The fourth genus of the metallic irritants includes the preparations of antimony. Poisoning with antimonial preparations is not common. They are employed extensively in medicine, however, and consequently accidents have sometimes occurred with them. One of them is also often foolishly used, in the way of amusement, to cause sickness and purging, and likewise to detect servants who are suspected of making free with their mistress’s tea-box or whisky-bottle; and in both of these ways alarming effects have sometimes been produced. In 1837 a woman was tried in England for attempting to poison a child with tartar-emetic; but the poison appeared to have been given through ignorance.[1129] In large doses some of the antimonial compounds may cause death; and one of them, the chloride of antimony, now very little used in this country, is a violent corrosive.
Metallic antimony has a bluish-white colour, not liable to tarnish. Its specific gravity is 6·7. It is easily fused, but is not very volatile. In certain circumstances, however, it easily undergoes a spurious sublimation, by being carried along with gases disengaged while it is in the act of being reduced.
A great number of preparations of antimony were at one time to be found in the shop of the apothecary; but they are now reduced to a few. Those which require notice here are the oxide, chloride, and tartar-emetic.
The oxide [sesquioxide] is a white heavy powder, which is best known by its solubility in tartaric acid, and the effects of the tests for tartar-emetic on the solution.
The chloride [sesquichloride], as usually seen, is a yellow or reddish liquid, but when pure is colourless. It is highly corrosive. It is readily known by the effect of water in decomposing it,—an insoluble white subchloride being thrown down, and hydrochloric acid remaining in solution. The latter is detected by nitrate of silver; and the precipitate is known by being soluble in a solution of tartaric acid, and then presenting the reactions of tartar-emetic.
In its solid state tartar-emetic forms regular tetraedral or more generally octaedral crystals, which are colourless when pure, efflorescent, and of a slightly metallic taste. As commonly seen in the shops it is in the form of a white, or pale yellowish-white powder.
When heated it decrepitates and then chars; and if the heat be increased the oxide of antimony is reduced by the carbonaceous matter, and little globules appear, like those of quicksilver in point of colour. The best way of reducing tartar-emetic is to char it in a porcelain vessel or watch-glass, and then to increase the heat till the charred mass takes fire. Or the charred mass may be introduced into a tube and heated strongly with the blowpipe, after which globules of antimony will be found lining the bottom of the glass where the material has been. None of it is ever sublimed. It is not easy to procure distinct globules by heating tartar-emetic at once in a small tube.
According to Dr. Duncan, tartar-emetic is soluble in three parts of boiling and fifteen of temperate water. The solution presents the following characters with reagents.
1. Caustic potass precipitates a white sesquioxide, but only if the solution is tolerably concentrated. The first portions of the test have no effect. The precipitate is redissolved by an excess of potass.
2. Nitric acid throws down a white precipitate, and takes it up again when added in excess.
3. The Infusion of Galls causes a dirty, yellowish-white precipitate; but it will not act on a solution which contains much less than two grains per ounce.
4. The best liquid reagent is Hydrosulphuric acid. In a solution containing only an eighth part of a grain per ounce, it strikes an orange-red colour, which, when the excess of gas is expelled by heat, becomes an orange-red precipitate; and if the proportion of salt is greater, the precipitate is thrown down at once.—The colour of the precipitate is so peculiar as to distinguish it from every other sulphuret; but if any doubt regarding its nature should occur, it may be known by collecting it, dissolving it with the aid of gentle heat in hydrochloric acid, and adding water to the solution; which will then yield a white precipitate, the sesquioxide of antimony in union with a little chlorine.
5. When the solution is put into Marsh’s apparatus for detecting arsenic [p. 211], the flame yields a dark brownish-black, obscurely shining crust on a surface of porcelain held across it, and a white crystalline powder if the porcelain be held just above the flame. The dark crust is antimony, the white one its oxide. The former has only a distant resemblance to the brilliant stain of arsenic, notwithstanding all that has been said of their similarity. It is well, however, to use some other test for distinguishing the two metals besides their appearance; and the most convenient is a solution of chloride of lime, which instantly makes an arsenical crust disappear, but does not affect an antimonial one.
