Chapter XXV: Part V: More or Less Volatile Poisonous Substances Capable of Being (5)

Casper has rightly recommended the head to be opened and examined first, so as to detect the odour, if present, in the brain. The abdominal and chest cavities usually possess a putrefactive smell, but the brain is longer conserved, so that, if this course be adopted, there is a greater probability of detecting the odour.

The stomach in poisoning by hydric cyanide is not inflamed, but if alcohol has been taken at the same time, or previously, there may be more or less redness.

In poisoning by potassic cyanide, the appearances are mainly the same as those just detailed, with, it may be, the addition of caustic local action. I have, however, seen, in the case of a gentleman who drank accidentally a considerable dose of potassic cyanide just after a full meal, not the slightest trace of any redness, still less of corrosion. Here the contents of the stomach protected the mucous membrane, or possibly the larger amount of acid poured out during digestion sufficiently neutralised the alkali. Potassic cyanide, in very strong solution, may cause erosions of the lips, and the caustic effect may be traced in the mouth, throat, gullet, to the stomach and duodenum; but this is unusual, and the local effects are, as a rule, confined to the stomach and duodenum. The mucous membrane is coloured blood-red, reacts strongly alkaline,[250] is swollen, and it may be even ulcerated. The upper layers of the epithelium are also often dyed with the colouring-matter of the blood, which has been dissolved out by the cyanide. This last change is a _post-mortem_ effect, and can be imitated by digesting the mucous membrane of a healthy stomach in a solution of cyanide. The intensity of these changes are, of course, entirely dependent on the dose and emptiness of the stomach. If the dose is so small as just to destroy life, there may be but little redness or swelling of the stomach, although empty at the time of taking the poison. In those cases in which there has been vomiting, and a part of the vomit has been drawn into the air-passages, there may be also inflammatory changes in the larynx. If essence of almonds has been swallowed, the same slight inflammation may be seen which has been observed with other essential oils, but no erosion, no strong alkaline reaction, nor anything approaching the effects of the caustic cyanide.

[250] The following case came under my own observation:--A stout woman, 35 years of age, the wife of a French polisher, drank, in a fit of rage, a solution of cyanide of potassium. It was estimated that about 15 grains of the solid substance were swallowed. She died within an hour. The face was flushed, the body not decomposed; the mouth smelt strongly of cyanide; the stomach had about an ounce of bloody fluid in it, and was in a most intense state of congestion. There was commencing fatty degeneration of the liver, the kidneys were flabby, and the capsule adherent. The contents of the stomach showed cyanide of potassium, and the blood was very fluid. The woman was known to be of intemperate habits.

In poisoning by bitter almonds no inflammatory change in the mucous membrane of the coats of the stomach would be anticipated, yet in one recorded case there seems to have been an eroded and inflamed patch.

§ 265. =Tests for Hydrocyanic Acid and Cyanide of Potassium.=--(1.) The addition of silver nitrate to a solution containing prussic acid, or a soluble cyanide,[251] produces a precipitate of argentic cyanide. 100 parts of argentic cyanide are composed of 80·60 Ag and 19·4 CN, equivalent to 20·1 HCN. It is a white anhydrous precipitate, soluble either in ammonia or in a solution of cyanide of potassium. It is soluble in hot dilute nitric acid, but separates on cooling. A particle of silver cyanide, moistened with strong ammonia, develops needles; silver chloride treated similarly, octahedral crystals. It is insoluble in water. Upon ignition it is decomposed into CN and metallic silver, mixed with a little paracyanide of silver.

[251] In the case of testing in this way for the alkaline cyanides, the solution must contain a little free nitric acid.

A very neat process for the identification of cyanide of silver is the following:--Place the perfectly dry cyanide in a closed or sealed tube, containing a few crystals of iodine. On heating slightly, iodide of cyanogen is sublimed in beautiful needles. These crystals again may be dissolved in a dilute solution of potash, a little ferrous sulphate added, and hydrochloric acid, and in this way Prussian blue produced. If the quantity to be tested is small, the vapour of the acid may be evolved in a very short test-tube, the mouth of which is closed by the ordinary thin discs of microscopic glass, the under surface of which is moistened with a solution of nitrate of silver; the resulting crystals of silver cyanide are very characteristic, and readily identified by the microscope.

(2.) If, instead of silver nitrate, the disc be moistened with a solution of sulphate of iron (to which has been added a little potash), and exposed to the vapour a short time, and then some dilute hydrochloric acid added, the moistened surface first becomes yellow, then green, lastly, and permanently, blue. No other blue compound of iron (with the exception of Prussian blue) is insoluble in dilute hydrochloric acid.

(3.) A third, and perhaps the most delicate of all, is the so-called sulphur test. A yellow sulphide of ammonium, containing free sulphur, is prepared by saturating ammonia by SH₂, first suspending in the fluid a little finely-precipitated sulphur (or an old, ill-preserved solution of sulphide of ammonium may be used). Two watch-glasses are now taken; in the one the fluid containing prussic acid is put, and the second (previously moistened with the sulphide of ammonium described) is inverted over it. The glasses are conveniently placed for a few minutes in the water-oven; the upper one is then removed, the moist surface evaporated to dryness in the water-bath, a little water added, and then a small drop of solution of chloride of iron. If hydrocyanic acid is present, the sulphocyanide of iron will be formed of a striking blood-red colour.

(4.) The reaction usually called Schönbein’s, or Pagenstecher and Schönbein’s[252] (but long known,[253] and used before the publication of their paper), consists of guaiacum paper, moistened with a very dilute solution of sulphate of copper (1 : 2000). This becomes blue if exposed to the vapour of hydrocyanic acid. Unfortunately, the same reaction is produced by ammonia, ozone, nitric acid, hypochlorous acid, iodine, bromine, chromate of potash, and other oxidising agents, so that its usefulness is greatly restricted.

[252] _Neues Repert. de Pharm._, 18, 356.

[253] This reaction (with tincture of guaiacum and copper) has been long known. “I remember a pharmaceutist, who attended my father’s laboratory, showing me this test in 1828 or 1829.”--Mohr’s _Toxicologie_, p. 92.

