§ 755. Dose.—A medicinal dose of a soluble antimonial salt should not exceed 97·2 mgrms. (1¹⁄₂ grain). With circumstances favouring its action, a dose of 129·6 mgrms. (2 grains) has proved fatal;[803] but this is quite exceptional, and few medical men would consider so small a quantity dangerous for a healthy adult, especially since most posological tables prescribe tartar emetic as an emetic in doses from 64·8 to 194·4 mgrms. (1 to 3 grains). The smallest dose which has killed a child appears to be 48·5 mgrms. (³⁄₄ grain).[804] The dose of tartar emetic for horses and cattle is very large, as much as 5·832 grms. (90 grains) being often given to a horse in his gruel three times a day. 3·8 grms. (60 grains) are considered a full, but not an excessive, dose for cattle; ·38 grm. (6 grains) is used as an emetic for pigs, and half this quantity for dogs.

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§ 756. Effects of Tartar Emetic and of Antimony Oxide on Animals.—Large doses of tartar emetic act on the warm-blooded animals as on man; whether the poison is taken by the mouth, or injected subcutaneously, all animals able to vomit[805] do so. The heart’s action, at first quickened, is afterwards slowed, weakened, and lastly paralysed. This action is noticed in cold as well as in warm-blooded animals. It is to be ascribed to a direct action on the heart; for if the brain and spinal cord of the frog be destroyed—or even if a solution of the salt be applied direct to the frog’s heart separated from the body—the effect is the same. The weak action of the heart, of course, causes the blood-pressure to diminish, and the heart stops in diastole. The voluntary muscles of the body are also weakened; the breathing is affected, partly from the action on the muscles. The temperature of the body is depressed (according to F. A. Falck’s researches) from 4·4° to 6·2°.

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The effect of small doses given repeatedly to animals has been several times investigated. Dr. Nevin[806] experimented upon eleven rabbits, giving them tartar emetic four times a day in doses of 32·4 mgrms. (¹⁄₂ grain), 64·8 mgrms. (1 grain), and 129·6 mgrms. (2 grains). Five died, the first after four, the last after seventeen days; three were killed after one, three, and four days respectively, two after an interval of fourteen days, and one thirty-one days after taking the last dose. There was no vomiting; diarrhœa was present in about half the number; one of the rabbits, being with young, aborted. The chief symptoms were general dulness, loss of appetite, and in a few days great emaciation. Four of the five that died were convulsed before death, and several of the animals exhibited ulcers of the mucous membrane of the mouth, in places with which the powder had come in contact. Caillol and Livon have also studied the action of small doses of the white oxide of antimony given in milk to cats. A cat took in this way in 109 days ·628 grm. The animal passed gradually into a cachectic state, diarrhœa supervened, and it died miserably thin and exhausted.

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§ 757. Effects of Tartar Emetic on Man.[807]—The analogy between the symptoms produced by arsenic and antimony is striking, and in some acute cases of poisoning by tartar emetic, there is but little (if any) clinical difference. If the dose of tartar emetic is very large, there may be complete absence of vomiting, or only a single evacuation of the stomach. Thus, in a case mentioned by Taylor, in which a veterinary surgeon swallowed by mistake 13 grms. (200 grains) of tartar emetic, vomiting after fifteen minutes could only be induced by tickling the throat. So, again, in the case reported by Mr. Freer, a man, aged 28, took 7·77 grms. (120 grains) of tartar emetic by mistake for Epsom salts; he vomited only once; half an hour after taking the poison he had violent pain in the stomach and abdomen, and spasmodic contraction of the abdomen and arms; the fingers were firmly contracted, the muscles quite rigid, and there was involuntary aqueous purging. After six hours, during which he was treated with green tea, brandy, and decoction of oak-bark, he began to recover, but suffered for many nights from profuse perspirations.

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With more moderate and yet large doses, nausea and vomiting are very prominent symptoms, and are seldom delayed more than half an hour. The regular course of symptoms may therefore be summed up thus:—A metallic taste in the mouth, repeated vomitings, which are sometimes bloody, great faintness and depression, pains in the abdomen and stomach, and diarrhœa, which may be involuntary. If the case is to terminate fatally, the urine is suppressed, the temperature falls, the face becomes cyanotic, delirium and convulsions supervene, and death occurs in from two to six days. Antimony, like arsenic, often produces a pustular eruption. Solitary cases deviate more or less from the course described, i.e., severe cramps affecting all the muscles, hæmorrhage from the stomach, kidney, or bowel, and death from collapse in a few hours, have all been noticed. In a case recorded by Mr. Morley,[808] a surgeon’s daughter, aged 18, took by mistake an unknown quantity of antimonial wine; she soon felt sleepy and powerless, and suffered from the usual symptoms in combination with tetanic spasms of the legs. She afterwards had enteritis for three weeks, and on recovery her hair fell off. Orfila relates a curious case of intense spasm of the gullet from a large dose of tartar emetic.

