon’s Blood, 22 „
=Frères Come’s Cancer Paste= is composed of arsenious acid, 1; charcoal,
1; red mercury sulphide, 4; water, q. s.
The tasteless “_ague drops_” used in the fen countries are simply a
solution of arsenite of potash.
=Davidson’s Cancer Remedy= consists, according to Dr. Paris, of equal
parts of arsenious acid and powdered hemlock.
In India, arsenic given as a medicine by native practitioners, or
administered as a poison, may be found coloured and impure, from having
been mixed either with cow’s urine, or with the juice of leaves,
&c.[712]
[712] Chevers, _Med. Jurisprudence for India_, p. 116.
Arsenious acid is used by dentists to destroy the nervous pulp of
decayed and painful teeth, about the twenty-fifth of a grain (2·5
mgrms.) being placed in the cavity. A common formula is arsenious acid,
2; sulphate of morphine, 1; creasote, q. s. to make a stiff paste. There
is no record of any accident having resulted from this practice
hitherto; but since the dentist seldom weighs the arsenic, it is not
altogether free from danger.
(5) =Pigments, &c.=--_King’s yellow_ should be As₂S₃, the trisulphide of
arsenic or orpiment. It is frequently adulterated with 80 to 90 per
cent. of arsenious acid, and in such a case is, of course, more
poisonous. King’s yellow, if pure, yields to water nothing which gives
any arsenical reaction.
A blue pigment, termed _mineral blue_, consists of about equal parts of
arsenite of copper and potash, and should contain 38·7 per cent. of
metallic arsenic (= to 51·084 As₂O₃H) and 15·6 of copper.
=Schweinfurt green= (Syn. _Emerald-green_), (CuAs₂O₄)₃Cu(C₂H₃O₂)₂ is a
cupric arsenite and acetate, and should contain 25 per cent. of copper
and 58·4 per cent. of arsenious acid. In analysis, the copper in this
compound is readily separated from the arsenic by first oxidising with
nitric acid, and then adding to the nitric acid solution ammonia, until
the blue colour remains undissolved. At this point ammonium oxalate is
added in excess, the solution is first acidified by hydrochloric or
nitric acid, and, on standing, the copper separates completely (or
almost so) as Oxalate, the arsenic remaining in solution.
Another method is to pass SH₂ to saturation, collect the sulphides on a
filter, and, after washing and drying the mixed sulphides, oxidise with
fuming nitric acid, evaporate to dryness, and again treat with nitric
acid. The residue is fused with soda and potassic nitrate, the fused
mass is dissolved in water, acidulated with nitric acid, and the copper
is precipitated by potash; the solution is filtered, and in the filtrate
the arsenic is precipitated as ammonio-magnesian arseniate or as
trisulphide.[713]
[713] P. Gucci, _Chem. Centrbl._, 1887, 1528.
=Scheele’s green= (CuHAsO₃) is a hydrocupric arsenite, and contains 52·8
per cent. of arsenious anhydride and 33·8 per cent. of copper.
(6) =External Application of Arsenic for Sheep, &c.=--Many of these are
simply solutions of arsenic, the solution being made by the farmer. Most
of the yellow sheep-dipping compounds of commerce are made up either of
impure carbonate of potash, or of soda ash, arsenic, soft soap, and
sulphur. The French _bain de Tessier_ is composed of:--
Arsenious Acid, 1·00 kgrm.
Ferrous Sulphate, 10·00 „
Peroxide of Iron, 0·40 „
Gentian Powder, 0·20 „
This is to be added to 100 kgrms. of water. Another common application
consists of alum and arsenic (10 or 12 to 1), dissolved in two or three
hundred parts of water.
(7) =Arsenical Soaps, &c.=--Arsenic is used in preserving the skins of
animals. One of the compounds for this purpose, known under the name of
_Bécoeur’s arsenical soap_, has the following composition:--
Camphor, 3·4 per cent.
Arsenic, 20·2 „
Carbonate of Potash, 56·2 „
Lime,[714] 20·2 „
[714] The dust from the preserved skins of animals has caused, at least,
one case of poisoning. _Ann. d’Hyg. Pub. et de Méd. Lég._, 2 sér., 1870,
t. xxxiii, p. 314.
(8) =Arsenical compounds= used in pyrotechny:--
Parts.
Blue fires--(1) Realgar, 2
Charcoal, 3
Potassic Chlorate, 5
Sulphur, 13
Nitrate of Baryta, 77
-----
(2) Sulphur, 40·9
Nitre, 36·8
Sulphide of Antimony, 12·3
„ Arsenic, 5
Charcoal, 5
-----
Green fires--Metallic Arsenic, 2
Charcoal, 3
Chlorate of Potash, 5
Sulphur, 13
Nitrate of Baryta, 7
------
Light green fire--Charcoal, 1·75
Sulphide of Arsenic, 1·75
Sulphur, 10·50
Chlorate of Potash, 23·25
Nitrate of Baryta, 62·50
------
White fire--(1) Arsenious Acid, ·76
Charcoal, 1·63
Sulphide of Antimony, 12·27
Nitrate of Potash, 36·59
Sulphur, 48·75
------
(2) Realgar, 6·1
Sulphur, 21·2
Nitrate of Potash, 72·7
------
§ 717. =Statistics.=--During the ten years 1883-92 there were registered
in England and Wales 113 deaths from arsenic; of these 57, or about
half, were suicidal deaths, and 5 were classed under the head of
“murder”; the rest were due to accident. The age and sex distribution of
persons dying from accidental or suicidal arsenical poisoning are
detailed in the following table:--
DEATHS FROM ARSENIC DURING THE TEN YEARS 1883-1892.
ACCIDENT OR NEGLIGENCE.
Ages, 1-5 5-15 15-25 25-65 65 and Total
above
Males, 1 4 3 23 6 37
Females, 4 ... 3 4 3 14
---------------------------------------
Total, 5 4 6 27 9 51
---------------------------------------
SUICIDE.
Ages, 15-25 25-65 65 and Total
above
Males, 3 32 2 37
Females, 5 12 3 20
----------------------------
Total, 8 44 5 57
----------------------------
§ 718. =Law Relative to the Sale of Arsenic.=--By the 14th of Vict. c.
12, every person selling arsenic is bound to keep a written record of
every particular relative to each transaction, such as the name, abode,
and calling of the purchaser, the purpose for which the poison is
required, and the quantity sold, &c. These particulars are to be signed
also by the purchaser. No person (sec. 2) is allowed to sell arsenic to
any one unknown to the seller, unless in the presence of a witness whom
the seller is acquainted with. The arsenic sold (sec. 3) is to be mixed
with soot or indigo in the proportion of half an ounce of indigo to a
pound of arsenic. It, therefore, follows that the coloured substance
should not contain more than 70 per cent. of arsenious acid. The Act
applies to all the colourless preparations of arsenic: but it is not to
affect chemists in making up prescriptions for medical men, or in
supplying medical men; nor is it to affect the wholesale dealers in
supplying arsenic to retail shops, &c. The penalty for conviction is
£20, or less.[715]
[715] Commercial arsenic is often much adulterated, especially with
gypsum, chalk, &c. These are most readily detected by subliming the
arsenic. The sublimed arsenic itself may not be entirely pure, sometimes
containing arsenical sulphides and antimonious oxide.
§ 719. =Dose.=--The smallest dose of arsenic known to have proved fatal
to a human being is ·16 grm. (2½ grains). Farriers and grooms are in the
habit of giving as much as l·3 grm. (20 grains) a day to a horse, so
that the poisonous dose for this animal must be very large.
The maximum dose for the horned cattle appears to be from ·32 to ·38
grm. (5 to 6 grains); that for a dog is 16 mgrms. (¼ grain), and even
this may, in the smaller kinds, cause illness.
The following may be considered as _dangerous doses_ of arsenic:--·13
grm. (2 grains) for an adult; 1·9 grm. (30 grains) for a horse; ·64 grm.
(10 grains) for a cow; and 32 to 64 mgrms. (½ to 1 grain) for a dog.
§ 720. =Effects of Arsenious Acid on Plants.=--If the root or stem of a
plant is immersed in a solution of arsenious acid, the hue of the leaves
soon alters in appearance, the green colour becomes of a whitish or
brownish hue, and the plant withers; the effect being very similar to
that produced by hot water. The toxic action may be traced from below
upwards, and analysis will detect minute quantities of arsenic in all
portions of the plant.
It has, however, been shown by Gorup-Besanez,[716] that if arsenious
acid be mixed with earth, and plants grown in such earth, they only take
up infinitesimal quantities of arsenic. Hence, in cases of cattle
poisoning, any defence based upon the alleged presence of arsenic in the
pasture will be more ingenious than just.
[716] _Annal. d. Chemie u. Pharmacie_, Bd. cxxvii., H. 2, 243.
The influence of arsenical fumes as evolved from manufactories upon
shrubs and trees is in general insignificant. Pines and firs, five to
six years old, have been known to suffer from a disease in which there
is a shedding of the leaves, the more tender herbage being at the same
time affected. Whatever dangers the practice of steeping corn intended
for seed in a solution of arsenious acid, as a preventive of “smut,” may
possess, it does not appear to influence deleteriously the growth of the
future plant.
Superphosphate of manure is frequently rich in arsenic. Dr. Edmund Davy
asserts that plants to which such manure is applied take up arsenic in
their tissues, and M. Andonard has made a similar statement. Tuson[717]
has also undertaken some experiments, which confirm Andonard and Davy’s
researches. The bearing of this with relation to the detection of
arsenic in the stomachs of the herbivora needs no comment.
[717] Cooley’s _Dictionary_, Art. “Arsenic.”
§ 721. =Effects on Animal Life--Animalcules.=--All infusoria and forms
of animalcule-life hitherto observed perish rapidly if a minute quantity
of arsenious acid is dissolved in the water in which they exist.
=Insects.=--The common arsenical fly-papers afford numerous
opportunities for observing the action of arsenic on ordinary flies;
within a few minutes (five to ten after taking the poison into their
digestive organs) they fall, apparently from paralysis of the wings, and
die. Spiders and all insects into which the poison has been introduced
exhibit a similar sudden death. It is said that in the neighbourhood of
arsenical manufactories there is much destruction among bees and other
forms of insect life.
=Annelids.=--If arsenious acid is applied to the external surface of
worms or leeches, the part which it touches perishes first, and life is
extinguished successively in the others. If a wound is made first, and
the arsenious acid then applied to it, the effects are only intensified
and hastened. There is always noticed an augmentation of the excretions;
the vermicular movements are at first made more lively, they then become
languid, and death is very gradual.
=Birds.=--The symptoms with birds are somewhat different, and vary
according to the form in which the poison is administered, viz., whether
as a vapour or in solution. In several experiments made by Eulenberg on
pigeons, the birds were secured under glass shades, and exposed to the
vapour of metallic arsenic vaporised by heat. It is scarcely necessary
to remark that in operating in this way, the poisoning was not by
metallic arsenic vapour, but by that of arsenious acid. One of these
experiments may be cited:--A pigeon was made to breathe an atmosphere
charged with vapour from the volatilisation of metallic arsenic. The
bird was immediately restless; in thirty minutes it vomited repeatedly,
and the nasal apertures were noticed to be moist; after a little while,
the bird, still breathing the arsenious acid atmosphere, was much
distressed, shook its head repeatedly, and yawned; in fifty minutes the
respiration was laboured, and in fifty-nine minutes there was much
vomiting. On removing the bird, after it had been exposed an hour to the
vapour (·16 grm. of metallic arsenic having been evaporated in all), it
rapidly recovered.