(5.) A very delicate test for prussic acid is as follows:--About one-half centigrm. of ammonia, ferrous sulphate (or other pure ferrous salt), and the same quantity of uranic nitrate, are dissolved in 50 c.c. of water, and 1 c.c. of this test-liquid is placed in a porcelain dish. On now adding a drop of a liquid containing the smallest quantity of prussic acid, a grey-purple colour, or a distinct purple precipitate is produced.[254]

[254] M. Carey Lea, _Amer. Journ. of Science_ [3], ix. pp. 121-123; _J. C. Society_, 1876, vol. i. p. 112.

(6.) A hot solution of potassic cyanide, mixed with picric acid, assumes a blood-red colour, due to the formation of picro-cyanic acid. Free HCN does not give this reaction, and therefore must first be neutralised by an alkali.

(7.) =Schönbein’s Test.=--To a few drops of defibrinated ox-blood are added a few drops of the carefully-neutralised distillate supposed to contain prussic acid, and then a little neutral peroxide of hydrogen is added. If the distillate contains no prussic acid, then the mixture becomes of a bright pure red and froths strongly; if, on the other hand, a trace of prussic acid be present, the liquid becomes brown and does not froth, or only slightly does so.

(8.) =Kobert’s Test.=--A 1-4 per cent. solution of blood, to which a trace of ferridcyanide of potassium is added, is prepared, and the neutralised distillate added to this solution. If hydric cyanide be present, then the liquid becomes of a bright red colour, and, examined spectroscopically, instead of the spectrum of methæmoglobin, will be seen the spectrum of cyanmethæmoglobin. Kobert proposes to examine the blood of the poisoned, for the purpose of diagnosis, during life. A drop of blood from a healthy person, and a drop of blood from the patient, are examined side by side, according to the process just given.

§ 266. =Separation of Hydric Cyanide or Potassic Cyanide from Organic Matters, such as the Contents of the Stomach, &c.=--It is very necessary, before specially searching for hydric cyanide in the contents of the stomach, to be able to say, by careful and methodical examination, whether there are or are not any fragments of bitter almonds, of apples, peaches, or other substance likely to produce hydric cyanide. If potassic cyanide has been taken, simple distillation will always reveal its presence, because it is found partly decomposed into hydric cyanide by the action of the gastric acids. Nevertheless, an acid should always be added, and if, as in the routine process given at p. 48, there is reasonable doubt for suspecting that there will be no cyanide present, it will be best to add tartaric acid (for this organic acid will in no way interfere with subsequent operations), and distil, as recommended, in a vacuum. If, however, from the odour and from the history of the case, it is pretty sure to be a case of poisoning by hydric or potassic cyanide, then the substances, if fluid, are at once placed in a retort or flask, and acidified with a suitable quantity of sulphuric acid, or if the tissues or other solid matters are under examination, they are finely divided, or pulped, and distilled, after acidifying with sulphuric acid as before. It may be well here, as a caution, to remark that the analyst must not commit the unpardonable error of first producing a cyanide by reagents acting on animal matters, and then detecting as a poison the cyanide thus manufactured. If, for example, a healthy liver is carbonised by nitric acid, saturated with potash, and then burnt up, cyanide of potassium is always one of the products; and, indeed, the ashes of a great variety of nitrogenous organic substances may contain cyanides--cyanides not pre-existing, but manufactured by combination. By the action of nitric acid even on sugar,[255] hydric cyanide is produced.

[255] _Chemical News_, 68, p. 75.

The old method of distillation was to distil by the gentle heat of a water-bath, receiving the distillate in a little weak potash water, and not prolonging the process beyond a few hours. The experiments of Sokoloff, however, throw a grave doubt on the suitability of this simple method for quantitative results.

N. Sokoloff[256] recommends the animal substances to be treated by water strongly acidified with hydric sulphate, and then to be distilled in the water-bath for from two to three days; or to be distilled for twenty-four hours, by the aid of an oil-bath, at a high temperature. He gives the following example of quantitative analysis by the old process of merely distilling for a few hours, and by the new:--

[256] _Ber. d. deutsch. chem. Gesellsch._, Berlin, ix. p. 1023.

=Old Process.=--(1.) Body of a hound--age, 2 years; weight, 5180 grms.; dose administered, 57 mgrms. HCN; death in fifteen minutes. After five days there was found in the saliva 0·6 mgrm., stomach 3·2 mgrms., in the rest of the intestines 2·6 mgrms., in the muscles 4·1--total, 10·5.

(2.) Weight of body, 4000 grms.; dose given, 38 mgrms.; death in eleven minutes. After fifteen days, in the saliva 0·8, in the stomach 7·2, in the rest of the intestines 2·2, in the muscles 3·2--total, 13·4.

=New Process.=--Weight of body, 5700 grams; dose, 57 mgrms.; death in twenty-four minutes. After fifteen days, in the saliva 1·1 mgrm., in the stomach 2·6, in the rest of the intestines 9·6, in the muscles 31·9, and in the whole, 45·2 mgrms. Duration of process, thirteen hours.

From a second hound, weighing 6800 grms.; dose, 67 mgrms.; 25·1 mgrms. were separated three days after death.

From a third hound, weighing 5920 grms.; dose, 98 mgrms.; after forty days, by distillation on a sand-bath, there were separated 2·8 mgrms. from the saliva, 4·8 from the stomach, 16·8 from the intestines, 23·6 from the muscles--total, 48 mgrms.

It would also appear that he has separated 51·2 mgrms. of anhydrous acid from the corpse of a dog which had been poisoned by 57 mgrms. of acid, and buried sixty days.[257]

[257] Without wishing to discredit the statements of M. Sokoloff, we may point out that a loss of half-a-dozen mgrms. only appears rather extraordinary.

From another canine corpse, three days laid in an oven, and left for twenty-seven days at the ordinary temperature, 5·1 mgrms. were recovered out of a fatal dose of 38 mgrms.

The estimation was in each case performed by titrating the distillate with argentic nitrate, the sulphur compounds having been previously got rid of by saturating the distillate with KHO, and precipitating by lead acetate.

Venturoli[258] has, on the contrary, got good quantitative results without distillation at all. A current of pure hydrogen gas is passed through the liquid to be tested and the gas finally made to bubble through silver nitrate. He states that the whole of the hydric cyanide present is carried over in an hour. Metallic cyanides must be decomposed by sulphuric acid or tartaric acid. Mercury cyanide must be decomposed with SH₂, the solution acidified with tartaric acid, neutralised with freshly precipitated calcic carbonate to fix any ferro- or ferri-cyanides present, and hydrogen passed in and the issuing gases led first through a solution of bismuth nitrate to remove SH₂ and then into the silver solution.