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§ 758. Chronic Antimonial Poisoning.—The cases of Palmer and J. P. Cook, M. Mullen, Freeman, Winslow, Pritchard, and the remarkable Bravo case have, in late years, given the subject of chronic antimonial poisoning a considerable prominence. In the trials referred to, it was shown that medical men might easily mistake the effects of small doses of antimony given at intervals for the action of disease—the symptoms being great nausea, followed by vomiting, chronic diarrhœa, alternating with constipation, small frequent pulse, loss of voice, great muscular weakness, depression, with coldness of the skin and a clammy perspiration. In the case of Mrs. Pritchard,[809] her face was flushed, and her manner so excited as to give an ordinary observer the idea that she had been drinking; and with the usual symptoms of vomiting and purging, she suffered from cramps in the hands. Dr. Pritchard tried to make it appear that she was suffering from typhoid fever, which the symptoms in a few respects only resembled.

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According to Eulenberg, workmen, exposed for a long period to the vapour of the oxide of antimony, suffer pain in the bladder and a burning sensation in the urethra, and continued inhalation even leads to impotence and wasting of the testicles.[810]

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§ 759. Post-mortem Appearances.—The effect of large doses of tartar emetic is mainly concentrated upon the gastro-intestinal mucous membrane. There is an example in the museum of University College Hospital of the changes which resulted from the administration of tartar emetic in the treatment of pneumonia. These are ascribed in the catalogue, in part to the local action of the medicine, and in part to the extreme prostration of the patient. In the preparation (No. 1052) the mucous membrane over the fore border of the epiglottis and adjacent part of the pharynx has been destroyed by sloughing; the ulceration extends into the upper part of the œsophagus. About an inch below its commencement, the mucous membrane has been entirely removed by sloughing and ulceration, the circular muscular fibres being exposed. Above the upper limit of this ulcer, the mucous membrane presents several oval, elongated, and ulcerated areas, occupied by strips of mucous membrane which have sloughed. In other places, irregular portions of the mucous membrane, of a dull ashen-gray colour, have undergone sloughing; the edges of the sloughing portion are of colours varying from brown to black.

It is seldom that so much change is seen in the gullet and pharynx as this museum preparation exhibits; but redness, swelling, and the general signs of inflammation are seldom absent from the stomach and some parts of the intestines. On the lining membrane of the mouth, ulcers and pustules have been observed.

In Dr. Nevin’s experiments on the chronic poisoning of rabbits already referred to, the post-mortem appearances consisted in congestion of the liver in all the rabbits; in nearly all there was vivid redness of the stomach; in two cases there was ulceration; in some, cartilaginous hardness of the pylorus; while, in others, the small intestines presented patches of inflammation. In two of the rabbits the solitary glands throughout the intestines were prominent, yellow in colour, and loaded with antimony. The colon and rectum were healthy, the kidneys congested; the lungs were in most congested, in some actually inflamed, or hepatised and gorged with blood. Bloody extravasations in the chest and abdomen were frequent.

Saikowsky,[811] in feeding animals daily with antimony, found invariably in the course of fourteen to nineteen days fatty degeneration of the liver, and sometimes of the kidney and heart. In the experiment of Caillol and Livon also all the organs were pale, the liver had undergone fatty degeneration, and the lung had its alveoli filled with large degenerated cells, consisting almost entirely of fat. The mesenteric glands also formed large caseous masses, yellowish-white in colour, which, under the microscope, were seen to be composed of fatty cells, so that there is a complete analogy between the action of arsenic and antimony on the body tissues.

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§ 760. Elimination of Antimony.—Antimony is mainly eliminated by the urine. In 1840, Orfila showed to the Académie de Médecine metallic antimony, which he had extracted from a patient who had taken ·12 grm. of tartar emetic in twenty-four hours. He also obtained antimony from an old woman, aged 80, who twelve hours before had taken ·6 grm. (9¹⁄₄ grains)—a large dose, which had neither produced vomiting nor purging. In Dr. Kevin’s experiments on rabbits, antimony was discovered in the urine after the twelfth dose, and even in the urine of an animal twenty-one days after the administration of the poison had been suspended.