Six days after, the pigeon was again exposed in the same way to the
vapour, but this time ·56 grm. of metallic arsenic was volatilised. In
fifteen minutes there was retching, followed by vomiting. On taking it
out after an hour it remained very quiet, ate nothing, and often puffed
itself out; the breathing was normal, movements free, but it had unusual
thirst. On the second and third day the excretions were frequent and
fluid; the cardiac pulsations were slowed, and the bird was disinclined
to move. On the fourth day it continued in one place, puffing itself
out; towards evening the respirations slowed, the beak gaping at every
inspiration. On attempting flight, the wings fluttered and the bird fell
on its head. After this it lay on its side, with slow, laboured
respiration, the heart-beats scarcely to be felt, and death took place
without convulsions, and very quietly. On examining the organs after
death, the brain and spinal cord were very bloodless; there were
ecchymoses in the lungs; but little else characteristic. The experiment
quoted has a direct bearing upon the breathing of arsenical dust; as,
for example, that which floats in the air of a room papered with an
easily detached arsenical pigment. Other experiments on birds generally
have shown that the symptoms produced by arsenious acid in solution, or
in the solid form, in a dose insufficient to destroy life, are languor,
loss of appetite, and the voidance of large quantities of liquid excreta
like verdigris. With fatal doses, the bird remains quiet; there are
fluid, sometimes bloody, excretions; spasmodic movements of the pharynx,
anti-peristaltic contraction of the œsophagus, vomiting, general
trembling of the body, thirst, erection of the feathers, and laboured
respiration. The bird becomes very feeble, and the scene mostly closes
with insensibility and convulsions.
=Mammals=, such as cats, dogs, &c., suffer from symptoms fairly
identical with those observed in man; but the nervous symptoms
(according to P. Hugo) do not predominate, while with rabbits and
guinea-pigs, nervous symptoms are more marked and constant.[718] There
are vomiting, purging, and often convulsions and paralysis before death.
It has been noticed that the muscles after death are in a great state of
contraction. The slow poisoning of a dog, according to Lolliot,[719]
produced an erythematous eruption in the vicinity of the joints, ears,
and other parts of the body; there were conjunctivitis, increased
lachrymal secretion, and photophobia; the hair fell off.
[718] _Archiv f. exper. Path. u. Pharmakol_, Leipzig, 1882.
[719] _Étude Physiol. d’Arsène_, Thèse, Paris, 1868.
§ 722. =Effects of Arsenious Acid on Man.=--The symptoms produced by
arsenious acid vary according to the form of the poison--whether solid,
vaporous, or soluble--according to the condition of bodily health of the
person taking it, and according to the manner in which it is introduced
into the animal economy, while they are also in no small degree modified
by individual peculiarities of organisation and by habit, as, for
instance, in the arsenic-eaters.
=Arsenic-Eaters.=--In all European countries grooms and horse-dealers
are acquainted with the fact that a little arsenic given daily in the
corn improves the coat, increases, probably, the assimilation of the
food, and renders the horse plump and fat. On the Continent grooms have
been known to put a piece of arsenic, the size of a pea, in a little
oatmeal, make it into a ball, tie it up in a linen rag, and attach it to
the bit; the saliva dissolves, little by little, the poison, while both
the gentle irritation and physiological action excite a certain amount
of salivation, and the white foam at the mouth, and the champing of the
horse, are thought vastly to improve the appearance. Shot, which
contains a small quantity of arsenic, have been used for the same
purpose, and from half a pound to a pound of small shot has been given
to horses. When a horse has been for a long time dosed with arsenic, it
seems necessary to continue the practice; if this is not done, the
animal rapidly loses his condition. The explanation probably is, that
the arsenic stimulates the various cells and glands of the intestinal
tract to a superaction, the natural termination of which is an
enfeeblement of their secreting power--this especially in the absence of
the stimulus. Turning from equine involuntary arsenic-eaters, we find
the strange custom of arsenic-eating voluntarily pursued by the races of
lower Austria and Styria, especially by those dwelling on the mountains
separating Styria from Hungary. In India also (and especially in the
Punjaub) the same practice prevails, and here it is often taken as an
aphrodisiac. The mountaineers imagine that it increases the respiratory
power, nor is there wanting some evidence to show that this is actually
the fact, and medicinal doses of arsenic have been in use for some time
in cases of asthma and other diseases of the chest. The arsenic-eaters
begin with a very small dose, which is continued for several weeks or
months, until the system gets accustomed to it. The amount is then
slightly augmented until relatively large doses are taken with impunity.
In one case[720] it appears that a countryman, in good health, and sixty
years of age, took daily 4 grains of arsenious acid, a habit which he
had inherited from his father, and which he in turn bequeathed to his
son.
[720] Tardieu, _op. cit._
The existence of such a custom as arsenic-eating, in its literal sense,
has more than once been doubted, but all who have travelled over Styria
and other places where the habit prevails have convinced themselves that
the facts have not been overstated. For example, Dr. Maclagan, in
company with Dr. J. T. Rutter,[721] visited Styria in 1865, and having
carefully weighed 5 or 6 grains of arsenic, saw these doses actually
swallowed by two men. On collecting their urine, about two hours
afterwards, abundant quantitative evidence of its presence was found;
but in neither of the men were there the slightest symptoms of
poisoning. It is obvious that the existence of such a habit might
seriously complicate any inquiry into arsenical poisoning in these
regions.
[721] _Edin. Med. Journ._, April 1865; _Brit. and For. Med. Chir.
Journ._, Oct. 1865.
§ 723. =Manner of Introduction of Arsenic.=--Arsenious acid exerts a
poisonous action, whether it is taken by the stomach, or introduced into
the system by any other channel whatever. The differences in the
symptoms produced by external application (as through a wound), and by
swallowing arsenious acid in substance or in solution, are not so marked
as might be expected. It was probably Hunter who first distinctly
recognised the fact that arsenic, even when introduced outwardly by
application to an abraded surface, exerts a specific effect on the
mucous membrane of the stomach. Brodie[722] states, “Mr. Home informed
me that in an experiment made by Mr. Hunter himself, in which arsenic
was applied to a wound in a dog, the animal died in twenty-four hours,
and the stomach was found to be considerably inflamed. I repeated this
experiment several times, taking the precaution of always applying a
bandage to prevent the animal licking the wound. The result was that the
inflammation of the stomach was commonly more violent and more immediate
than when the poison was administered internally, and that it preceded
in appearance the inflammation of the wound.”
[722] _Phil. Trans._, 1812.
§ 724. =Cases of Poisoning by the External Application of Arsenic.=--A
mass-poisoning by the external use of arsenical violet powder to infants
occurred in England some years ago. Two deaths from this cause were
established by coroners’ inquests.[723] Dr. Tidy found the violet
powders used in the two cases to have the following composition:--
[723] “Gleanings in Toxicology,” by C. Meymott Tidy, M.B.--_Lancet_,
Aug. 21, 1878.
1. 2.
Per cent. Per cent.
Arsenious Acid, 38·5 38·3
Starch (Potato), 54·8 55·4
Magnesia, &c. 6·7 6·3[724]
[724] Two recipes were handed in at the coroner’s inquest which pretty
fairly represent the composition of ordinary commercial violet powder:--
_First Quality, sold at 7s. per gross._
Starch Powder, 28 lbs.
Magnesia, 1½ lb.
Orris-root, 1 lb.
Violet Perfume, 1 oz.
Essence of Roses, 5 drops.
_Second Quality, sold at 6s. per gross._
Terra Alba (Sulphate of Lime), 14 lbs.
Potato Starch, 21 lbs.
Magnesia, 3 lbs.
Orris-root, 1½ lb.
Violet Perfume, 1½ oz.
Essence of Roses, 5 drops.
Although the children were poisoned by absorption through the skin
(unless it is allowed that some may have found its way in the form of
arsenical dust into the throat, or, what is still more probable, that
the infants may from time to time have seized the puff-ball and _sucked_
it), the large quantity of ·421 grm. (6·5 grains) of arsenious acid was
separated in the one case, and ·194 grm. (3 grains) in the other. In
these cases arose the question which is sure to recur in legal inquiries
into poisoning by absorption, viz., whether the poison lying on the
surface and folds of the skin could not have been mixed during the
_post-mortem_ examination with the organs of the body? In these
particular cases special care appears to have been taken, and the answer
was satisfactory. It is not amiss, however, to call attention to the
extreme precaution which such instances necessitate.
A woman, aged 51, had used a solution of arsenious acid to cure the
itch; erysipelas of the body, however, followed, and she died after a
long illness--one of the symptoms noted being trembling and paresis of
the limbs.[725] In a case recorded by Desgranges,[726] a young
chambermaid had applied to the unwounded scalp an arsenical ointment for
the purpose of destroying vermin. She also suffered from a severe
erysipelas, and the hair fell off. Quacks have frequently applied
various arsenical pastes to ulcers and cancerous breasts with a fatal
result. Instances of this abound; in one, a charlatan applied to a
chronic ulcer of the leg an arsenical caustic; the patient showed
symptoms of violent poisoning, and died on the sixth day.[727] In
another, a lady suffering from some form of tumour of the breast,
applied to an unqualified practitioner, who made from fifteen to twenty
punctures with a lancet in the swelling, covered a piece of bread with
an arsenical compound, and applied the bread thus prepared to the
breast. Twelve hours afterwards symptoms of violent gastric irritation
commenced; and vomiting and a sanguinolent diarrhœa followed, with death
on the fifth day. Arsenic was found in all the organs.[728] Such
examples might be multiplied. Arsenic has been in more than one case
introduced criminally into the vagina with a fatal result.[729] Foderé,
_e.g._, has recorded the case of a maid-servant who poisoned her
mistress by intentionally administering several arsenical enemata.[730]
Arsenious acid again has been respired in the form of vapour. One of the
best instances of this is recorded by Taylor, and was the subject of a
trial at the York Lent Assizes, 1864. The prisoner placed some burning
pyrites at the doorway of a small room, in which there were eight
children, including an infant in the cradle. The other children were
removed speedily, but the infant was exposed to the vapour for an hour;
it suffered from vomiting and diarrhœa, and died in twenty-four hours.
There was slight inflammation of the stomach and intestines, the brain
and lungs were congested, and the lining membrane of the trachea of a
bright red colour. Arsenic was detected in the stomach, in the lungs,
and spleen. The pyrites contained arsenic, and the fatal fumes were in
effect composed of sulphurous and arsenious acids.
[725] Belloc, _Méd. Lég._, t. iv. p. 124.
[726] _Recueil de la Soc. de Méd. de Paris_, t. vi. p. 22, An. vii.;
also Tardieu, _Étude Méd. Légale, sur l’Empoisonnement_, Obs. xxvii. p.
457.
[727] Mean, _Bibliothèque Méd._, t. lxxiv., 1821, p. 401.
[728] Tardieu, _op. cit._, Obs. xxix.; Dr. Vernois, _Ann. d’Hyg. et de
Méd. Lég._, t. xxxvi., 1st ser., p. 141, 1846.
[729] Ansiaulx, _Clinique Chirurgicale_. Mangor (_Acta. Societ. Reg.
Hafniens_, iii. p. 178) gives the case of a man who poisoned his three
wives successively with arsenic--the two last by introducing into the
vagina a powder composed of flour and arsenic. Another similar case is
related by Brisken. Mangor made experiments on mares, showing that when
arsenic is applied to the vagina, death may result from inflammation.
[730] _Méd. Légale_, iv.
§ 725. =Arsenic in Wall-Papers.=--It is now an accepted fact that
arsenical colours on wall-papers cause illness. The symptoms are those
of chronic poisoning, and present nothing distinctive from the effects
produced from small doses of arsenic.