[258] L’Orosi. xv. 85-88.

§ 267. =How long after Death can Hydric or Potassic Cyanides be Detected?=--Sokoloff appears to have separated prussic acid from the body of hounds at very long periods after death--in one case sixty days. Dragendorff recognised potassic cyanide in the stomach of a hound after it had been four weeks in his laboratory,[259] and in man eight days after burial. Casper also, in his 211th case, states that more than 18 mgrms. of anhydrous prussic acid were obtained from a corpse eight days after death.[260] Dr. E. Tillner[261] has recognised potassic cyanide in a corpse four months after death. Lastly, Struve[262] put 300 grms. of flesh, 400 of common water, and 2·378 of KCy in a flask, and then opened the flask after 547 days. The detection was easy, and the estimation agreed with the amount placed there at first. So that, even in very advanced stages of putrefaction, and at periods after death extending beyond many months, the detection of prussic acid cannot be pronounced impossible.

[259] Dragendorff, G., _Beitr. zur gericht. Chem._, p. 59.

[260] Casper’s _Pract. Handbuch der gerichtlichen Medicin_, p. 561.

[261] _Vierteljahr. f. gerichtl. Med._, Berlin, 1881, p. 193.

[262] _Zeitschrift f. anal. Chemie_, von Fresenius, 1873, xii. p. 4.

§ 268. =Estimation of Hydrocyanic Acid or Potassic Cyanide.=--In all cases, the readiest method of estimating prussic acid (whether it be in the distillate from organic substances or in aqueous solution) is to saturate it with soda or potash, and titrate the alkaline cyanide thus formed with nitrate of silver. The process is based on the fact that there is first formed a soluble compound (KCy, AgCy), which the slightest excess of silver breaks up, and the insoluble cyanide is at once precipitated. If grains are used, 17 grains of nitrate of silver are dissolved in water, the solution made up to exactly 1000 grain measures, each grain measure equalling ·0054 grain of anhydrous hydrocyanic acid. If grammes are employed, the strength of the nitrate of silver solution should be 1·7 grm. to the litre, each c.c. then = ·0054 hydrocyanic acid, or ·01302 grm. of potassic cyanide.

Essential oil of bitter almonds may also be titrated in this way, provided it is diluted with sufficient spirit to prevent turbidity from separation of the essential oil. If hydrocyanic acid is determined gravimetrically (which is sometimes convenient, when only a single estimation is to be made), it is precipitated as cyanide of silver, the characters of which have been already described.

§ 269. =Case of Poisoning by Bitter Almonds.=--Instances of
poisoning by bitter almonds are very rare. The following interesting
case is recorded by Maschka:--

A maid-servant, 31 years of age, after a quarrel with her lover, ate
a quantity of bitter almonds. In a few minutes she sighed,
complained of being unwell and faint; she vomited twice, and, after
about ten minutes more had elapsed, fell senseless and was
convulsed. An hour afterwards, a physician found her insensible, the
eyes rolled upwards, the thumb clenched within the shut fists, and
the breathing rattling, the pulse very slow. She died within an
hour-and-a-half from the first symptoms.

The autopsy showed the organs generally healthy, but all, save the
liver, exhaling a faint smell of bitter almonds. The right side of
the heart was full of fluid dark blood, the left was empty. Both
lungs were rich in blood, which smelt of prussic acid. The stomach
was not inflamed--it held 250 grms. of a yellow fluid, containing
white flocks smelling of bitter almond oil. In the most dependent
portion of the stomach there was a swollen patch of mucous membrane,
partially denuded of epithelium. The mucous membrane of the duodenum
was also swollen and slightly red. The contents of the stomach were
acid, and yielded, on distillation, hydride of benzole and hydric
cyanide. Residues of the almonds themselves were also found, and
the whole quantity taken by the woman from various data was
calculated to be 1200 grains of bitter almonds, equal to 43 grains
of amygdalin, or 2·5 grains of pure hydric cyanide.

Poisonous Cyanides other than Hydric and Potassic Cyanides.

§ 270. The action of both _sodic and ammonic cyanides_ is precisely
similar to that of potassic cyanide. With regard to ammonic cyanide,
there are several experiments by Eulenberg,[263] showing that its
vapour is intensely poisonous.

[263] _Gewerbe Hygiene_, p. 385.

A weak stream of ammonic cyanide vapour was passed into glass
shades, under which pigeons were confined. After a minute, symptoms
of distress commenced, then followed convulsions and speedy death.
The _post-mortem_ signs were similar to those produced by prussic
acid, and this substance was separated from the liver and lungs.

§ 271. With regard to the _double cyanides_, all those are poisonous
from which hydric cyanide can be separated through dilute acids,
while those which, like potassic ferro-cyanide, do not admit of this
decomposition, may be often taken with impunity, and are only
poisonous under certain conditions.

Sonnenschein records the death of a colourist, after he had taken a
dose of potassic ferro-cyanide and then one of tartaric acid; and
Volz describes the death of a man, who took potassic ferro-cyanide
and afterwards equal parts of nitric and hydrochloric acids. In this
latter case, death took place within the hour, with all the symptoms
of poisoning by hydric cyanide; so that it is not entirely true, as
most text-books declare, that ferro-cyanide is in no degree
poisonous. Carbon dioxide will decompose potassic ferro-cyanide at
72°-74°, potass ferrous cyanide being precipitated--K₂Fe₂(CN)₆. A
similar action takes place if ferro-cyanide is mixed with a solution
of peptone and casein, and digested at blood heat[264] (from 37° to
40° C.), so that it is believed that when ferro-cyanide is swallowed
HCN is liberated, but the quantity is usually so small at any given
moment that no injury is caused: but there are conditions in which
it may kill speedily.[265]

[264] Autenrieth, _Arch. Pharm._, 231, 99-109.

[265] The presence of ferro-cyanide is easily detected. The liquid is, if necessary, filtered and then acidified with hydrochloric acid and a few drops of ferric chloride added; if the liquid contains ferro-cyanide, there is immediate production of Prussian blue. It may happen that potassic or sodic cyanide has been taken as well as ferro-cyanide, and it will be necessary then to devise a process by which only the prussic acid from the simple cyanide is distilled over. According to Autenrieth, if sodium hydrocarbonate is added to the liquid in sufficient quantity and the liquid distilled, the hydric cyanide that comes over is derived wholly from the sodium or potassium cyanide. Should mercury cyanide and ferro-cyanide be taken together, then this process requires modification; bicarbonate of soda is added as before, and then a few c.c. of water saturated with hydric sulphide; under these circumstances, only the hydric cyanide derived from the mercury cyanide distils over. If the bicarbonate of soda is omitted, the distillate contains hydric cyanide derived from the ferro-cyanide.