§ 761. Antidotes for Tartar Emetic.—Any infusion containing tannin or allied astringent principles, such as decoctions of tea, oak-bark, &c., may be given with advantage in cases of recent poisoning by tartar emetic, for any of the salt which has been expelled by vomiting may in this way be decomposed and rendered harmless. The treatment of acute poisoning which has proved most successful, has been the encouraging of vomiting by tickling the fauces, giving strong green tea and stimulants. (See Appendix.)

§ 762. Effects of Chloride or Butter of Antimony.—Only a few cases of poisoning by butter of antimony are on record: its action, generally speaking, on the tissues is like that of an acid, but there has been considerable variety in the symptoms. Five cases are recorded by Taylor; three of the number recovered after taking respectively doses of 7·7 grms. (2 drachms) and 15·5 grms. (4 drachms), and two died after taking from 56·6 to 113 grms. (2 to 4 ounces). In one of these cases the symptoms were more like those of a narcotic poison, in the other fatal case there was abundant vomiting with purging. The autopsy in the first case showed a black appearance from the mouth to the jejunum, as if the parts had been charred, and extensive destruction of the mucous membrane. In the other case there were similar changes in the stomach and the upper part of the intestines, but neither the lips nor the lower end of the gullet were eroded. In a case recorded by Mr. Barrington Cooke,[812] a farmer’s wife, aged 40, of unsound mind, managed to elude the watchfulness of her friends, and swallowed an unknown quantity of antimony chloride about 1.30 P.M. Shortly afterwards she vomited several times, and had diarrhœa; at 2.30 a medical man found her lying on her back insensible, and very livid in the face and neck. She was retching, and emitting from her mouth a frothy mucous fluid, mixed with ejected matter of a grumous colour; the breathing was laboured and spasmodic; the pulse could not be felt, and the body was cold and clammy. She expired at 3.30, about one hour and a half from the commencement of symptoms, and probably within two hours from the taking of the poison. The autopsy showed no corrugation of the tongue or inner surface of the lining membrane of the mouth, and no appearance of the action of a corrosive upon the lips, fauces, or mucous membrane of the œsophagus. The whole of the mucous membrane of the stomach was intensely congested, of a dark and almost black colour, the rest of the viscera were healthy. Chemical analysis separated antimony equivalent to nearly a grm. (15 grains) of the chloride, with a small quantity of arsenic, from the contents of the stomach.

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§ 763. Detection of Antimony in Organic Matters.—In acute poisoning by tartar emetic it is not impossible to find a mere trace only in the stomach, the greater part having been expelled by vomiting, which nearly always occurs early, so that the most certain method is, where possible, to analyse the ejected matters. If it should be suspected that a living person is being slowly poisoned by antimony, it must be remembered that the poison is mainly excreted by the kidneys, and the urine should afford some indication. The readiest way to test is to collect a considerable quantity of the urine (if necessary, two or three days’ excretion), concentrate by evaporation, acidify, and then transfer the liquid to a platinum dish, in which is placed a slip of zinc. The whole of the antimony is in time deposited on the platinum dish, and being thus concentrated, may be subsequently identified in any way thought fit.

Organic liquids are boiled with hydrochloric acid; organic solids are extracted with the same acid in the manner described (p. 51); or, if the distillation process given at p. 576 be employed, the antimony may be found partly in the distillate, and partly in the retort. In any case, antimony in solution may be readily detected in a variety of ways—one of the most convenient being to concentrate on tin or platinum, to dissolve out the antimonial film by sulphide of ammonium, and thus produce the very characteristic orange sulphide.

If a slip of pure tinfoil be suspended for six hours in a solution, which should not contain more than one-tenth of its bulk of ClH, and exhibit no stain or deposit, it is certain that antimony cannot be present. It may also conveniently be deposited on a platinum dish,[813] by filling the same with the liquid properly acidulated, and inserting a rod of zinc; the metallic antimony can afterwards be washed, dried, and weighed.