Kirschgasser[731] has described the symptoms in detail of twenty-six
cases. That arsenic is actually present in patients suffering is often
susceptible of proof, by examining skilfully and carefully a
considerable volume (from one to two days’ collection) of the urine; in
most of the cases thus examined arsenic has been discovered. This
poisoning is produced, sometimes from the dust, at others from a
volatile compound of arsenic, which has the following properties:--It is
very volatile (perhaps a gas), it has a strong alliaceous odour, it is
not entirely decomposed by a solution of silver nitrate, but is
apparently decomposed by a boiling acid solution of potassic
permanganate. The author suggests that it may be a compound of CO and
As, but this is only a supposition. The existence of this volatile
substance has been settled beyond all question by the experiments of
Gosio,[732] confirmed by those of Charles Robert Sanger.[733]
[731] _Vierteljahr. f. gericht Med._, N. F., ix. 96.
[732] _Azione di alcune Muffe sui Compositi fissi d’Arsenico. Ministero
dell’ Interno, Laboratori Scientifici della Direzione di Sanita_, Roma,
1892.
[733] “On the Formation of Volatile Compounds of Arsenic from Arsenical
Wall-Papers,” _American Academy of Arts and Sciences_, vol. xxix.
This substance appears to be readily enough produced by the action of
the common moulds upon organic matter in the presence of small amounts
of arsenic; the moulds vary in this property: _Mucor_, _Mucedo_, and
_Aspergillum glaucum_ react well; on the contrary, _Penicillium
glaucum_, _Mucor ramosus_, and several others have either no action, or
the action is but slight. One mould, the _Penicillium brevicaule_, has
quite a special endowment in forming this peculiar arsenical compound;
so much so, that Gosio has proposed its use as a reagent for arsenic,
the garlic odour being perceived when the fungus is made to grow in
solutions containing organic matter and only traces of arsenic.
§ 726. =Forms of Arsenical Poisoning.=--There are at least four distinct
forms of arsenical poisoning, viz., an acute, subacute, a nervous, and a
chronic form.
=Acute Form.=--All those cases in which the inflammatory symptoms are
severe from the commencement, and in which the sufferer dies within
twenty-four hours, may be called acute. The commencement of the symptoms
in these cases is always within the hour; they have been known, indeed,
to occur within eight minutes, but the most usual time is from twenty
minutes to half an hour. There is an acrid feeling in the throat, with
nausea; vomiting soon sets in, the ejected matters being at first
composed of the substances eaten; later they may be bilious or even
bloody, or composed of a whitish liquid. Diarrhœa follows and
accompanies the vomiting, the motions are sometimes like those met with
in ordinary diarrhœa and English cholera, and sometimes bloody. There is
coldness of the extremities, with great feebleness, and the pulse is
small and difficult to feel. The face, at first very pale, takes a
bluish tint, the temperature falls still lower; the patient sinks in
collapse, and death takes place in from five to twenty hours after the
taking of the poison.
There can scarcely be said to be any clinical feature which
distinguishes the above description from that of cholera; and supposing
that cholera were epidemic, and no suspicious circumstance apparently
present, there can be little doubt that a most experienced physician
might mistake the cause of the malady, unless surrounding circumstances
give some hint or clue to it. In the acute form diarrhœa may be absent,
and the patient die, as it were, from “shock.” This was probably the
cause of death in a case related by Casper,[734] that of Julius Bolle,
poisoned by his wife. He took an unknown quantity of arsenic in
solution at seven in the morning, and in about three-quarters of an hour
afterwards suffered from pain and vomiting, and died in little more than
three hours. There were no signs of inflammation in the stomach and
intestines, but from the contents of the stomach were separated ·0132
grm. of arsenious acid, and ·00513 grm. from pieces of the liver,
spleen, kidneys, lung, and blood. The dose actually taken is supposed
not to have been less than ·388 grm. (6 grains).
[734] Case 188 in Casper’s _Handbuch_.
§ 727. =The Subacute Form.=--The subacute form is that which is most
common; it exhibits some variety of phenomena, and individual cases vary
much in the matter of time. The commencement of symptoms is, as in the
most acute form, usually within the hour, but exceptions to this rule
occur. In a case quoted by Taylor,[735] and recorded by M. Tonnelier,
the poison did not cause any marked illness for eight hours; it was
found, on _post-mortem_ examination, that a cyst had been formed in the
stomach which sheathed the arsenic over, and in some degree explained
this delay. In another case, again, ten hours elapsed, and this is
considered to be the maximum period yet observed. As with the acute
form, there is a feeling of nausea, followed by vomiting, which
continues although the stomach is quite empty; at first the ejected
matter is a watery fluid, but later it may be streaked with blood. The
tongue is thickly coated; there is great thirst, but the drinking of any
liquid (even of ice-cold water) increases the vomiting. Nearly always
pain is felt in the epigastrium, spreading all over the abdomen, and
extending to the loin (which is tense and tender on pressure).
Deglutition is often painful, and is accompanied by a sort of spasmodic
constriction of the pharyngeal muscles. Diarrhœa follows the vomiting,
and has the same characters as that previously described; occasionally,
however, this feature is absent. In the case recorded by Martineau,[736]
a man, aged 25, was seized at 10 A.M. suddenly with vomiting, which
persisted all that day and the next, during which time the bowels were
obstinately confined. On the second day a purgative was administered,
whereupon diarrhœa set in, and continued until his death, which occurred
in about two days and sixteen hours from the commencement of the
symptoms. This case is also remarkable from the absence of pain or
tenderness of the abdomen.
[735] Taylor’s _Principles and Practice of Jurisprudence_, vol. i. p.
251; Flandin, vol. i. p. 535.
[736] Tardieu, _op. cit._, Obs. xix.
In subacute cases the urine has several times been suppressed, and it is
generally scanty and red in colour. Irregularity of the heart’s action
and feebleness are tolerably constant phenomena. As the end approaches,
there is excessive muscular weakness, the face is pale, the eyes hollow;
the mucous membranes first, and then the skin, take a bluish tint; the
skin itself is covered with perspiration, and there has been noticed a
peculiar odour, which has been likened to arsine (arseniuretted
hydrogen). The respiration is troubled, convulsive movements of the
limbs have been observed, and cramps in the calves of the legs; death
follows in a variable time--from twenty-four hours to several days. In
certain cases there is a curious remission after violent symptoms, the
patient rallies and seems to have recovered; but the appearance is
deceptive, for the symptoms recur, and death follows. Recovery may also
take place partially from the primary effects, and then inflammatory
changes in the stomach, &c., set in, with fever and the ordinary
symptoms which are common in all internal inflammation.
A single dose of arsenious acid may cause a prolonged and fatal illness,
one of the best known examples being that of the suicide of the Duc de
Praslin,[737] who took, with suicidal intent, on Wednesday, August 18,
1847, a dose of arsenious acid. The exact time of the act could not be
ascertained, but the first effects appeared at 10 P.M.; there were the
usual signs of vomiting, followed on the next day by diarrhœa, fainting,
and extreme feebleness of the pulse. On Friday there was a remission of
the symptoms, but great coldness of the limbs, intermittency and
feebleness of the heart’s action, and depression. On Saturday there was
slight fever, but no pain or tenderness in the abdomen, vomiting, or
diarrhœa; on this day no urine was passed. On the Sunday he complained
of a severe constriction of the throat, and deglutition was extremely
painful; thirst was extreme, the tongue intensely red, as well as the
mucous membrane of the mouth and pharynx, and the patient had a
sensation of burning from the mouth to the anus. The abdomen was painful
and distended, the heat of the skin was pronounced, the pulse frequent
and irregular,--sometimes strong, at others feeble,--the bowels had to
be relieved by injections, the urine was in very small quantity; during
the night there was no sleep. The duke died at 4.35 A.M. on Tuesday the
24th, the sixth day; intelligence was retained to the last. As the end
approached, the respiration became embarrassed, the body extremely cold,
and the pulse very frequent.
[737] Tardieu, “Relation Médico-Légale de l’Assassinat de la Duchesse de
Praslin,” _Ann. d’Hyg. Pub. et de Médico-Lég._, 1847, t. xxxviii. p.
390; also _op. cit._, Obs. xi.
§ 728. =In the nervous form= the ordinary vomiting and purging are
either entirely suppressed, or present in but feeble degree; and under
this heading are classed the rare cases in which, in place of the
ordinary symptoms, affections of the nervous system predominate.
Narcotism, paresis, deepening into paralysis, delirium, and even acute
mania, as well as epileptiform convulsions, have all been recorded. In
short, the symptoms show so much variety, that an idea of the malady
produced in this very rare form can only be obtained by studying the
clinical history of cases which have presented this aspect. In a case
recorded by Guilbert,[738] a man, thirty-five years of age, had
swallowed a solution of arsenic, half of which was immediately rejected
by vomiting. A little while afterwards his respiration became laborious;
the eyes were bathed with tears, which were so acrid as to inflame the
eyelids and the cheeks; the muscles of the face were from time to time
convulsed; he perspired much, and the perspiration had a fœtid odour;
there was some diarrhœa, the urine was suppressed, and from time to time
he was delirious. Afterwards the convulsions became general, and the
symptoms continued with more or less severity for five days. On the
sixth a copious miliary eruption broke out, and the symptoms became less
severe. The eruption during fifteen days every now and again reappeared,
and at the end of that time the patient was convalescent, but weak,
liable to ophthalmia, and had a universal trembling of the limbs.
[738] _Journal de Van der Monde_, 1756, t. iv. p. 353; Tardieu, _op.
cit._, Obs. xiii. p. 430.
In one of Brodie’s[739] experiments on rabbits, 7 grains of arsenious
acid were inserted in a wound in the back; the effect of which was to
paralyse the hind legs. In other experiments on animals, paralysis of
the hind legs has been frequently noticed, but paralysis certainly is
rare in man; in the case, however, recorded by Barrier,[740] of the five
men who took by mistake a solution of arsenious acid, one of them was
found stretched on the ground with the inferior extremities paralysed.
[739] “The Action of Poisons,” _Phil. Trans._, 1812.
[740] _Journ. de Médecine_, 1783, p. 353; Tardieu, _op. cit._, Obs. xiv.
p. 431.
In a case of “mass” poisoning reported by Dr. Coqueret,[741] three
persons ate by mistake an unknown quantity of arsenious acid--two of
them only suffered slightly, but the third severely, vomiting occurring
almost immediately, and continuing with frequency until the end of the
fourth day. Two hours after swallowing the poison, the patient took the
hydrated oxide of iron as an antidote. On the sixth day there was stupor
and a semi-delirious state, with an eruption of a pustular character
compared to that of the small-pox. These symptoms continued more or less
until the fifteenth day, when they diminished, and ultimately the
patient recovered. In a case related by Tardieu,[742] in which a person
died on the eleventh day from the effects of the poison, towards the
end, as a specially marked symptom, there was noted hyperæsthesia of the
inferior extremities, so that the least touch was painful.
[741] _Journ. de Connaiss. Méd. Chirurg._, 1839, p. 155; Tardieu, _op.
cit._, Obs. xv. p. 482.
[742] _Op. cit._, Obs. xvii. p. 434.
§ 729. =Absence of Symptoms.=--In a few cases there have been a
remarkable absence of symptoms, and this both in man and animals. Seven
horses were fed with oats accidentally mixed with arseniate of soda.
The first succumbed three hours after taking the poison, without having
presented any symptom whatever; he fell suddenly, and in a short time
expired.[743] It is related by Orfila,[744] that a woman, aged 27,
expired in about twelve hours from a large dose of arsenious acid; there
were the usual _post-mortem_ appearances, but in life no sign of pain,
no vomiting, and but little thirst.
[743] Bouley (Jeune), _Ann. d’Hyg. et de Médico-Lég._, 1834, t. xii. p.
393.
[744] Tome i. Obs. iv. p. 314.