=Mercuric cyanide=, it has been often said, acts precisely like
mercuric chloride (corrosive sublimate), and a poisonous action is
attributed to it not traceable to cyanogen; but this is erroneous
teaching. Bernard[266] declares that it is decomposed by the gastric
juice, and hydric cyanide set free; while Pelikan puts it in the
same series as ammonic and potassic cyanides. Lastly,
Tolmatscheff,[267] by direct experiment, has found its action to
resemble closely that of hydric cyanide.[268]

[266] _Substances Toxiques_, pp. 66-103.

[267] “_Einige Bemerkungen über die Wirkung von Cyanquecksilber_,” in Hoppe-Seyler’s _Med. Chem. Untersuchungen_, 2 Heft, p. 279.

[268] Mercury cyanide may be detected in a liquid after acidifying with tartaric acid, and adding a few c.c. of SH₂ water and then distilling. S. Lopes suggests another process: the liquid is acidified with tartaric acid, ammonium chloride added in excess, and the liquid is distilled. A double chloride of ammonium and mercury is formed, and HCN distils over with the steam.--_J. Pharm._, xxvii. 550-553.

=Silver cyanide= acts, according to the experiments of Nunneley,
also like hydric cyanide, but very much weaker.

=Hydric sulphocyanide= in very large doses is poisonous.

=Potassic sulphocyanide=, according to Dubreuil and Legros,[269] if
subcutaneously injected, causes first local paralysis of the
muscles, and later, convulsions.

[269] _Compt. rend._, t. 64, 1867, p. 561.

=Cyanogen chloride= (CNCl) and also the compound (C₃N₃Cl₃)--the one
a liquid, boiling at 15°, the other a solid, which may be obtained
in crystals--are both poisonous, acting like hydric cyanide.

=Methyl cyanide= is a liquid obtained by distillation of a mixture
of calcic methyl sulphate and potassic cyanide. It boils at 77°, and
is intensely poisonous. Eulenberg[270] has made with this substance
several experiments on pigeons. An example of one will suffice:--A
young pigeon was placed under a glass shade, into which methyl
cyanide vapour, developed from calcic methyl sulphate and potassic
cyanide, was admitted. The pigeon immediately became restless, and
the fæces were expelled. In forty seconds it was slightly convulsed,
and was removed after a few minutes’ exposure. The pupils were then
observed not to be dilated, but the respiration had ceased; the legs
were feebly twitching; the heart still beat, but irregularly; a
turbid white fluid dropped out of the beak, and after six minutes
life was extinct.

[270] _Gewerbe Hygiene_, p. 392.

The pathological appearances were as follows:--In the beak much
watery fluid; the membranes covering the brain weakly injected; the
_plexus venosus spinalis_ strongly injected; in the region of the
cervical vertebra a small extravasation between the dura mater and
the bone; the right lung of a clear cherry-red colour, and the left
lung partly of the same colour, the parenchyma presented the same
hue as the surface; on section of the lungs a whitish froth exuded
from the cut surface. In the cellular tissue of the trachea, there
were extravasations 5 mm. in diameter; the mucous membrane of the
air-passages was pale; the right ventricle and the left auricle of
the heart were filled with coagulated and fluid dark red blood;
liver and kidneys normal; the blood dark red and very fluid,
becoming bright cherry-red on exposure to the air; blood corpuscles
unchanged. Cyanogen was separated, and identified from the lungs and
the liver.

=Cyanuric acid= (C₃O₃N₃H₃), one of the decomposition products
obtained from urea, is poisonous, the symptoms and pathological
effects closely resembling those due to hydric cyanide. In
experiments on animals, there has been no difficulty in detecting
prussic acid in the lungs and liver after poisoning by cyanuric
acid.

XIII.--Phosphorus.

§ 272. =Phosphorus.=--Atomic weight 31, specific gravity 1·77 to 1·840. Phosphorus melts at from 44·4° to 44·5° to a pale yellow oily fluid. The boiling-point is about 290°.

The phosphorus of commerce is usually preserved under water in the form of waxy, semi-transparent sticks; if exposed to the air white fumes are given off, luminous in the dark, with a peculiar onion-like odour. On heating phosphorus it readily inflames, burning with a very white flame.

At 0° phosphorus is brittle; the same quality may be imparted to it by a mere trace of sulphur. Phosphorus may be obtained in dodecahedral crystals by slowly cooling large melted masses. It may also be obtained crystalline by evaporating a solution in bisulphide of carbon or hot naphtha in a current of carbon dioxide. It is usually stated to be absolutely insoluble in water, but Julius Hartmann[271] contests this, having found in some experiments that 100 grms. of water digested with phosphorus for sixty-four hours at 38·5° dissolved ·000127 grm. He also investigated the solvent action of bile, and found that 100 grms. of bile under the same conditions, dissolved ·02424 grm., and that the solubility of phosphorus rose both in water and bile when the temperature was increased. Phosphorus is somewhat soluble in alcohol and ether, and also, to some extent, in fatty and ethereal oils; but the best solvent is carbon disulphide.

[271] _Zur acuten Phosphor-Vergiftung_, Dorpat, 1866.

The following is the order of solubility in certain menstrua, the figures representing the number of parts by weight of the solvent required to dissolve 1 part of phosphorus:--

Carbon Disulphide, 4
Almond Oil, 100
Concentrated Acetic Acid,[272] 100
Ether, 250
Alcohol, specific gravity ·822, 400
Glycerin, 588

[272] Phosphorus is very little soluble in cold acetic acid, and the solubility given is only correct when the boiling acid acts for some time on the phosphorus.

Phosphorus exists in, or can be converted into, several allotropic modifications, of which the red or amorphous phosphorus is the most important. This is effected by heating it for some time, in the absence of air, from 230° to 235°. It is not poisonous.[273] Commercial red phosphorus does, however, contain very small quantities of unchanged or ordinary phosphorus--according to Fresenius, from ·6 per cent. downwards; it also contains phosphorous acid, and about 4·6 per cent. of other impurities, among which is graphite.[274]

[273] A hound took 200 grms. of red phosphorus in twelve days, and remained healthy.--Sonnenschein.