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Reinsch’s and Marsh’s tests have been already described (pp. 558 and 559), and require no further notice. There is, however, a very beautiful and delicate means of detecting antimony, which should not be omitted. It is based upon the action of stibine (SbH₃) on sulphur.[814] When this gas is passed over sulphur, it is decomposed according to equation, 2SbH₃ + 6S = Sb₂S₃ + 3SH₂, the action taking place slowly in diffused daylight, but very rapidly in sunshine. An ordinary flask for the evolution of hydrogen (either by galvanic processes or from zinc and sulphuric acid), with its funnel and drying-tubes, is connected with a narrow tube having a few fragments of sulphur, kept in place by plugs of cotton wool. The whole apparatus is placed in sunshine; if no orange colour is produced when the hydrogen has been passing for some time, the liquid to be tested is poured in gradually through the funnel, and if antimony should be present, the sulphur acquires a deep orange colour. This is distinct even when so small a quantity as ·0001 grain has been added through the funnel. The sulphide of antimony thus mixed with sulphur can, if it is thought necessary, be freed from the sulphur by repeated exhaustion with bisulphide of carbon. The stibine does not, however, represent all the antimony introduced, a very large proportion remaining in the evolution flask;[815] hence it cannot be employed for quantitative purposes. Moreover, the test can, of course, only be conveniently applied on sunny days, and is, therefore, in England more adapted for summer.[816] Often, however, as mentioned elsewhere, when the analyst has no clue whatever to the nature of the poison, it is convenient to pass SH₂ in the liquid to saturation.[817] In such a case, if antimony is present (either alone or in combination with other sulphides), it remains on the filter, and must be separated and identified as follows:—The sulphides are first treated with a solution of carbonate of ammonia, which will dissolve arsenic, if present, and next saturated in situ with pure sulphide of sodium, which will dissolve out sulphide of antimony, if present. The sulphide of antimony will present the chemical characters already described, more particularly—

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(1) It will evolve SH₂ when treated with HCl, and at the same time pass into solution.[818]

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(2) The solution evaporated to get rid of free HCl gives with water a thick cheesy precipitate of basic chloride of antimony. This may be seen if only a drop or two of the solution be taken and tested in a watch-glass.

(3) If tartaric acid be added to the solution, this precipitation does not occur.

(4) The solution from (3) gives an orange precipitate with SH₂.

Such a substance can only be sulphide of antimony. With regard to (2), bismuth would act similarly, but under the circumstances could not be present, for the sulphide of bismuth is insoluble in sodic sulphide.

§ 764. Quantitative Estimation.—The quantitative estimation of antimony is best made by some volumetric process, e.g., the sulphide can be dissolved in HCl, some tartrate of soda added, and then carbonate of soda to weak alkaline reaction. The strength of the solution of tartarised antimony thus obtained can now be estimated by a decinormal solution of iodine, the end reaction being indicated by the previous addition of a little starch solution, or by a solution of permanganate of potash, either of which should be standardised by the aid of a solution of tartar emetic of known strength.

3. CADMIUM.

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II.—PRECIPITATED BY HYDRIC SULPHIDE IN HYDROCHLORIC ACID SOLUTION—BLACK.
Lead—Copper—Bismuth—Silver—Mercury.

1. LEAD.

§ 772. Lead, Pb = 207.—Lead is a well-known bluish-white, soft metal; fusing-point, 325°; specific gravity, 11·36.

Oxides of Lead.—The two oxides of lead necessary to notice here briefly are—litharge and minium.

Litharge, or Oxide of Lead, PbO = 223; specific gravity, 9·2 to 9·5—Pb 92·82 per cent., O 7·18—is either in crystalline scales, a fused mass, or a powder, varying in colour (according to its mode of preparation) from yellow to reddish-yellow or orange. When prepared below the temperature of fusion it is called “massicot.” It may be fused without alteration in weight; in a state of fusion it dissolves silicic acid and silicates of the earths. It must not be fused in platinum vessels.

Minium, or Red Lead, 2PbO, PbO₂; specific gravity, 9·08, is a compound of protoxide of lead with the dioxide. It is of a brilliant red colour, much used in the arts, and especially in the preparation of flint-glass.

§ 773. Sulphide of Lead, PbS = 239; Pb, 86·61 per cent., S, 13·39 per cent., occurring in the usual way, is a black precipitate insoluble in water, dilute acids, alkalies, and alkaline sulphides. It dissolves in strong nitric acid with separation of sulphur, and in strong hydrochloric acid, with evolution of SH₂. Fuming nitric acid does not separate sulphur, but converts the sulphide into sulphate.

§ 774. Sulphate of Lead, PbSO₄ = 303; specific gravity, 6·3; PbO, 73·61 per cent., SO₃, 26·39 per cent., when produced artificially is a heavy white powder, of great insolubility in water, 22,800 parts of cold water dissolving only one of lead sulphate; and if the water contains sulphuric acid, no less than 36,500 parts of water are required. The salts of ammonia (especially the acetate and tartrate) dissolve the sulphate, and it is also soluble in hyposulphite of soda. The sulphate can be readily changed into the carbonate of lead, by boiling it with solutions of the alkaline carbonates. The sulphate of lead, fused with cyanide of potassium, yields metallic lead; it may be also reduced on charcoal, and alone it may be fused without decomposition, provided reducing gases are excluded.