§ 730. =Slow Poisoning.=--Slow poisoning has been caused accidentally by
arsenical wall-paper, in the manufacture of arsenical pigments, by the
admixture of small quantities of arsenic with salt or other condiments,
and repeated small doses have been used for criminally producing a fatal
illness intended to simulate disease from natural causes. The illness
produced by small intermittent doses may closely resemble in miniature,
as it were, those produced by large amounts; but, on the other hand,
they may be different and scarcely to be described otherwise than as a
general condition of ill-health and _malaise_. In such cases there is
loss of appetite, feebleness, and not unfrequently a slight yellowness
of the skin. A fairly constant effect seen, when a solution of arsenious
acid is given continuously for a long time, is an inflammation of the
conjunctivæ, as well as of the nasal mucous membrane--the patient
complains of “always having a cold.” This inflammatory action also
affects the pharynx, and may extend to the air-passages, and even to the
lung-tissue. At the same time there is often seen an exanthem, which has
received a specific name--“_eczema arsenicale_.” Salivation is present,
the gums are sore, at times lacerated. In chronic poisoning by arsenic,
nervous symptoms are almost constant, and exhibit great variety; there
may be numbness, or the opposite condition, hyperæsthesia, in the
extremities. In certain cases fainting, paresis, paralysis, and
sometimes convulsions occur; towards the end a sort of hectic fever
supervenes, and the patient dies of exhaustion.
§ 731. =The Maybrick Case.=[745]--The Maybrick case may be
considered an example of poisoning extending over a considerable
period of time:--Mr. James Maybrick, a Liverpool cotton-broker, aged
49, married Florence Elizabeth, an American lady, aged 21. They had
two children. The marriage proved an unhappy one. Some two years
before his death in May 1889 they had occupied two separate rooms.
Seven weeks before the husband’s death, Mrs. Maybrick went to London
on a false pretext, and lived for some days at an hotel, ostensibly
the wife of another man. Two days after her return, Mr. and Mrs.
Maybrick attended the Grand National race meeting, and there a
serious quarrel arose between them respecting the man with whom she
had cohabited in London; they returned from the race, each
separately, and she slept apart. Next day an apparent reconciliation
took place through the intervention of Dr. Fuller, the family
medical attendant.
[745] “The Maybrick Trial and Arsenical Poisoning,” by Thos. Stevenson,
M.D., _Guy’s Hosp. Rep._, 1889.
On or about April 12-19th, 1889, Mrs. Maybrick purchased arsenical
fly-papers. On April 13-20th Mr. Maybrick visited London, and
consulted Dr. Fuller for dyspepsia, who prescribed nux vomica,
acids, and mild remedies (but no arsenic); in one bottle of
medicine, ostensibly made according to Dr. Fuller’s prescription,
arsenic was subsequently found.
Up to Saturday, April 27th, Mr. Maybrick was in his usual health; he
was then sick, numbed, and in pain, and had cramps; he told his
clerk he had been an hour in the water-closet, but whether for
diarrhœa or constipation does not appear; he ascribed the symptoms
to an overdose of Fuller’s medicine. About this date fly-papers were
found by the servants soaking in Mrs. Maybrick’s bedroom in a
sponge-basin, carefully covered up. On the 29th she again purchased
two dozen fly-papers from another chemist. On April 28th Mr.
Maybrick was sick and ill; at 11 A.M. Dr. R. Humphreys was called
in; Mr. Maybrick complained of a peculiar sensation about his heart,
and said he was in dread of paralysis. He attributed his illness to
a strong cup of tea taken before breakfast. On the following day he
was better, and on the 30th still improving. On May 1st and 2nd Mr.
Maybrick went to his office and lunched, both days, off revalenta
food, prepared at home and warmed at his office in a new saucepan
purchased for the occasion; on one of these days the lunch was
forgotten, and was sent to Mr. Maybrick by his wife; and on one of
the two days, it is not clear which, Mr. Maybrick complained that
his lunch did not agree with him, and he attributed it to inferior
sherry put into his food.
In a jug found at the office, and in which food had been taken
there, a trace of the food still remained after Mr. Maybrick’s
death, and arsenic was found therein.
On May 3rd the last fatal illness set in. It is uncertain what food
he had after breakfast; he went to the office, and returned home
between 5 and 6 P.M. He had been seen by Dr. Humphreys in the
morning, and appeared then not quite so well; he found him at
midnight suffering from what he thought was severe sciatica; the
patient said he had been sick from revalenta. On May 4th he was
continually sick, nothing could be retained on the stomach, but the
sciatic pain was gone; on May 5th the vomiting continued, the
patient complained of the sensation of a hair sticking in the
throat, and of a filthy taste in the mouth. The throat and fauces
were only slightly reddened, the tongue was furred.
On May 6th there was less vomiting, but otherwise the condition was
the same, and Fowler’s solution ordered, but only a quantity equal
to 1/300 grain was actually taken.
May 7th the condition was improved, but there was no increase of
power. Dr. W. Carter was called in consultation. The vomiting was
passing away, and diarrhœa commencing. The throat was red, dry, and
glazed; there were incessant attempts to cough up an imaginary hair.
No cramps, no pain in the stomach or intestines, nor conjunctivitis.
On this day the first direct evidence of diarrhœa is recorded, the
medical men actually seeing a loose motion. The result of the
consultation was that Mr. Maybrick must have taken some irritant in
his food or drink.
On the 8th a professional nurse took charge. During the 8th and 9th
severe tenesmus set in with diarrhœa, and blood was observed in the
fæces. Now arsenic was suspected, the urine was examined by Dr.
Humphreys, and a rough analysis was made of some Neaves’ food which
the patient had been taking.
The patient died on the 10th, at 8.30 P.M.
The _post-mortem_ appearances were as follows:--
The tongue was dark, the top of the gullet slightly red, but
otherwise healthy, save at the lower end, where the mucous membrane
was gelatinous, and was dotted over with black dots, like frogs’
spawn.
There was a small shallow ulcer in the mucous membrane of the larynx
at the back of the epiglottis. The free margin of the epiglottis was
rough and eroded; and on the posterior aspect of the ericoid
cartilage there were two small red patches. In the stomach were
from 5-6 ozs. of brownish fluid. At the cardiac end there was a
large vermilion-red patch, interspersed here and there with small
dark ecchymoses (spoken of by Dr. Humphreys as a flea-bitten
appearance); to this followed a non-inflamed space, and near the
pyloric orifice, and extending 2 inches from it, was another red
inflamed portion of mucous membrane. In the small intestine the
mucous membrane was red and inflamed, from 3 inches below the
pylorus to about 3 feet downwards. About 18 or 20 feet lower down,
_i.e._, a little below the ileo-cæcal valve, the mucous membrane was
again inflamed to a lesser extent over a space of about 2 feet; the
lower end of the rectum was also red and inflamed. No arsenic was
found in the stomach or its contents, or in the spleen. Arsenic was
present in the liver, in the intestines, and in the kidneys. The
quantity separated altogether amounted to over 0·1 grain. The liver
weighed 48 ozs., and from 12 ozs. of the liver 0·076 grain of
arsenic, reckoned as As₂O₃, was separated.
The whole course of the symptoms and the _post-mortem_ examination
showed that the deceased died from an irritant poison; and from the
fact of a small quantity of arsenic having been found in the body,
there can be little doubt but that the poison was arsenic. The
symptoms were somewhat anomalous, but not more so than in other
recorded cases of undoubted arsenical poisoning. The facts that
tended to connect the accused with the death were as follows:--On
the night of either May 9th or the 10th Mrs. Maybrick was observed
to remove from the table an opened bottle of Valentine’s meat juice,
and take it into an inner dressing-room, and then replace it--the
acts being surreptitious. In replacing it, she was observed to take
it either from the pocket of her dressing-gown or from an inner
pocket. The lining of this pocket was found to be impregnated with
As₂O₃. The juice was found to contain 0·5 grain As₂O₃, and the
liquid was of lower gravity than commercial juice; it had probably,
therefore, been diluted.
The following is a list of things containing arsenic:--
1. Mrs. Maybrick’s dressing-gown.
2. „ apron.
3. A handkerchief wrapped around a bottle.
4. Packet of arsenic “for cats.” (Arsenious acid mixed with char-
coal.) Tumbler containing milk, with handkerchief soaking in it;
at least 20 grains of As₂O₃ in the tumbler mixed with charcoal.
5. A portion of a handkerchief.
6. A bottle containing a strong solution of arsenious acid and
several grains of undissolved arsenious acid.
7. A bottle containing from 15-20 grains of solid arsenic and a few
drops of solution.
8. A saturated solution of arsenious acid and some solid arsenious
acid.
9. Valentine’s meat juice.
10. Price’s glycerin; ⅔ grain in the whole bottle.
11. A bottle containing 0·1 grain of arsenious acid.
12. A bottle from Mr. Maybrick’s office containing a few drops of
medicine prescribed by Dr. Fuller (decidedly arsenical).
13. Jug from the office with remains of food.
14. Sediment from trap of w.c. and lavatory drain containing As₂O₃.
Mrs. Maybrick was convicted, but afterwards the sentence was
commuted to penal servitude for life.
§ 732. =Post-mortem Appearances in Animals.=--P. Hugo[746] has made some
minute researches as to the pathological appearances met with in
animals. His experiments were made on seven dogs, eight guinea-pigs,
five rabbits, two pigeons, and five cats--all poisoned by arsenious
acid. According to Hugo, so far as these animals were concerned, changes
were more constant in the intestine than in the stomach.
[746] _Beiträge zur Pathologie der acuten Arsenikvergiftung., Archiv für
exper. Pathol. u. Pharmakol._, Leipzig, 1882.
=Stomach.=--Changes in the mucous membrane were especially noticed in
the great curvature and towards the pylorus; the pylorus itself, and a
part of the cardiac portion, remained unchanged. The mucous membrane in
dogs and cats was red, with a tinge of blue--in many cases the redness
was in streaks, with injection of the capillaries. The stomach of
plant-eaters was less altered, and a microscopical examination of the
mucous tissues did not show any fatty change.
=The Intestines.=--In dogs and cats changes were evident; in rabbits and
guinea-pigs they were not so marked, but the intestines of the last were
extremely tender and brittle, very moist, and filled with a slimy,
serous, grey-white fluid; nevertheless, the changes in all these animals
appear to be of essentially the same nature. The most striking effect is
the shedding of a pseudo-membrane; in quite recent cases there is a
layer of from 1 to 1½ mm. wide of a transparent, frog-spawn-like jelly
streaking the intestine. In later stages it becomes thicker, while
occasionally it resembles a diphtheritic exudation. The mucous membrane
itself is deep purple-red, showing up by the side of the
pseudo-membrane. With regard to the villi, the epithelial layer is
detached, and the capillary network filled with blood and enlarged.
=The Liver.=--Hugo met only occasionally with fatty degeneration of the
liver, but there was marked steatosis of the epithelium of the
gall-bladder of dogs. A fact not prominently noticed before, is (at all
events, in dogs) a serous transudation into the pleural sac and acute
œdema of the lungs; the exudation may be excessive, so that more than
100 c.c. of serous fluid can be obtained from the thorax; there is also
usually much fluid in the pericardium. In two of Hugo’s experiments
there was fluid in the cerebral ventricles; and in all there was
increased moisture of the brain substance with injection of the
capillary vessels, especially of the pia.
§ 733. =Post-mortem Appearances.=--A remarkable preservation of the body
is commonly, but not constantly, observed. When it does occur it may
have great significance, particularly when the body is placed under
conditions in which it might be expected to decompose rapidly. In the
celebrated Continental case of the apothecary Speichert (1876),
Speichert’s wife was exhumed eleven months after death. The coffin stood
partly in water, the corpse was mummified. The organs contained arsenic,
the churchyard earth no arsenic. R. Koch was unable to explain the
preservation of the body, under these conditions, in no other way than
from the effect of arsenic; and this circumstance, with others, was an
important element which led to the conviction of Speichert.