[274] Schrotter, _Chem. News_, vol. xxxvi. p. 198.

§ 273. =Phosphuretted Hydrogen.=--=Phosphine= (PH₃), mol. weight 34, specific gravity 1·178, percentage composition, phosphorus 91·43, hydrogen 8·57 by weight. The absolutely pure gas is not spontaneously inflammable, but that made by the ordinary process is so. It is a colourless, highly poisonous gas, which does not support combustion, but is itself combustible, burning to phosphoric acid (PH₃ + 2O₂ = PO₄H₃). Extremely dangerous explosive mixtures may be made by combining phosphine and air or oxygen. Phosphine, when quite dry, burns with a white flame, but if mixed with aqueous vapour, it is green; hence a hydrogen flame containing a mixture of PH₃ possesses a green colour.

If sulphur is heated in a stream of phosphine, hydric sulphide and sulphur phosphide are the products. Oxides of the metals, heated with phosphine, yield phosphides with formation of water. Iodine, warmed in phosphine, gives white crystals of iodine phosphonium, and biniodide of phosphorus, 5I + 4PH₃ = 3PIH₄ + PI₂. Chlorine inflames the gas, the final result being hydric chloride and chloride of phosphorus, PH₃ + 8Cl = 3ClH + PCl₅. One of the most important decompositions for our purpose is the action of phosphine on a solution of nitrate of silver; there is a separation of metallic silver, and nitric and phosphoric acids are found in solution, thus--8AgNO₃ + PH₃ + 4OH₂ = 8Ag + 8HNO₃ + PO₄H₃. This is, however, rather the end reaction; for, at first, there is a separation of a black precipitate composed of phosphor-silver. The excess of silver can be separated by hydric chloride, and the phosphoric acid made evident by the addition of molybdic acid in excess.

§ 274. =The medicinal preparations of phosphorus= are not numerous; it is usually prescribed in the form of pills, made by manufacturers of coated pills on a large scale. The pills are composed of phosphorus, balsam of Tolu, yellow wax, and curd soap, and 3 grains equal 1/30 grain of phosphorus. There is also a _phosphorated oil_, containing about 1 part of phosphorus in 100; that of the French Pharmacopœia is made with 1 part of dried phosphorus dissolved in 50 parts of warm almond oil; that of the German has 1 part in 80; the strength of the former is therefore 2 per cent., of the latter 1·25 per cent. The medicinal dose of phosphorus is from 1/100 to 1/30 grain.

§ 275. =Matches and Vermin Pastes.=--An acquaintance with the percentage of phosphorus in the different pastes and matches of commerce will be found useful. Most of the vermin-destroying pastes contain from 1 to 2 per cent. of phosphorus.

A phosphorus paste that was fatal to a child,[275] and gave rise to serious symptoms in others, was composed as follows:--

[275] Casper’s 204th case.

Per cent.
Phosphorus, 1·4
Flowers of sulphur, 42·2
Flour, 42·2
Sugar, 14·2
------
100·00

Three common receipts give the following proportions:--

Per cent.
Phosphorus, 1·5
Lard, 18·4
Sugar, 18·4
Flour, 61·7
------
100·00

Per cent.
Phosphorus, 1·2
Warm water, 26·7
Rye flour, 26·7
Melted butter, 26·7
Sugar, 18·7
------
100·00

Per cent.
Phosphorus, 1·6
Nut oil, 15·7
Warm water, 31·5
Flour, 31·5
Sugar, 19·7
------
100·00

A very common phosphorus paste, to be bought everywhere in England, is sold in little pots; the whole amount of phosphorus contained in these varies from ·324 to ·388 grm. (5 to 6 grains), the active constituent being a little over 4 per cent. Matches differ much in composition. Six matchheads, which had been placed in an apple for criminal purposes, and were submitted to Tardieu, were found to contain 20 mgrms. of phosphorus--_i.e._, ·33 grm. in 100. Mayet found in 100 matches 55 mgrms. of phosphorus. Gonning[276] analysed ten different kinds of phosphorus matches with the following result:--Three English samples contained in 100 matches 34, 33, and 32 mgrms. of phosphorus: a Belgian sample, 38 mgrms.; and 5 others of unknown origin, 12, 17, 28, 32, and 41 mgrms. respectively. Some of the published formularies are as follows:--

[276] _Nederlandsch Tijdschr. voor Geneesk._, Afl. i., 1866.

(1.) Glue, 6 parts.
Phosphorus, 4 „ or 14·4 per cent.
Nitre, 10 „
Red ochre, 5 „
Blue smalts, 2 „

(2.) Phosphorus, 9 parts, or 16·3 per cent.
Gum, 16 „
Nitre, 14 „
Smalts, 16 „

(3.) Phosphorus, 4 parts, or 14·4 per cent.
Glue, 6 „
Nitre, 10 „
Red lead, 5 „
Smalts, 2 „

(4.) Phosphorus, 17 parts, or 17 per cent.
Glue, 21 „
Nitre, 38 „
Red lead, 24 „

Phosphorus poisoning by matches will, however, shortly become very rare, for those containing the ordinary variety of phosphorus are gradually being superseded by matches of excellent quality, which contain no phosphorus whatever.

§ 276. =Statistics.=--The following table gives the deaths for ten years from phosphorus poisoning in England and Wales:--

DEATHS FROM PHOSPHORUS IN ENGLAND AND WALES DURING THE TEN YEARS ENDING 1892.

ACCIDENT OR NEGLIGENCE.

Ages, 1-5 5-15 15-25 25-65 65 and Total
above
Males, 11 1 2 8 ... 22
Females, 15 2 11 5 ... 33
-------------------------------------------
Totals, 26 3 13 13 ... 55
-------------------------------------------

SUICIDE.

Ages, 5-15 15-25 25-65 65 and Total
above
Males, 1 6 20 1 28
Females, 6 33 24 1 64
-------------------------------------
Totals, 7 39 44 2 92
-------------------------------------

Phosphorus as a cause of death through accident or negligence occupies the eighth place among poisons, and as a cause of suicide the ninth.