Tartar-emetic, like the soluble salts of mercury and copper, is decomposed by various organic principles. All vegetable substances that contain a considerable quantity of tannin have this effect; of which an example has been already mentioned in the action of infusion of galls. Decoctions of cinchona-bark decompose it still more effectually. The animal principles do not act on tartar-emetic, with the exception of milk, which is slightly coagulated by a concentrated solution. Many vegetable and animal substances, though they do not decompose it, alter the operation of the fluid tests. Thus tea, though it does not effect any distinct decomposition of the salt, will prevent the action of gall-infusion; and French wine gives a violet tint to the precipitates with that test and with acids.[1130] Hydrosulphuric acid, however, acts under all circumstances, and always characteristically, whatever the colour of the fluid may be. Dr. Turner found that when transmitted through a diluted solution in tea, porter, broth, and milk, with certain precautions to be mentioned presently, he procured a precipitate which either showed its proper colour at once, or did so at the margin of the filter on which it was collected.[1131]
The circumstances now referred to render it necessary to resort to other means, besides the simple application of liquid reagents, for the purpose of detecting tartar-emetic in complex organic mixtures. This subject has been ably investigated, first by Dr. Turner,[1132] and afterwards by Professor Orfila.[1133] The result of the researches of both seems to me to be that the most convenient method yet proposed is the following.
Process for Tartar-emetic in Organic Mixtures.—If the subject of analysis be not already liquid enough, add distilled water. Then acidulate with a little hydrochloric and tartaric acids; the former of which throws down some animal principles, while the latter dissolves readily all precipitates formed with tartar-emetic by reagents or organic principles except the sulphuret. Filter the product.
1. Subject a small portion of the liquid to a stream of hydrosulphuric acid gas, and if it be perceptibly coloured orange-red, treat the whole liquid in the same way; boil to expel the excess of gas, collect the precipitate, dry it, and reduce it by hydrogen gas in the following manner. Put the sulphuret in a little horizontal tube, transmit hydrogen through the tube by means of the apparatus represented in Figure 9, and when all the air of the apparatus is expelled, apply heat to the sulphuret with a spirit-lamp. Hydrosulphuric acid gas is evolved, and metallic antimony is left, if the current of hydrogen be gentle, or it is sublimed if the current be rapid.—When there is much animal or vegetable matter present in the sulphuret, the metal is not always distinctly visible. In that case, dissolve the antimony by the action of nitric acid on the mixed material and broken fragments of the tube, and throw down the orange sulphuret again from the neutralized solution by hydrosulphuric acid.
2. If hydrosulphuric acid do not distinctly affect the liquid, or if no precipitate be separated after boiling, or so small a quantity as cannot well be collected,—evaporate the liquid to dryness, char it by means of nitric acid and chlorate of potash, as directed for copper (p. 357), boil the carbonaceous mass for half an hour in a mixture of eight parts of hydrochloric acid and one of nitric acid, and introduce the filtered solution into the modification of Marsh’s apparatus for detecting arsenic described in page 204, but without the tube e h. Kindle the gas at e, and try whether a black, dull stain, not removable by solution of chloride of lime, be produced on a surface of porcelain held across the flame. If no stain be produced, there was no antimony in the liquid under examination. If the porcelain be stained, apply the heat of a spirit-lamp flame to the tube d e. Antimony will be deposited within the tube where the heat is applied. In order to ascertain its nature, break the tube, heat the portion containing the crust with nitro-hydrochloric acid, evaporate to dryness, dissolve the residue in hydrochloric acid, decompose a part of this solution with water, and subject the rest to a stream of hydrosulphuric acid gas, which will produce the usual orange sulphuret of antimony.
3. If antimony be not indicated in either of these ways in the fluid part of the subject of analysis, the solid portion may next be subjected to the second process; but success will very seldom attend the search when the previous steps have failed.
The first branch of this process,—a slight modification of Dr. Turner’s,—is a very delicate and satisfactory method of detecting antimony in organic mixtures. Some practice is required to transmit the hydrogen gas with the proper rapidity. The gas ought to be allowed to pass for some time before the spirit-lamp flame is applied, otherwise the oxygen remaining in the apparatus may cause an explosion, or will oxidate the metallic antimony, formed by the reduction of the sulphuret. As soon as the reduction of the sulphuret begins, the tube is blackened on account of the action of the sulphuretted-hydrogen on the lead contained in the glass. This obscures the operations within the tube; but on subsequently breaking it, a metallic button or a sublimate will be easily seen. When the sulphuret is considerable in quantity and the gaseous current slow, the metal remains where the sulphuret was; but if the mass of sulphuret is small and the current rapid, then the metal is sublimed and condensed in minute scaly brilliant crystals.