When arsenious acid is swallowed in substance or solution, the most
marked change is that in the mucous membrane of the stomach and
intestines; and, even when the poison has been absorbed by the skin, or
taken in any other way, there may be a very pronounced inflammatory
action. On the other hand, this is occasionally absent. Orfila[747]
relates a case in which a man died in thirteen hours after having taken
12 grms. of arsenious acid:--“The mucous membrane of the stomach
presented in its whole extent no trace of inflammation, no redness, and
no alteration of texture.” Many other similar cases are on record; and,
according to Harvey’s statistics, in 197 cases, 36 (about 18·2 per
cent.) presented no lesion of the stomach.
[747] Tome i. Obs. v.
The usual changes produced by arsenious acid may be studied in the
museums of the London hospitals. In Guy’s Hospital Museum there are
three preparations. In preparation 1798³² is seen a large stomach with
the mucous membrane at certain points abraded, and at the great
curvature the whole coats are thinned; it is also somewhat congested. In
preparation 1798⁶⁴ is a portion of coagulated lymph, from the stomach of
a lad, aged 14, who had taken accidentally a piece of cheese charged
with arsenious acid, prepared for the purpose of destroying rats. He
lived twenty-eight hours, and presented the ordinary symptoms. The lymph
has a membranous appearance, and the rugæ of the stomach are impressed
upon it. It is said when recent to have presented numerous bright bloody
spots, although there was no visible breach of substance on the surface
of the stomach. The mucous membrane of the stomach is stated to have
been injected, and there was also diffuse injection of the duodenum.
Preparation 1798⁸⁰ is the stomach of a person who survived thirteen
hours after taking a fatal dose of arsenious acid; and in the same
museum there is a wax model of the appearances which the fresh
preparation exhibited, showing a large oval patch coated with mucus and
the poison. The stomach was intensely inflamed, the cæcum injected. The
rest of the intestine was healthy.
In the museum of University College there are two preparations, one[748]
exhibiting intense swelling and congestion of the gastric mucous
membrane, which is of a perfectly vermilion colour. Another preparation
(No. 2868) shows the effect of a small dose of arsenic on the stomach;
there are spots of arborescent extravasation, and slight congestion of
the summits of the rugæ, but in other respects it is normal. There is
also a cast of Peyer’s patches from the same case, showing great
prominence of the glands, with some injection of the intestinal mucous
membrane.
[748] This preparation at the time of my visit had no number.
In St. Thomas’ Hospital there is an interesting preparation (No. 8)
showing the gastric mucous membrane dotted all over with minute ulcers,
none of which have an inflammatory zone.[749] I have not, however, seen
in any museum a preparation of the curious emphysematous condition of
the mucous membrane, which has more than once been met with. For
example, in a case related by Tardieu,[750] Schwann, a labourer, died
from the effects of arsenic in thirty-six hours. The autopsy showed that
the mucous membrane of the stomach and small intestine was covered with
a pasty coating, and was elevated in nearly its whole extent by bullæ
filled with gas, forming true emphysematous swellings which encroached
upon the diameter of the intestine. There was neither redness nor
ulceration, but the mucous membrane was softened.
[749] In a case related by Orfila, t. i. Obs. xv., death resulted from
the outward application of arsenic; the mucous membrane of the stomach
was natural in colour, but there were four ulcers, one of which was 50
centimetres in diameter.
[750] _Op. cit._, Obs. i. p. 468.
The author saw, many years ago, at Barnard Castle, an autopsy made on a
gentleman who died from arsenic. In this case the mucous membrane of the
stomach presented a peculiar appearance, being raised here and there by
little blebs, and very slightly reddened.
§ 734. The inflammatory and other changes rarely affect the gullet.
Brodie[751] never observed inflammation of the œsophagus as an effect of
arsenic; but, when arsenic is swallowed in the solid state, as in the
suicide of Soufflard, graphically described by Orfila,[752] it may be
affected. In Soufflard’s case there was a vivid injection of the pharynx
and gullet.
[751] _Phil. Trans._, 1812.
[752] T. i. p. 319.
In many instances, when the arsenic has been taken in the solid form,
the crystals with mucus and other matters adhere to the lining membrane.
I have seen in the stomach of a horse, poisoned by an ounce of arsenic,
an exquisite example of this. The inflammatory changes may be recognised
many months after death owing to the antiseptic properties of arsenic;
nevertheless, great caution is necessary in giving an opinion, for there
is often a remarkable redness induced by putrefactive changes in healthy
stomachs. Casper,[753] on this point, very justly observes:--“If Orfila
quotes a case from Lepelletier, in which the inflammatory redness of the
mucous membrane of the stomach was to be recognised after nine months’
interment, and if Taylor cites two cases in which it was observed
nineteen and twenty-one months after death respectively, this is in
contradiction of all that I, on my part, have seen in the very numerous
exhumed corpses examined by me in relation to the gradual progress of
putrefaction and of saponification, and I cannot help here suspecting a
confusion with the putrefactive imbibition redness of the mucous
membrane.”
[753] _Handbuch_, vol. ii. p. 420.
If examined microscopically, the liver and kidneys show no change, save
a fatty degeneration and infiltration of the epithelial cells. In the
muscular substance of the heart, under the endocardium, there is almost
constantly noticed ecchymosis. In the most acute cases, in which a
cholera-like diarrhœa has exhausted the sufferer, the blood may be
thickened from loss of its aqueous constituents, and the whole of the
organs will present that singularly dry appearance found in all cases in
which there has been a copious draining away of the body fluids. In the
narcotic form of arsenical poisoning, the vessels of the brain have been
noted as congested, but this congestion is neither marked nor
pathognomonic. Among the rare pathological changes may be classed
glossitis, in which the whole tongue has swollen, and is found so large
as almost to fill the mouth. This has been explained, in one case, as
caused by solid arsenious acid having been left a little time in the
mouth before swallowing it. On the other hand, it has also been observed
when the poison has been absorbed from a cutaneous application. When
arsenic has been introduced into the vagina, the ordinary traces of
inflammatory action have been seen, and, even without direct contact, an
inflammation of the male and female sexual organs has been recorded,
extending so far as gangrene. As a rule, putrefaction is remarkably
retarded, and is especially slow in those organs which contain arsenic;
so that, if the poison has been swallowed, the stomach will retain its
form, and, even to a certain extent, its natural appearance, for an
indefinite period. In corpses long buried of persons dying from
arsenical poisoning, the ordinary process of decay gives place to a
saponification, and such bodies present a striking contrast to others
buried in the same graveyard. This retardation of putrefaction is what
might, _à priori_, be expected, for arsenic has been long in use as a
preservative of organic tissues.
§ 735. =Physiological Action of Arsenic.=--The older view with regard to
the essential action of arsenic was, without doubt, that the effects
were mainly local, and that death ensued from the corrosive action on
the stomach and other tissues--a view which is in its entirety no longer
accepted; nevertheless, it is perfectly true that arsenic has a
corrosive local action; it will raise blisters on the skin, will inflame
the tongue or mucous membranes with which it comes in contact; and, in
those rapid cases in which extensive lesions have been found in the
alimentary canal, it can hardly be denied that instances of death have
occurred more from the local than the constitutional action. In the vast
majority of cases, however, there is certainly insufficient local action
to account for death, and we must refer the lethal result to a more
profound and intimate effect on the nervous centres. The curious fact,
that, when arsenic is absorbed from a cutaneous surface or from a
wound, the mucous membrane of the stomach inflames, is explained by the
absorption of the arsenic into the blood and its separation by the
mucous membrane, in its passage exerting an irritant action. The
diarrhœa and hyperæmia of the internal abdominal organs have been
referred to a paralysis of the splanchnic nerves, but Esser considers
them due to an irritation of the ganglia in the intestinal walls. Binz
has advanced a new and original theory as to the action of arsenious
acid; he considers that the protoplasm of the cells of many tissues
possess the power of oxidising arsenious acid to arsenic acid, and this
arsenic acid is again, by the same agency, reduced to arsenious acid, in
this way, by the alternate oxidation and reduction of the arsenious
acid, the cells are decomposed, and a fatty degeneration takes place.
Thus arsenic causes fatty changes in the liver, kidney, and other cells
by a process analogous to the action of phosphorus. T. Araki[754] also
considers that both arsenic and phosphorus lessen oxidation, and points
out that lactic acid appears in the urine when either of these poisons
are taken, such acid being the result of insufficient oxidation. A
notable diminution of arterial pressure has been observed. In an
experiment by Hugo[755] ·03 grm. of As₂O₃ was injected intravenously,
the normal arterial pressure being 178 mm. Ten minutes after injection
the pressure sank to 47 mm.; in sixteen minutes it again rose to 127 mm.
Accumulative action of arsenic does not occur. Hebra has given, in skin
diseases, during many months, a total quantity of 12 grms. without evil
result.
[754] _Zeit. physiol. Chem._, xvii. 311-339.
[755] _Op. cit._
§ 736. =Elimination of Arsenic.=--Arsenic is separated especially by the
urine,[756] then through the bile, and by the perspiration. The eruption
often observed on the skin has been referred to the local action of
small quantities of arsenic in this way eliminated. It is found in the
urine first after from five to six hours, but the elimination from a
single dose is not finished till a period of from five to eight days; it
has often been looked for twelve days after taking it, but very seldom
found. According to Vitali, the arsenic in the urine is not free, but
probably displaces phosphorus in phospho-glyceric acid; possibly it may
also replace phosphorus in lecithin.
[756] An old experiment of Orfila’s has some practical bearings, and may
be cited here. A dog was treated by ·12 grm. of arsenious acid, and
supplied plentifully with liquid to drink; his urine, analysed from time
to time during ten days, gave abundant evidences of arsenic. On killing
the animal by hanging on the tenth day, no arsenic could be detected in
any of the organs of the body; it had been, as it were, washed out.
§ 737. =Antidote and Treatment.=--In any case in which there is
opportunity for _immediate_ treatment, ferric hydrate should be
administered as an antidote. Ferric hydrate converts the soluble
arsenious acid into the insoluble ferric arseniate, the ferric oxide
being reduced to ferrous oxide. It is necessary to use ferric hydrate
recently prepared, for if dried it changes into an oxyhydrate, or even
if kept under water the same change occurs, so that (according to the
experiments of Messrs. T. & H. Smith) after four months the power of the
moist mass is reduced to one-half, and after five months to one-fourth.
It is obvious that ferric hydrate is not in the true sense of the word
an antidote, for it will only act when it comes in contact with the
arsenious acid; and, when once the poison has been removed from the
stomach by absorption into the tissues, the administration of the
hydrate is absolutely useless. Ferric hydrate may be readily prepared by
adding strong ammonia to the solution or tincture of ferric chloride,
found in every medical man’s surgery and in every chemist’s shop, care
being taken to add no caustic excess of ammonia; the liquid need not be
filtered, but should be at once administered. With regard to other
methods of medical treatment, they are simply those suggested by the
symptoms and well-known effects of the poison. When absorbed, the
drinking of water in excess cannot but assist its elimination by the
kidneys.
§ 738. =Detection of Arsenic.=--The analyst may have to identify arsenic
in substance, in solution, in alloys, in wall-papers, in earth, and in
various animal, fatty, resinous, or other organic matters.
=Arsenious Acid in Substance.=--The general characters of arsenious acid
have been already described, and are themselves so marked as to be
unmistakable. The following are the most conclusive tests:--
(1) A small fragment placed in the subliming cell (p. 258), and heated
to about the temperature of 137·7° (286° F.), at once sublimes in the
form of an amorphous powder, if the upper glass disc is cool; but if
heated (as it should be) to nearly the same temperature as the lower,
characteristic crystals are obtained, remarkable for their brilliancy
and permanency, and almost always distinct and separate. The prevailing
form is the regular octahedron, but the rhombic dodecahedron, the
rectangular prism, superimposed crystals, half crystals, deep triangular
plates like tetrahedra, and irregular and confused forms, all
occasionally occur.