A far greater number of cases of poisoning by phosphorus occur yearly in France and Germany than in England. Phosphorus may be considered as the favourite poison which the common people on the Continent employ for the purpose of self-destruction. It is an agent within the reach of anyone who has 2 sous in his pocket, wherewith to buy a box of matches, but to the educated and those who know the horrible and prolonged torture ensuing from a toxic dose of phosphorus, such a means of exit from life will never be favoured.

Otto Schraube[277] has collected 92 cases from Meischner’s work,[278] and added 16 which had come under his own observation, giving in all 108 cases. Seventy-one (or 65 per cent.) of these were suicidal--of the suicides 24 were males, 47 females (12 of the latter being prostitutes); 21 of the cases were those of murder, 11 were accidental, and in 3 the cause was not ascertained. The number of cases in successive years, and the kind of poison used, is given as follows:--

[277] Schmidt’s _Jahrbuch der ger. Med._, 1867, Bd. 186, S. 209-248.

[278] _Die acute Phosphorose und einige Reflexionen über die acute gelbe Leberatrophie, &c., Inaug. Diss._, Leipzig, 1864.

Phosphorus in Phosphorus
Number of Cases. In the Years Substance, Matches.
or as Paste.

15 1798-1850 13 2
36 1850-1860 15 21
41 1860-1864 6 35
16 1864-1867 5 11

Of the 108 cases, 18 persons recovered and 90 (or 83·3 per cent.) died.

Falck also has collected 76 cases of poisoning from various sources during eleven years; 55 were suicidal, 5 homicidal[279] (murders), and the rest accidental. Of the latter, 2 were caused by the use of phosphorus as a medicine, 13 by accidents due to phosphorus being in the house; in 1 case phosphorus was taken intentionally to try the effects of an antidote.[280] With regard to the form in which the poison was taken, 2 of the 76, as already mentioned, took it as prescribed by physicians, the remaining 74 were divided between poisonings by phosphorus paste (22) and matches (52) = 70 per cent. Of the 76 cases, 6 were children, 43 adult males, 13 adult females, and 14 adults, sex not given. Of the 76 cases, 42, or 55·3 per cent., died--a much smaller rate of mortality than that shown by Schraube’s collection.

[279] Dr. Dannenberg has shown by direct experiment that a poisonous dose of phosphorus may be introduced into spirits or coffee, and the mixture have but little odour or taste of phosphorus.--Schuchardt in Maschka’s _Handbuch_.

[280] Géry, “_Ueber Terpentinessenz als Gegenmittel gegen Phosphor_,” in _Gaz. Hebd. de Méd._, 2 sér., x. 2, 1873.

§ 277. =Fatal Dose.=--The smallest dose on record is that mentioned by Lobenstein Lobel, of Jena, where a lunatic died from taking 7·5 mgrms. (·116 grain). There are other cases clearly indicating that this small quantity may produce dangerous symptoms in a healthy adult.

§ 278. =Effects of Phosphorus.=--Phosphorus is excessively poisonous, and will destroy life, provided only that it enters the body in a fine state of division, but if taken in coarse pieces no symptoms may follow, for it has been proved that single lumps of phosphorus will go the whole length of a dog’s intestinal canal without causing appreciable loss of weight, and without destroying life.[281] Magendie injected _oleum phosphoratum_ into the veins, and although the animals experimented on exhaled white fumes, and not a few died asphyxiated, yet no symptoms of phosphorus poisoning resulted--an observation confirmed by others--the reason being that the phosphorus particles in a comparatively coarse state of division were arrested in the capillaries of the lung, and may be said to have been, as it were, outside the body. On the other hand, A. Brunner,[282] working in L. Hermann’s laboratory, having injected into the veins phosphorus in such a fine emulsion that the phosphorus could pass the lung capillaries, found that there were no exhalations of white fumes, but that the ordinary symptoms of phosphorus poisoning soon manifested themselves. Phosphorus paste, by the method of manufacture, is in a state of extreme sub-division, and hence all the phosphorus pastes are extremely poisonous.

[281] Reveil, _Ann. d’Hygiène Publ._ (3), xii. p. 370.

[282] _Arch. f. d. Ges. Physiologie_, iii. p. 1.

§ 279. In a few poisons there is a difference, more or less marked, between the general symptoms produced on man, and those noticeable in the different classes of animals; but with phosphorus, the effects on animals appear to agree fairly with those witnessed most frequently in man. Tardieu (who has written perhaps the best and most complete clinical record of phosphorus poisoning extant) divides the cases under three classes, and to use his own words:--“I think it useful to establish that poisoning by phosphorus in its course, sometimes rapid, sometimes slow, exhibits in its symptoms three distinct forms--a common form, a nervous form, and a hæmorrhagic form. I recognise that, in certain cases, these three forms may succeed each other, and may only constitute periods of poisoning; but it is incontestable that each of them may show itself alone, and occupy the whole course of the illness produced by the poison.”[283] Premising that the common form is a blending of irritant, nervous, and hæmorrhagic symptoms, I adopt here in part Tardieu’s division. The name of “hæmorrhagic form” may be given to that in which hæmorrhage is the predominant feature, and the “nervous” to that in which the brain and spinal cord are from the first affected. There yet remain, however, a few cases which have an entirely anomalous course, and do not fall under any of the three classes.

[283] _Étude Médico-Légale et Clinique sur l’Empoisonnement_, Paris, 1875, p. 483.

From a study of 121 recorded cases of phosphorus poisoning, I believe the relative frequency of the different forms to be as follows:--The common form 83 per cent., hæmorrhagic 10 per cent., nervous 6 per cent., anomalous 1 per cent. The “anomalous” are probably over-estimated, for the reason that cases presenting ordinary features are not necessarily published, but others are nearly always chronicled in detail.

§ 280. =Common Form.=--At the moment of swallowing, a disagreeable taste and smell are generally experienced, and there may be immediate and intense pain in the throat, gullet, and stomach, and almost immediate retching and vomiting. The throat and tongue also may become swollen and painful; but in a considerable number of cases the symptoms are not at once apparent, but are delayed from one to six hours--rarely longer. The person’s breath may be phosphorescent before he feels in any way affected, and he may go about his business and perform a number of acts requiring both time and mental integrity. Pain in the stomach (which, in some of the cases, takes the form of violent cramp and vomiting) succeeds; the matters vomited may shine in the dark, and are often tinged with blood. Diarrhœa is sometimes present, sometimes absent; sleeplessness for the first night or two is very common. The pulse is variable, sometimes frequent, sometimes slow; the temperature in the morning is usually from 36·0° to 36·5°, in the evening 37° to 38°.