The second branch of the process is a modification of the method lately employed by Professor Orfila for detecting antimony in the textures and secretions of animals poisoned with tartar-emetic. It is probably more delicate than the other, but not more satisfactory.
The method of analysis here recommended, as well as every other yet proposed for organic mixtures, merely detects the presence of antimony. It does not indicate the state in which the metal was combined. It is a process in short for antimony in every state of combination.
It is almost unnecessary to observe that when the contents of the stomach or vomited matters are the subject of analysis, care must be taken to ascertain that tartar-emetic was not administered as a remedy.
There is little peculiarity in what is hitherto known of the symptoms of poisoning with tartar-emetic in man. Cases in which it has been taken to the requisite extent are rarely met with; and it has seldom remained long enough in the stomach to act deleteriously. But its action on animals would appear from the experiments of Magendie to be in some respects peculiar.
He found that dogs, like man, may take a large dose with impunity, for example half an ounce, if they are allowed to vomit; but that if the gullet is tied, from four to eight grains will kill them in a few hours. His subsequent experiments go to prove that death is owing to the poison exciting inflammation in the lungs. When six or eight grains dissolved in water were injected into a vein, the animal was attacked with vomiting and purging, and death ensued commonly within an hour. In the dead body he found not only redness of the whole villous coat of the stomach and intestines, but also that the lungs were of an orange-red or violet colour throughout, destitute of crepitation, gorged with blood, dense like the spleen, and here and there even hepatized. A larger quantity caused death more rapidly without affecting the alimentary canal; a smaller quantity caused intense inflammation there and death in twenty-four hours; but the lungs were always more or less affected.[1134]
It is a fact, too, worthy of notice, that in whatever way this poison enters the body its effects are nearly the same. This is shown not only by the researches of Magendie already mentioned, but likewise by the experiments of Schloepfer, who found that a scruple dissolved in twelve parts of water and injected into the windpipe, caused violent vomiting, difficult breathing, and death in three days; and in the dead body the lungs and stomach were much inflamed, particularly the former.[1135] It farther appears from an experiment related by Dr. Campbell, that, when applied to a wound, it acts with almost equal energy as when injected into a vein. Five grains killed a cat in this way in three hours, causing inflammation of the wound, and vivid redness of the stomach.[1136] He did not find the lungs inflamed.
Magendie infers from his own researches that tartar-emetic occasions death when swallowed, not by inflaming the stomach, but through means of a general inflammatory state of the whole system subsequent to its absorption,—of which disorder the affection of the stomach and intestines and even that of the lungs are merely parts or symptoms. The later experiments of Rayer tend in some measure to confirm these views, by showing that death may occur without inflammation being excited any where. In animals killed in twenty-five minutes by tartar-emetic applied to a wound, he, like Dr. Campbell, could see no trace of inflammation in any organ of the great cavities.[1137]
Orfila has proved by analysis the important fact that tartar-emetic is absorbed in the course of its action, and may be detected in the animal tissues and secretions. He found that, when it is applied to the cellular tissue of small dogs, two grains disappear before death: That antimony may be detected by his process given above throughout the soft textures generally, but especially in the liver and kidneys: but that it is quickly discharged from these quarters through the medium of the urine. Hence in an animal that died in four hours he found it abundantly in the liver and still more in the urine; in one that survived seventeen hours, the liver presented mere traces of the poison, but the urine contained it in abundance; and in one that lived thirty-six hours, there was a large quantity in the urine, but none at all in the liver. He also ascertained that antimony is generally to be found in the urine of persons who are taking tartar-emetic continuously in large doses for pneumonia according to Rasori’s mode of administering it.[1138] These results have been confirmed by the conjoined researches of Panizza and Kramer, who found antimony in the urine and blood of a man during a course of tartar-emetic.[1139] And Flandin and Danger also satisfied themselves that in animals it may be generally detected in the liver.[1140]
Effects on Man.—When tartar-emetic is swallowed by man, it generally causes vomiting very soon and is all discharged; and then no other effect follows. But if it remains long in the stomach before it excites vomiting, or if the dose be large, more permanent symptoms are sometimes induced. The vomiting recurs frequently, and is attended with burning pain in the pit of the stomach, and followed by purging and colic pains. There is sometimes a sense of tightness in the throat, which may be so great as to prevent swallowing. The patient is likewise tormented with violent cramps. Among the cases hitherto recorded no notice is taken of pulmonary symptoms; which might be expected to occur if Magendie’s experiments are free of fallacy.