[Illustration]
(2) A beautiful and well-known test is that of Berzelius:--A small
hard-glass tube is taken, and the closed end drawn out to the size of a
knitting needle. Within the extreme point of this fine part is placed
the fragment (which may be no more than a milligramme) and a splinter of
charcoal, fine enough to enter freely the narrow part, as shown in the
figure. The portion of the tube containing the charcoal (_e_) is first
heated until it glows, and then the extreme end; if arsenic is present,
a mirror-like coating is easily obtained in the broader portion of the
tube (_d_). That this coating is really arsenical can be established by
the behaviour of metallic crusts of arsenic towards solvents (as given
at p. 557). The portion of the tube containing the crust may also be
broken up, put in a very short, wide test-tube (the mouth of which is
occupied by a circle of thin microscopic glass) and heated, when the
arsenic will sublime on to the glass disc, partly as a metal and partly
as crystalline arsenious acid.
(3) Arsenious acid, itself inodorous, when heated on coal, after mixing
it with moist oxalate of potash, evolves a peculiar garlic-like odour.
To this test oxide of antimony adulterated with arsenic will respond, if
there is only a thousandth part present. Simply projecting arsenious
acid on either red-hot charcoal or iron produces the same odour.
(4) A little bit of arsenious acid, heated in a matrass with two or
three times its weight of acetate of potash, evolves the unsupportable
odour of kakodyl.
=Arsenites and Arseniates=, mixed with oxalate of soda and heated in a
matrass, afford distinct mirrors, especially the arsenites of the earths
and silver; those of copper and iron are rather less distinct.
=Sulphides of Arsenic= are reduced by any of the processes described on
p. 573 _et seq._
=In Solution.=--An acid solution of arsenious acid gives, when treated
with SH₂, a canary-yellow precipitate, soluble in ammonia, carbonate of
ammonia, and bisulphite of potash, and also a metallic sublimate when
heated in a tube with the reducing agents in the manner described at p.
575. By these properties the sulphide is distinguished and, indeed,
separated from antimony, tin, and cadmium.
The sulphides of tin and cadmium are certainly also yellow, but the
latter is quite insoluble in ammonia, while the former gives no metallic
sublimate when heated with reducing substances.
The sulphide of antimony, again, is orange, and quite insoluble in
potassic bisulphite, and scarcely dissolves in ammonia.
A small piece of sodium amalgam placed in a test-tube or flask
containing an arsenic-holding liquid, or the liquid made alkaline with
soda or potash and a little bit of aluminium added, produces in a short
time arsine, which will blacken a piece of paper, soaked in nitrate of
silver, and inserted in the mouth of the flask. This is certainly the
most convenient test for arsenic. No antimoniuretted hydrogen
(_stibine_) is given off from an alkaline solution and no SH₂.
=Marsh’s Original Test for Arsenic= consisted in evolving nascent
hydrogen by zinc and sulphuric acid, and then adding the liquid to be
tested. The apparatus for Marsh’s test, in its simplest form, consists
of a flask provided with a cork conveying two tubes, one a funnel
reaching nearly to the bottom of the flask; the other, a delivery tube,
which is of some length, is provided with a chloride of calcium
bulb,[757] and towards the end is turned up at right angles, the end
being narrowed. By evolving hydrogen from zinc and sulphuric acid, and
then adding portions of the liquid through the funnel, arseniuretted
hydrogen in a dry state is driven along the leading tube, can be ignited
on its issue, and on depressing a piece of cold porcelain, a dark
metallic spot of arsenic is obtained.[758] Or, if any portion of the
tube be made red-hot, the metal is deposited in the same way as a ring.
The apparatus admits of much complication and variety. One of the most
useful additions is, perhaps, the interposition of a small gasometer.
This consists of a cylindrical glass vessel with entrance and exit
tubes, open at the bottom, immersed in water in a larger vessel, and
counterpoised by weights and rollers, exactly like the large gasometers
used at gasworks; the exit tube must have a stop-cock, and the gas must
pass over calcic chloride in order to dry it thoroughly.
[757] Otto recommends the first half of the drying tube connected with
the development flask to be filled with caustic potash, the latter half
with chloride of calcium (_Ausmittelung der Gifte_). Dragendorff
approves of this, but remarks that it should be used when arsenic alone
is searched for, since caustic potash decomposes stibine. The potash
fixes SH₂, and prevents the formation of chloride of arsenic; on the
other hand, it absorbs some little AsH₃.
[758] For identification of arsenical films, see p. 557.
M. Blondlot has observed[759] that if pure zinc, a weak solution of
arsenious acid, and a sulphuric acid containing nitric acid or nitrous
compounds, be mixed together, the arsenic passes into a solid hydrate,
which is deposited on the surface of the zinc; this is, however,
prevented by the addition of a little stannous chloride dissolved in
hydrochloric acid.
[759] Blondlot, “Transformation de l’arsenic en hydrure solide par
l’hydrogène aissant sous l’influence des composés nitreux.”--_Jour. de
Pharm. et de Chim._, 3e sér., t. xliv. p. 486.
The precautions to be observed in Marsh’s test are:--
(1) Absolute freedom of the reagents used from arsenic, antimony,[760]
and other impurities.
[760] With regard to purity of reagents, Sonnenschein states that he has
once found chlorate of potash contaminated with arsenic.--Sonnenschein,
_Gericht. Chemie_, p. 139.
(2) The sulphuric acid should be diluted with five times its weight of
water, and if freshly prepared should be cooled before use. Strong acid
must not be employed.[761]
[761] M. A. Gautier uses sulphuric acid diluted with five times its
weight of water; when the hydrogen has displaced the air, he adds to the
arsenical matter 45 grms. of this acid and 5 grms. of pure sulphuric
acid.--_Bull. de la Société Chim. de Paris_, 1875, t. xxiv.
(3) The fluid to be tested should be poured in little by little.
(4) Nitrous compounds, nitric acid, hydrochloric acid, chlorides, are
all more or less prejudicial.
(5) The gas should come off regularly in not too strong a stream, nor
out of too small an opening.
(6) The gas should pass through the red-hot tube at least one hour, if
no stain is at once detected.
(7) Towards the end of the operation, a solution of stannous chloride in
hydrochloric acid is to be added to the contents of the flask. This
addition precipitates any arsenic present in a finely divided state, in
which it is readily attacked by nascent hydrogen.[762]
[762] F. W. Schmidt, _Zeit. anorg. Chem._, i. 353-359.
The characteristics of the metallic stains which may occur either on
glass or porcelain in the use of Marsh’s test, may be noted as under:--
MIRROR OR CRUST OF ARSENIC MIRROR OR CRUST OF ANTIMONY
Is deposited at a little distance Is deposited close to the flame,
from the flame. and on both sides of it, and is
therefore notched.
An arsenical stain is in two The stain is tolerably homo-
portions, the one brownish, the geneous, and usually has a tin-
other a glittering black. like lustre.
On heating, it is rapidly Volatilisation very slow; no
volatilised as arsenious acid. crystalline sublimate obtainable.
On transmission of a stream of The same process applied in the
SH₂, whilst immediately behind the case of antimony produces the
stain a gentle heat is applied, orange or black sulphide; and on
the arsenic is changed to yellow passing dry ClH, chloride of
sulphide;[763] if dry ClH is now antimony volatilises without the
transmitted, the arsenical application of heat.
sulphide is unchanged.
Chloride of lime dissolves the Antimony not affected. Dissolves
arsenic completely. slowly but completely the
antimony stain.
Protochloride of tin has no action No precipitate with antimony.
on metallic arsenic.
The arsenic stain, dissolved in
_aqua regia_, or ClH and chlorate
of potash, and then treated with
tartaric acid, ammonia, and
magnesia mixture, gives a
precipitate of ammonia magnesian
arseniate.[764]
[763] It is desirable to dissolve away the free sulphur often deposited
with the arsenical sulphide by bisulphide of carbon.
[764] Schönbein has proposed ozone as an oxidiser of arsenical stains.
The substance containing the stain, together with a piece of moist
phosphorus, is placed under a shade, and left there for some time; the
oxidisation product is, of course, coloured yellow by SH₂ if it is
arsenious acid, orange if antimony. The vapour of iodine colours
metallic arsenic pale yellow, and later a brownish hue; on exposure to
the air it loses its colour. Iodine, on the other hand, gives with
antimony a carmelite brown, changing to orange.
An arsenical ring may be also treated as follows:--Precipitated zinc
sulphide is made into a paste with a little water, and introduced into
the end of the tube; the same end is then plunged into dilute sulphuric
acid, and the ring heated, when the arsenical sulphide will be
produced.
The mirror or crust of arsenic is usually described and weighed as being
composed of the pure metal, but J. W. Rettgers has investigated the
matter, and the following is an abstract of his results:--
There is no amorphous form of arsenic, the variety generally thus called
being crystalline. Two modifications can be distinguished: the one being
a hexagonal silver-white variety possessed of metallic lustre,
specifically heavier and less volatile than the second kind, which is
black in colour, crystallises apparently in the regular system, and
constitutes the true arsenic mirror. The former modification corresponds
to red hexagonal phosphorus (red phosphorus having been recently proved
by the author to be crystalline), and the latter to yellow phosphorus,
which crystallises in the regular system. Both modifications of arsenic
are perfectly opaque; deposits which are yellow or brown, and more or
less transparent, consist of the suboxide and hydride, As₂O and AsH. The
brown spot on porcelain produced by contact with a flame of
arseniuretted hydrogen is not a thin film of As, but one of the brown
solid hydride AsH, formed by the decomposition of AsH₃. This view is
confirmed by the fact that arsenic sublimed in an indifferent gas
(_e.g._, CO₂) is deposited in one or other of the modifications
described above, the brown transparent product being obtained only in
the presence of H or O. Moreover, pure arsenic is insoluble in all
solvents, whereas the film on porcelain (AsH) is soluble in many
solvents, including hydrocarbons of the benzene series (_e.g._, xylene),
warm methylene iodide, and hot caustic potash.
Hence quantitative results from weighing arsenical mirrors can never be
accurate, because the mirrors consist of mixtures of hydride and
suboxide.
=Reinsch’s Test.=--A piece of bright copper foil, boiled in an acid
liquid containing either arsenic or antimony, or both, becomes coated
with a dark deposit of antimony or arsenic, as the case may be. The
arsenical stain, according to Lippert, is a true alloy, consisting of 1
arsenic to 5 copper.[765] Properly applied, the copper will withdraw
every trace of arsenic or antimony from a solution. Dr. John Clark[766]
has lately introduced some improvements in Reinsch’s process. His
experiments have been directed to the means of proving the presence of
arsenic or antimony in the stain on the copper with greater certainty,
and at the same time estimating the amount when they occur together.
[765] _Journ. f. pract. Chem._, xiii. 168.
[766] _Journ. Chem. Soc._, June 1893, 886.
The material to be tested is boiled gently in a porcelain vessel with
dilute hydrochloric acid and a small strip of copper about 1 inch long
by ¼ inch broad, till the absence of arsenic or antimony has been
ascertained, or a coating has been produced. When the coating is
decided, the piece of copper is taken out, washed first with water, then
with a little alcohol to get rid of fatty matter, and finally with
water. It is then placed in a mixture of dilute caustic potash and
peroxide of hydrogen, and allowed to digest in the cold. At the same
time a second piece of copper is introduced into the material which has
given a deposit on the first piece, the washings of the first piece
being added, and the boiling continued.