§ 775. Acetate of Lead, Sugar of Lead, Pb(C₂H₃O₂)₂3OH₂ = 379, is found in commerce in white, spongy masses composed of acicular crystals. It may, however, be obtained in flat four-sided prisms. It has a sweet metallic taste, is soluble in water, and responds to the usual tests for lead. The P.B. directs that 38 grains dissolved in water require, for complete precipitation, 200 grain measures of the volumetric solution of oxalic acid, corresponding to 22·3 grains of oxide of lead.

§ 776. Chloride of Lead, PbCl₂ = 278; specific gravity, 5·8; Pb, 74·48 per cent., Cl, 25·52 per cent., is in the form of brilliant crystalline needles. It is very insoluble in cold water containing hydrochloric or nitric acids. According to Bischof, 1635 parts of water containing nitric acid dissolve one part only of chloride of lead. It is insoluble in absolute alcohol, and sparingly in alcohol of 70 to 80 per cent. It fuses below red heat without losing weight; at higher temperatures it may be decomposed.

Carbonate of Lead.—The commercial carbonate of lead (according to the exhaustive researches of Wigner and Harland[821]) is composed of a mixture of neutral carbonate of lead and hydrate of lead, the best mixture being 25 per cent. of hydrate, corresponding to an actual percentage of 12·3 per cent. carbonic acid. The nearer the mixture approximates to this composition the better the paint; whilst samples containing as much as 16·33 per cent., or as little as 10·39 per cent., of CO₂ are practically useless.

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§ 777. Preparations of Lead used in Medicine, the Arts, &c.

(1) Pharmaceutical:—

Lead Plaster (Emplastrum plumbi) is simply a lead soap, in which the lead is combined with oleic and margaric acids, and contains some mechanically included glycerin.

Lead Iodide, PbI₂, is contained in the Emplastrum plumbi iodidi to the extent of 10 per cent., and in the Unguentum plumbi iodidi to the extent of about 12·5 per cent.

Acetate of Lead is contained in a pill, a suppository, and an ointment. The pill (Pilula plumbi cum opio) contains 75 per cent. of lead acetate, and 12·5 per cent. of opium, the rest confection of roses. The suppository (Suppositoria plumbi composita) contains 20 per cent. of acetate of lead, and 6·6 per cent. of opium, mixed with oil of theobroma. The ointment (Unguentum plumbi acetatis) contains 20·6 per cent. of lead acetate, mixed with benzoated lard.

The solution of subacetate of lead (Liquor plumbi subacetatis) is the subacetate, Pb(C₂H₃O₂)₂PbO, dissolved in water; it contains nearly 27 per cent. of subacetate.

A dilute solution of the stronger, under the name of Liquor plumbi subacetatis dilutus, and commonly called Goulard water, is prepared by mixing 1 part (by volume) of the solution and 1 part of spirit, and 78 parts of distilled water; the strength is equal to 1·25 per cent.

There is an ointment, called the Compound Ointment of subacetate of lead, which contains the subacetate in about the proportion of 2 per cent. of the oxide, the other constituents being camphor, white wax, and almond oil.

Carbonate of Lead.—The ointment (Unguentum plumbi carbonatis) should contain about 12·5 per cent. of the carbonate, and the rest simple ointment.

(2) Quack Nostrums, &c.:—

The quack medicines composed of lead are not very numerous.

Liebert’s Cosmetique Infaillible is said to have for its basis nitrate of lead.

One of “Ali Ahmed’s Treasures of the Desert,” viz., the antiseptic malagma, is a plaster made up of lead plaster 37·5 per cent., frankincense 25 per cent., salad oil 25 per cent., beeswax 12·5 per cent.

Lewis’ Silver Cream contains white precipitate and a salt of lead.

Goulard’s Balsam is made by triturating acetate of lead with hot oil of turpentine.

There are various ointments in use made up of litharge. Some herbalists in the country (from cases that have come under the writer’s own knowledge) apply to cancerous ulcers, &c., a liniment of linseed and other common oils mixed with litharge and acetate of lead.

Acetate of lead may also be found as a constituent of various eye-waters.

(3) Preparations of Lead used in the Arts, &c.:—

Ledoyen’s Disinfecting Fluid has for its basis nitrate of lead.

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