The next symptom is jaundice. I have notes of the exact occurrence of jaundice in 23 cases, as follows:--In 1 within twenty-four hours, in 3 within thirty-six hours, in 3 within two days, in 11 within three days, in 1 within four days, in 1 within five days, in 1 within nine days, in 1 within eighteen days, and in 1 within twenty-seven days; so that in about 78 per cent. jaundice occurred before the end of the third day. Out of 26 cases, in which the patients lived long enough for the occurrence of jaundice, in 3 (or 11 per cent.) it was entirely absent. In 132 cases recorded by Lewin, Meischner, and Heisler, jaundice occurred in 65, or about 49 per cent., but it must be remembered, that in many of these cases the individual died before it had time to develop. The jaundice having thoroughly pronounced itself, the system may be considered as not only under the influence of the toxic action of phosphorus, but as suffering in addition from all the accidents incidental to the retention of the biliary secretion in the blood; nor is there from this point any special difference between phosphorus poisoning and certain affections of the liver--such, for example, as acute yellow atrophy. There is retention of urine, sleeplessness, headache, frequent vomiting, painful and often involuntary evacuations from the bowels, and occasionally skin affections, such as urticaria or erythema. The case terminates either by acute delirium with fever, followed by fatal coma, or, in a few instances, coma comes on, and the patient passes to death in sleep without delirium. In this common form there is in a few cases, at the end of from twenty-four to thirty hours, a remission of the symptoms, and a non-medical observer might imagine that the patient was about to recover without further discomfort; but then jaundice supervenes, and the course is as described. Infants often do not live long enough for the jaundiced stage to develop, but die within twenty-four hours, the chief symptoms being vomiting and convulsions.

§ 281. =Hæmorrhagic Form.=--The symptoms set in as just detailed, and jaundice appears, but accompanied by a new and terrible train of events--viz., great effusion of blood. In some cases the blood has been poured out simultaneously from the nose, mouth, bladder, kidneys, and bowels. Among women there is excessive hæmorrhagia. The liver is found to be swollen and painful; the bodily weakness is great. Such cases are usually of long duration, and a person may die months after taking the poison from weakness, anæmia, and general cachexia. In many of its phases the hæmorrhagic form resembles scurvy, and, as in scurvy, there are spots of purpura all over the body.

§ 282. =The nervous form= is less common than the two forms just described. From the beginning, there are strange creeping sensations about the limbs, followed by painful cramps, repeated faintings, and great somnolence. Jaundice, as usual, sets in, erythematous spots appear on the skin, and, about the fifth day, delirium of an acute character breaks out, and lock-jaw and convulsions close the scene.

The following are one or two brief abstracts of anomalous cases in which symptoms are either wanting, or run a course entirely different from any of the three forms described:--

A woman, aged 20, took about 3 grains of phosphorus in the form of rat-paste. She took the poison at six in the evening, behaved according to her wont, and sat down and wrote a letter to the king. During the night she vomited once, and died the next morning at six o’clock, exactly twelve hours after taking the poison. There appear to have been no symptoms whatever, save the single vomiting, to which may be added that in the course of the evening her breath had a phosphorus odour and was luminous.[284]

[284] Casper’s 205th case.

A girl swallowed a quantity of phosphorus paste, but there were no marked symptoms until the fifth day, on which there was sickness and purging. She died on the seventh day. A remarkable blueness of the finger nails was observed a little before death, and was noticeable afterwards.[285]

[285] Taylor on _Poisons_, p. 277.

§ 283. =Sequelæ.=--In several cases in which the patients have recovered from phosphorus poisoning, there have been observed paralytic affections.[286] O. Bollinger has recorded a case in which paralysis of the foot followed;[287] in another, published by Bettelheim,[288] there were peculiar cerebral and spinal symptoms. Most of these cases are to be explained as disturbance or loss of function from small hæmorrhages in the nervous substance.

[286] See Gallavardin, _Les Paralyses Phosphoriques_, Paris, 1865.

[287] _Deutsches Archiv f. klin. Med._, Bd. 6, Hft. 1, S. 94, 1869.

[288] _Wiener Med. Presse_, 1868, No. 41.

§ 284. =Period at which the first Symptoms commence.=--The time when the symptoms commence is occasionally of importance from a forensic point of view. I find that out of 28 cases in which the commencement of evident symptoms--_i.e._, pain, or vomiting, or illness--is precisely recorded, in 8 the symptoms were described as either immediate or within a few minutes after swallowing the poison; in 6 the symptoms commenced within the hour; in 3 within two hours; in other 3 within four hours; and in 1 within six hours. One was delayed until the lapse of twelve hours, 1 from sixteen to eighteen hours, 1 two, and another five days. We may, therefore, expect that in half the cases which may occur, the symptoms will commence within the hour, and more than 80 per cent. within six hours.

§ 285. =Period of Death.=--In 129 cases death took place as follows:--In 17 within twenty-four hours, in 30 within two days, in 103 within seven days. Three patients lived eight days, 6 nine days, 13 ten days, 1 eleven days, 1 sixteen days, 1 seventeen days, and 1 survived eight months. It hence follows that 79·8 per cent. of the fatal cases die within the week.

§ 286. =Phosphorus Vapour.=--There are one or two cases on record of acute poisoning by phosphorus in the form of vapour. The symptoms are somewhat different from the effects produced by the finely-divided solid, and in general terms it may be said that phosphorus vapour is more apt to produce the rarer “nervous” form of poisoning than the solid phosphorus.

Bouchardat[289] mentions the case of a druggist who, while preparing a large quantity of rat-poison in a close room, inhaled phosphorus vapour. He fainted repeatedly, fell into a complete state of prostration, and died within a week.

[289] _Annuaire de Thérap._, 1874, p. 109; Schuchardt in Maschka’s _Handbuch_; also Schmidt’s _Jahrbuch_, 1846, Bd. 51, S. 101.