The treatment of the first piece of copper by caustic potash and
peroxide of hydrogen dissolves any antimony or arsenic and restores the
copper to its original brightness; when this is accomplished, the second
piece of copper is taken out and replaced by the first, and this second
piece, if stained, is digested with potash, peroxide of hydrogen, and
washed as in the former case. The process is repeated until the slips of
copper cease to be stained in the slightest degree--until, in short, the
whole arsenic or antimony has been withdrawn.
The alkaline liquid contains the arsenic, as arsenate of potassium; the
antimony, if present, as antimonate; and the solution is also
contaminated by a little hydrated copper oxide; this latter separates on
boiling, and can be filtered off, and the filtrate is boiled down to a
small bulk. The liquid is washed into a small distillation-flask with
strong hydrochloric acid, ferrous chloride is added, the flask, fitted
with a safety tube, is connected with a condenser, and the arsenic
distilled into water. To obtain the last traces of arsenic it may be
necessary to distil it twice in this way, adding, each time, fresh
strong acid and distilling to dryness. The distillate is then tested for
arsenic by adding an equal bulk of saturated SH₂ water. The sulphide of
arsenic may be dealt with as described (p. 573).
The residue in the flask is now tested for antimony by saturating with
SH₂; should antimony be present, the precipitate by SH₂ will probably be
dark coloured, because of a small quantity of copper. The precipitate is
collected, dissolved in dilute caustic soda, boiled, filtered to remove
copper sulphide, the filtrate acidified by hydrochloric acid, and
sulphuretted hydrogen water added. If antimony was present, this time
the precipitate will be of an orange colour, and may be dealt with as
described (p. 589).
The test experiments with regard to this combined process appear
satisfactory.
§ 739. =Arsenic in Glycerin.=--Arsenic has been frequently found in
commercial glycerin, the quantity varying from 0·1 to 1 mgrm. in 100
c.c. The best method to detect the presence of arsenic in glycerin is as
follows:--A mixture of 5 c.c. of hydrochloric acid (1 : 7) and 1 grm. of
pure zinc is placed in a long test-tube, the mouth of which is covered
with a disc of filter-paper previously moistened with one or two drops
of mercuric chloride solution, and dried. If arsenic is present, a
yellow stain is produced upon the filter-paper within fifteen minutes,
and it subsequently becomes darker.[767]
[767] “Arsenic in Glycerin,” by Dr. H. B. H. Paul and A. J. Cownley,
_Pharm. Journ._, Feb. 24, 1894.
§ 740. =Arsenic in Organic Matters.=--Orfila and the older school of
chemists took the greatest care, in searching for arsenic, to destroy
the last trace of organic matter. Orfila’s practice was to chop up the
substance and make it into a paste with 400 to 700 grms. of water; to
this ·010 grm. KHO in alcohol was added, and ·020 grm. of potassic
nitrate. The substances were heated up to from 80° to 90° for some time,
until they were pretty well dissolved; the organic matter was then burnt
off in a Hessian crucible heated to redness, on which small quantities
of the matters were placed at a time. When the whole had thus been
submitted to red heat, the melted mass was run into an almost red-hot
porcelain basin, and allowed to cool. Afterwards, it was again heated
with concentrated sulphuric acid, until all nitric and nitrous fumes
were dissipated; on dissolving and filtering in water, the liquid was
introduced into a Marsh’s apparatus. Orfila never seems to have failed
in detecting arsenic by this process. For an organ like the liver, he
considered that 100 grms. of potash and 86 of strong sulphuric acid were
necessary in order to destroy the organic matters.
The liability of the various reagents used to impurity, and the
probability of loss in these operations, have tended to discredit
destruction of the organic matter by a red heat, and chemists generally
have preferred to oxidise animal matters by a moist process. The organic
substance is divided finely and digested with dilute hydrochloric acid,
and from time to time crystals of potassic chlorate are thrown in until
all the fluid is very thin and capable of passing through a filter. The
filtrate must now be submitted to the prolonged action of sulphuretted
hydrogen,[768] and the sulphide of arsenic separated from free sulphur
by dissolving in sodic sulphide. After filtering, the arsenic sulphide
may be again thrown down by the addition of hydrochloric acid,
collected on a filter, and still further purified by solution in ammonic
carbonate; once more precipitated by hydrochloric acid, and lastly
identified by conversion into magnesia pyro-arseniate (see p. 572). The
above process is a general and safe way of detecting arsenic in almost
any organic tissue, but the author prefers the distillation process
described p. 575 _et seq._
[768] The SH₂ should be washed by passing it through two or more washing
bottles supplied with warm dilute HCl--a few samples of sulphide of iron
give off an arseniferous gas, so that this precaution is necessary.
From ordinary pills, quack extracts, and similar preparations, drying,
powdering, and exhaustion with boiling dilute HCl, will remove the whole
of the arsenic, if in a soluble state.
Oils and matters consisting almost entirely of fat, suspected of
containing arsenic, are gently heated, and allowed to deposit any
insoluble matter they may contain; the oil is then decanted, and, if
necessary, filtered from any deposit; saponified by alcoholic potash,
the soap decomposed by HCl, the fatty acids separated, and the arsenic
looked for both in the first deposit and in the solution, now fairly
free from fat, and easy to treat.
In searching for arsenic in the fluids or tissues of the body, the
analyst is generally at the mercy of the pathologist, and sometimes the
work of the chemist leads to a negative result, solely from not having
the proper organ sent to him.[769]
[769] For example, in cases of poisoning by external application, more
than once merely the empty stomach and a piece of intestine have been
forwarded to the writer.
Brodie long ago stated that when arsenious acid had been given in
solution to any animal capable of vomiting, no arsenic could be detected
in the stomach; this statement is too absolute, but in the majority of
cases true.
In all cases the chemist should have portions of the brain, spinal cord,
liver, kidneys, lungs, and muscular tissue, as well as the stomach and
its contents.
According to the experiments of Scolosuboff,[770] arsenic is generally
greatest in the marrow, then in the brain, next in the liver, and least
in the muscles, and the following may be taken as a fairly accurate
statement of the relative proportion in which arsenic is likely to be
found in the body, 100 grms. being taken of each:--
[770] _Bull. Soc. Chim._ (2), xxiv. p. 124.
Muscles, 1
Liver, 10·8
Brain, 36·5
Spinal Marrow, 37·3
But Ludwig’s[771] experiments and conclusions are entirely opposed to
this, since both in acute and chronic cases he found as follows (per
cent. As₂O₃):--
[771] _Ueber die Verhaltung des Arsens im thierischen Organismus nach
Einverleibung von Arseniger Säure. Med. Jahrbuch_, 1880.
Brain, ·0002
Liver, ·001
Kidney, ·0004
Muscle, ·00025
So that he detected in the liver five times more than in the brain. M.
P. Hamberg has also confirmed the fact, that more is found in the liver
and kidneys than in the nervous tissues.
Chittenden[772] found in a body the following quantities of arsenic
estimated as arsenious acid:--
[772] _American Chemical Journal_, v. 8.
Grain.
Stomach and gullet, 0·158
Intestines, 0·314
Liver, 0·218
Kidney, 0·029
Lungs and spleen, 0·172
Heart, 0·112
Brain, 0·075
Diaphragm, 0·010
The whole arsenic present was estimated as equal to 3·1 grains of
arsenious acid, viz., 2·628 grains absorbed, and 0·472 unabsorbed; of
the absorbed portion 8·3 per cent. was found in the liver.
With regard to the preliminary treatment of the stomach and fluids
submitted to the analyst, the careful noting of appearances, the
decantation, washing, and examination[773] (microscopical and chemical)
of any deposit, are precautions so obviously dictated by common sense,
that they need only be alluded to in passing. Of some considerable
moment is the question which may be put to the analyst in court, in
reference to the possible entrance of arsenic into the living body, by
accidental and, so to speak, _subtle_ means. Such are the inhaling of
the fumes from the burning of arsenical candles,[774] and of emanations
from papers (see p. 541),[775] as well as the possible entrance of
arsenic into the body after death from various sources, such as
arsenical earth, &c.[776]
[773] From some observations of Fresenius in a recent number of the
_Zeitschrift f. anal. Chem._, it would seem necessary to test all glass
vessels used; for it is difficult at present to purchase arsenic-free
glass.
[774] See a case of poisoning (non-fatal) of a lady by the use of
arsenical candles, _Med. Times and Gazette_, vol. iii., 1876, p. 367.
[775] To solve this question, it has been at times considered necessary
to analyse an extraordinary number of things. In the “affaire Danval”
(_Journ. d’Hygiène_, 2e sér., No. 108, July 1878), more than sixty
different articles, comprising drugs, drinks, perfumes, bed-curtains,
wall-paper, and other matters, were submitted to the experts.
[776] The following important case is related by Sonnenschein:--
Nicholas Nobel and his wife, Jerome, were buried two metres from each
other in the churchyard at Spinal, the earth of which notoriously
contained arsenic. A suspicion of poisoning arose. The bodies were
exhumed, and arsenic was found in the stomach and intestines of Nobel,
but not the slightest trace in the corpse of the wife. The remains of
the bodies were reinterred, and after six months, on a fresh suspicion
of poisoning arising, again exhumed. The corpse of the woman had been
put naked in the moist earth during a heavy shower, but this time also
no arsenic was detected in it.
§ 741. =Imbibition of Arsenic after Death.=--The arguments which are
likely to be used, in favour of a corpse having become arsenical may be
gathered from a case related by Sonnenschein:--Certain bodies were
exhumed in two churchyards; the evidence went to show that they had been
poisoned by arsenic, and this substance was actually found in the
bodies, while at the same time it was discovered to exist also in traces
in the earth of the churchyard. The theory for the defence was, that
although the arsenic in the earth was in an insoluble state, yet that it
might combine with lime as an arsenite of lime; this arsenite would
become soluble by the action of carbonic acid set free by vegetation,
and filter down to the corpse. Sonnenschein suspended a quantity of this
earth in water, and passed CO₂ through it for twelve hours; on
filtering, the liquid gave no evidence of arsenic. A similar result was
obtained when an artificial mixture of 1 grm. of arsenious acid and 1
pound of earth were submitted to the same process.
The fact would appear to stand thus: oxide of iron in ordinary earth
retains arsenic, and requires treatment with a concentrated acid to
dissolve it. It therefore follows that, if a defence of arsenical earth
is likely to be set up, and the analyst finds that by mere extraction of
the tissues by _water_ he can detect arsenic, the defence is in all
probability unsound. The expert should, of course, deal with this
question on its merits, and without prejudice. According to
Eulenberg,[777] in arsenical earth--if, after having been crushed and
washed, it lies for some time exposed to the disintegrating action of
the air--soluble arsenical salts are formed, which may find their way
into brooks and supplies of drinking water. We may infer that it is
hardly probable (except under very peculiar circumstances) for a corpse
to be contaminated internally with an estimable quantity of arsenic from
the traces of arsenic met with in a few churchyards.
[777] _Gewerbe Hygiene_, p. 234.
It occasionally happens that an exhumation is ordered a very long time
after death, when no organs or parts (save the bones) are to be
distinguished. In the case of a man long dead, the widow confessing that
she had administered poison, the bones were analysed by Sonnenschein,
and a small quantity of arsenic found. Conièrbe and Orfila have both
asserted that arsenic is a normal constituent of the bones--a statement
which has been repeatedly disproved. Sonnenschein relates:[778]--“I
procured from a churchyard of this place (Berlin) the remnants of the
body of a person killed twenty-five years previously, and investigated
several others in a similar way, without finding the least trace of
arsenic. Similar experiments in great number were repeated in my
laboratory, but in no case was arsenic recognised.” The opinion of the
expert, should he find arsenic in the bones, must be formed from the
amount discovered, and other circumstances.
[778] _Gerichtl. Chem._, p. 212.
A difficult case on which to form an opinion is one recorded by William
P. Mason,[779] as follows:--
[779] _Chem. News_, Feb. 23, 1894.
The deceased, a farmer, bachelor, sixty-five years of age, and in
good health, was taken violently sick shortly after breakfast, with
vomiting and distress in the stomach. Although a physician was
summoned, the symptoms increased in severity, and a little after
midnight death ensued. The funeral took place three days later.
Certain very damaging pieces of circumstantial evidence having been
collected, the housekeeper was arrested on the charge of murder, it
having been shown, among other things, that on the day preceding the
death she had purchased an ounce of white arsenic.
Thirty-five days after death (from March 20 to April 25) the body
was exhumed, and found in a state of remarkable preservation, and
free from cadaveric smell. The stomach presented evidences of
inflammation.
Portions sent for analysis were the stomach, portion of intestine,
portion of liver, one kidney, and the heart. Arsenic was found in
all these parts. White octahedral crystals were found in the
contents of the stomach, which on separation gave arsenical
reaction.
The arsenic found was:--
Stomach and intestine, 0·2376 grm.
Liver and kidney, 0·0032 „
Heart, 0·0007 „
------
Total as metallic arsenic, 0·2415 „
The amount of arsenic recovered and produced in court was in
quantity sufficient to produce death. Some time after the analytical
report was made to the coroner, it was learned that an embalming
fluid, highly arsenical in character, had been used upon the body by
the undertaker at the time of preparation for burial. No injection
of this embalming fluid was practised, but cloths wrung out in the
fluid were laid upon the face and chest, and were kept constantly
wet therewith during a period of many hours. In all about two quarts
of embalming fluid were so used. Its composition appeared to be a
strongly acidified solution of sodium arsenite and zinc sulphate.
Only the arsenic and zinc were determined quantitatively, and they
were found to be, zinc (metallic), 1·978 per cent., and arsenic
(metallic), 1·365 per cent. by weight. An amount of this fluid
measuring 15·7 c.c. would thus contain a weight of arsenic equal to
that actually recovered from the body.
Extended medical testimony was offered by the prosecution, tending
to show that, under the given circumstances, no fluid of any kind
could have reached the stomach through the nose or mouth after
death, thus anticipating what the defence afterwards claimed, that
the undertaker was responsible for the arsenic discovered in the
remains.
In order to gather further light upon the possibility of cadaveric
imbibition of embalming fluid through the unbroken skin, test was
made for zinc in the heart and stomach, and distinct traces of the
metal were found in each instance. That at least a portion of the
arsenic found in the body was due to _post-mortem_ causes was thus
distinctly proven. A weighed portion (62 grms.) of the stomach and
contents was then most carefully analysed quantitatively for both
zinc and arsenic with the following results:--Arsenic, 0·0648 grm.,
and zinc, 0·0079 grm. Bearing in mind the relative quantities of the
two metals in the embalming fluid, it will be seen that the arsenic
found in the 62 grms. of the stomach was nearly twelve times larger
than it should have been to have balanced the zinc which was also
present. This fact, together with the discovery of crystals of white
arsenic in the stomach, constituted the case for the prosecution, so
far as the chemical evidence was concerned.
The defence made an unsuccessful effort to show that the crystals of
the tri-oxide originated from the spontaneous evaporation of the
embalming fluid. The prosecution met this point by proving that such
fluid had been abundantly experimented upon by exposure to a very
low temperature during an interval of several months, and also by
spontaneous evaporation with a view of testing that very question,
and that the results had in every case been negative. Special
importance was given these experiments, because of the well-known
separation of octahedral crystals during the spontaneous evaporation
of a hydrochloric acid solution of the white oxide, it having also
appeared that, in the manufacture of the embalming fluid, the
arsenic was used as white arsenic.
A very strong point was finally raised for the defence by the
inability of the expert on the side of the prosecution to state
positively whether or not an embalming fluid of the above
composition would diffuse as a whole through dead tissue, or its
several parts would be imbibed at different rates of speed, the zinc
portion becoming arrested by albuminoid material and being therefore
outstripped by the arsenic, or _vice versa_. The prisoner was
ultimately acquitted.
In a case which occurred in the Western States of America, there was
good reason for believing that arsenic had been introduced into the
corpse of a man _after_ his decease. With regard to the imbibition of
arsenic thus introduced, Orfila[780] says:--“I have often introduced
into the stomach (as well as the rectum) of the corpses of men and dogs
2 to 3 grms. of arsenious acid, dissolved in from 400 to 500 grms. of
water, and have examined the different viscera at the end of eight, ten,
or twenty days. Constantly I have recognised the effects of cadaveric
imbibition. Sections of the liver or other organs which touch the
digestive canal, carefully cut and analysed, furnished arsenic, which
could not be obtained sensibly (or not at all) from sections which had
not been in contact with this canal. If the corpse remained long on the
back after arsenious acid had been introduced into the stomach, I could
obtain this metal from the left half of the diaphragm and from the
inferior lobe of the left lung, whilst I did not obtain it from other
portions of the diaphragm nor from the right lung.” Dr. Reece has also
made some experiments on the imbibition of arsenic after death. He
injected solutions of arsenious acid into the stomach of various
warm-blooded animals, and found at various periods arsenic, not alone in
the intestinal canal, but also in the spleen, liver, and kidneys.
[780] _Op. cit._, t. i. p. 309.
§ 742. =Analysis of Wall-Paper for Arsenic.=--The separation of arsenic
from paper admits of great variety of manipulation. A quick special
method is as follows:--The paper is saturated with chlorate of potash
solution, dried, set on fire in a suitable plate, and instantly covered
with a bell-glass. The ash is collected, pulverised, and exhausted with
cold water, which has previously thoroughly cleansed the plate and
bell-glass; the arsenic in combination with the potash is dissolved,
whilst oxides of chromium, copper, aluminium, tin, and lead remain in
the insoluble portion.[781]
[781] Kapferschlaeger: _Rev. Universelle des Mines_, 1876.
Fresenius and Hintz[782] have elaborated a method for the examination of
wall-papers, fabrics, yarns, and similar substances, which, provided the
reagents are pure, is accurate and easy. Twenty-five grms. of the
substance are placed in a half-litre distilling flask or retort, and 250
c.c. of HCl, specific gravity 1·19, added; after digestion for an hour,
5 c.c. of a saturated solution of ferrous chloride are added, and the
liquid slowly distilled until frothing stops any farther distillation. A
further quantity of 100 c.c. HCl is then added, and distilled over. The
receiver, in each case, contains water, and must be kept cool. The
united distillates are diluted to 800 c.c. and saturated with SH₂. The
arsenious sulphide is collected on an asbestos filter. After partial
washing, it is heated with bromine in HCl of 1·9 specific gravity, and
the solution again distilled with ferrous chloride. The distillate, on
now being treated with SH₂, gives arsenious sulphide free from organic
matter.
[782] _Zeit. anal. Chem._, xxvii. 179-182.
§ 743. =Estimation of Arsenic.=--Most of the methods for the
quantitative determination of arsenic are also excellent tests for its
presence. It may be regarded, indeed, as an axiom in legal chemistry,
that the precise amount of every substance detected, if it can be
weighed or estimated by any process whatever, should be accurately
stated. Indefinite expressions, such as “a small quantity was found,”
“traces were detected,” &c., are most objectionable. The more perfect of
the methods of evolving arsenic can be made quantitative. For example,
the galvanic process introduced by Bloxam may be utilised as follows:--A
fractional part of the arsenical solution is taken for the experiment;
the bottom of a narrow-necked bottle of about 100 c.c. capacity is
removed, and replaced by a piece of vegetable parchment. The neck of the
bottle carries a cork, which is pierced by (1) a platinum wire, which is
attached to a platinum electrode; (2) a short tube, bent at right
angles, and connected by piping with a longer tube, which has also a
rectangular bend, and dips into a solution of silver nitrate; (3) an
ordinary funnel-tube, reaching nearly to the bottom. The bottle is
placed in a beaker of such a size as to leave a small interval between
the two, and the whole apparatus stands in a large vessel of cold water.
Dilute sulphuric acid is now put into the bottle, and also into the
beaker, so that the fluid reaches exactly the same level in each. The
positive platinum electrode of a battery of six of Grove’s cells, or
other efficient combination, is immersed in the liquid outside the
bottle, connection with the negative plate is established, and hydrogen
very soon comes off, and passes over into the nitrate of silver
solution. When all the air is expelled, a portion of the rectangular
tube is heated to redness, and if there is no stain nor any reduction of
the silver, the acid is pure. If the gas is passed for a long time into
the silver solution, the silver will be reduced to some extent by the
hydrogen, although arsenic-free;[783] so that it is better to rely upon
the metallic ring or stain, which is certain to be formed on heating a
portion of the tube red-hot, and keeping it at that temperature for _at
least ten minutes_. The liquid is then passed through the funnel in
successive portions; if arsenic is present, there will be a decided
metallic ring on heating the tube as before, and if antimony is present,
there will also be a stain; the distinctions between these stains have
been described at p. 557.
[783] Nitrate of silver solution is reduced by H₂, CH₃, PH₃, and SbH₃;
hence it is absolutely necessary in any qualitative examination to prove
that arsenious acid has actually been produced in the silver solution.
The tube is kept red-hot until the stain is very distinct; then the
source of heat is removed, and the gas allowed to bubble through the
argentic nitrate solution, which it decomposes, as before detailed (p.
526). This process is continued until, on placing the delivery tube in a
sample of clear nitrate of silver solution, there is no darkening of
colour. In certain cases this may take a long time, but the apparatus,
once set to work, requires little superintendence. At the conclusion,
the whole of the arsenic is separated,--part is in the silver solution
as arsenious acid, part in the tube as a ring of metallic arsenic. The
portion of the tube containing the metallic arsenic should be cut off
with a file and weighed, the arsenic then removed and re-weighed; the
loss is the metal approximately. Or, the weight of the film may be
estimated by having a set of similar deposits of known weight or
quantities, in tubes exactly corresponding to those used in the
analysis, and comparing or matching them.
The arsenious acid in the nitrate of silver may be dealt with in several
ways. The equation given (p. 526) shows clearly that pure arsine, passed
into nitrate of silver solution, decomposes it in such a manner that, if
either the silver deposited or the free acid is estimated, the quantity
of arsenic can from such data be deduced. In operating on organic
liquids, ammonia and other products may be given off, rendering either
of the indirect processes inadvisable. A very convenient method,
applicable in many cases, is to throw out the silver by hydrochloric
acid, alkalise the filtrate by bicarbonate of soda, and titrate with
iodine solution. The latter is made by dissolving exactly 12·7 grms. of
pure dry iodine by the aid of 18 grms. of potassic iodide in one litre
of water, observing that the solution must take place in the cold,
without the application of heat. The principle of the titration is, that
arsenious acid, in the presence of water and free alkali, is converted
into arsenic acid--
As₂O₃ + 4I + 2Na₂O = As₂O₅ + 4NaI.
The end of the reaction is known by adding a little starch-paste to the
solution; as soon as a blue colour appears, the process is finished.
Another convenient way by which (in very dilute solutions of arsenious
acid) the arsenic may be determined, is a colorimetric method, which
depends on the fact that sulphuretted hydrogen, when arsenious acid is
present in small quantity, produces no precipitate at first, but a
yellow colour, proportionate to the amount of arsenic present. The
silver solution containing arsenious acid is freed from silver by
hydrochloric acid; a measured quantity of saturated SH₂ water is added
to a fractional and, if necessary, diluted portion, in a Nessler
cylinder or colorimetric apparatus, and the colour produced exactly
imitated, by the aid of a dilute solution of arsenious acid, added from
a burette to a similar quantity of SH₂ water in another cylinder, the
fluid being acidified with HCl.