The following interesting case came under the observation of Professor Magnus Huss:--A man, thirty-nine years old, married, was admitted into the Seraphin-Lazareth, Stockholm, on the 2nd of February 1842. He had been occupied three years in the manufacture of phosphorus matches, and inhabited the room in which the materials were preserved. He had always been well-conducted in every way, and in good health, until a year previously, when a large quantity of the material for the manufacture of the matches accidentally caught fire and exploded. In his endeavours to extinguish the flames, he breathed a large quantity of the vapour, and he fell for a time unconscious. The spine afterwards became so weak that he could not hold himself up, and he lost, in a great measure, power over his legs and arms. On admission, his condition was as follows:--He could make a few uncertain and staggering steps, his knees trembled, his arms shook, and if he attempted to grasp anything when he lay in bed, there were involuntary twitchings of groups of muscles. There was no pain; the sensibility of the skin was unchanged; he had formication in the left arm; the spine was neither sensitive to pressure, nor unusually sensitive to heat (as, _e.g._, to the application of a hot sponge); the organs of special sense were not affected, but his speech was somewhat thick. He lived to 1845 in the same condition, but the paralysis became worse. There does not seem to have been any autopsy.

The effects of phosphorus vapour may be still further elucidated by one of Eulenberg’s[290] experiments on a rabbit. The vapour of burning phosphorus, mixed with much air, was admitted into a wooden hutch in which a strong rabbit sat. After 5 mgrms. of phosphorus had been in this manner consumed, the only symptoms in half an hour were salivation, and quickened and somewhat laboured respiration. After twenty-four hours had elapsed there was sudden indisposition, the animal fell as if lifeless, with the hind extremities stretched out, and intestinal movements were visible; there was also expulsion of the urine. These epileptiform seizures seem to have continued more or less for twelve days, and then ceased. After fourteen days the experiment was repeated on the same rabbit. The animal remained exposed to the vapour for three-quarters of an hour, when the epilepsy showed itself as before, and, indeed, almost regularly after feeding. Between the attacks the respiration was slowed. Eight weeks afterwards there was an intense icterus, which disappeared at the end of ten weeks.

[290] _Gewerbe Hygiene_, p. 255.

§ 287. =Chronic phosphorus poisoning= has frequently been noticed in persons engaged either in the manufacture of phosphorus or in its technical application. Some have held that the symptoms are due to an oxidation product of phosphorus rather than to phosphorus itself; but in one of Eulenberg’s experiments, in which a dove was killed by breathing phosphorus fumes evolved by phosphorus oil, phosphorus was chemically recognised in the free state in the lungs. The most constant and peculiar effect of breathing small quantities of phosphorus vapour is a necrosis of the lower jaw. There is first inflammation of the periosteum of the jaw, which proceeds to suppuration and necrosis of a greater or smaller portion. The effects may develop with great suddenness, and end fatally. Thus Fournier and Olliver[291] relate the case of a girl, fourteen years old, who, after working four years in a phosphorus manufactory, was suddenly affected with periostitis of the upper jaw, and with intense anæmia. An eruption of purpuric spots ensued, and she died comatose. There is now little doubt, that minute doses of phosphorus have a specific action on the bones generally, and more especially on the bones of the jaw. Wegner[292] administered small daily doses to young animals, both in the state of vapour, and as a finely-divided solid. The condition of the bones was found to be more compact than normal, the medullary canals being smaller than in healthy bone, the ossification was quickened. The formation of callus in fractured limbs was also increased.

[291] _Gaz. hebd. de Méd._, 29, p. 461, 1868.

[292] Virchow’s _Arch. f. path. Anat._, lv. 11.

§ 288. =Changes in the Urinary Secretion.=--It has been before stated that, at a certain period of the illness, the renal secretion is scantier than in health, the urine diminishing, according to Lebert and Wyss’s[293] researches, to one-half on the third, fourth, or fifth day. It frequently contains albumen, blood, and casts. When jaundice is present, the urine has then all the characters noticed in icterus; leucin and tyrosin, always present in acute yellow atrophy of the liver, have been found in small quantity in jaundice through phosphorus; lactic acid is also present. The urea is much diminished, and, according to Schultzen and Riess,[294] may be towards death entirely absent. Lastly, it is said that there is an exhalation of either phosphorus vapour or phosphine from such urine. In some cases the urine is normal, _e.g._, in a case recorded by E. H. Starling, M.D., and F. G. Hopkins, B.Sc. (_Guy’s Hospital Report_, 1890), in which a girl, aged 18, died on the fifth day after taking phosphorus paste, the liver was fatty, and there was jaundice; but the urine contained neither leucin nor tyrosin, and was stated to be generally normal.

[293] _Archiv Générale de Méd._, 6 Sér., Tom. 12, 1868, p. 709.

[294] _Annalen der Charité_, Berlin.

§ 289. =Changes in the blood= during life have been several times observed. In a case attended by M. Romellære of Brussels,[295] in which a man took the paste from 300 matches, and under treatment by turpentine recovered, the blood was frequently examined, and the leucocytes found much increased in number. There is a curious conflict of evidence as to whether phosphorus prevents coagulation of the blood or not. Nasse asserted that phosphorated oil given to a dog fully prevented coagulation; P. I. Liebreck[296] also, in a series of researches, found the blood dark, fluid, and in perfect solution. These observations were also supported by V. Bibra and Schuchardt.[297] Nevertheless, Lebert and Wyss found the blood, whether in the veins or in extravasations, in a normal condition. Phosphorus increases the fatty contents of the blood. Ritter found that phosphorus mixed with starch, and given to a dog, raised the fatty content from the normal 2 per 1000 up to 3·41 and 3·47 per 1000. Eug. Menard[298] saw in the blood from the jugular and portal veins, as well as in extravasations, microscopic fat globules and fine needle-shaped crystals soluble in ether.

[295] Tardieu, _op. cit._, Case 31.

[296] _Diss. de Venefico Phosphoreo Acuto_, Upsal, 1845.

[297] V. Bibra u. Geist, _Die Krankheiten der Arbeiter in den Phosphorzundholz Fabriken_, 1847, S. 59, &c.; Henle u. v. Pfeuffer’s _Zeitschr. f. ration. Med._, N. F., Bd. 7, Hft. 3, 1857.

[298] _Étude Expérimentale sur quelques lésions de l’Empoisonnement aigu par le Phosphore (Thèse)_, Strasbourg, 1869.

§ 290. =Antidote--Treatment.=--After emptying the stomach by means of emetics or by the stomach-pump, oil of turpentine in full medicinal doses, say 2·5 c.c. (about 40 min.), frequently administered, seems to act as a true antidote, and a large percentage of cases treated early in this way recover.