The late introduction of large doses of tartar-emetic into medical practice having excited some doubt as to its poisonous properties, it becomes a matter of some moment to possess positive facts on the subject. The following cases may therefore be quoted, which will satisfy every one that this substance is sometimes an active irritant.
The first is particularly interesting from its close resemblance to cholera. It occurred in consequence of an apothecary having sold tartar-emetic by mistake for cream of tartar. The quantity taken was about a scruple. A few moments afterwards the patient complained of pain in the stomach, then of a tendency to faint, and at last he was seized with violent bilious vomiting. Soon after that he felt colic pains extending throughout the whole bowels, and accompanied ere long with profuse and unceasing diarrhœa. The pulse at the same time was small and contracted, and his strength failed completely; but the symptom which distressed him most was frequent rending cramp in the legs. He remained in this state for about six hours, and then recovered gradually under the use of cinchona and opium; but for some time afterwards he was liable to weakness of digestion.[1141]
The next case to be mentioned, where the dose was forty grains, proved fatal, although the person vomited soon after taking it. The symptoms illustrate well the compound narcotico-acrid action often observed in animals. The poison was taken voluntarily. Before the person was seen by M. Récamier, who relates the case, he had been nearly two days ill with vomiting, excessive purging, and convulsions. On the third day he had great pain and tension in the region of the stomach, and appeared like a man in a state of intoxication. In the course of the day the whole belly became swelled, and at night delirium supervened. Next day all the symptoms were aggravated; towards evening the delirium became furious; convulsions followed; and he died during the night, not quite five days after taking the poison.[1142]
Severe effects have also been caused by so small a dose as six grains. A woman, who swallowed this quantity, wrapped in paper, was seized in half an hour with violent vomiting, which soon became bloody. In two hours the decoction of cinchona was administered with much relief. But she had severe colic, diarrhœa, pain in the stomach, and some fever; of which symptoms she was not completely cured for five days.[1143] A case has been published, where a dose of only four grains caused pain in the belly, vomiting, and purging, followed by convulsions, failure of the pulse, and loss of speech; and recovery took place very slowly.[1144] Under the head of the treatment another case will be noticed where half a drachm excited severe symptoms, and was probably prevented from proving fatal only by the timely use of antidotes.
While these examples prove that tartar-emetic is occasionally an active irritant in the dose of a scruple or less, it must at the same time be admitted to be uncertain in its action as a poison. This appears from the late employment of it in large doses as a remedy for inflammation of the lungs. The administration of tartar-emetic in large doses was a common enough practice so early as the seventeenth century, and was also occasionally resorted to by physicians between that and the present time. But it is only in late years that, by the recommendations of Professor Rasori of Milan,[1145] and M. Laennec of Paris, it has again become a general method of treatment. According to this method, tartar-emetic is given to the extent of twelve, twenty, or even thirty grains a day in divided doses; and not only without producing any dangerous irritation of the alimentary canal, but even also not unfrequently without any physiological effect whatever. Doubts were at one time entertained of the accuracy of the statements to this effect published by foreign physicians; but these doubts are now dissipated, as the same practice has been tried, with the same results, by many in Britain. Rasori ascribes the power the body possesses of enduring large doses of tartar-emetic without injury, to a peculiar diathesis which accompanies the disease and ceases along with it. And it is said, that the same patients, who, while the disorder continues, may take large doses with impunity, are affected in the usual manner, if the doses are not rapidly lessened after the disease has begun to give way. The testimony of Laennec on the subject is impartial and decisive. He observes he has given as much as two grains and a half every two hours till twenty grains were taken daily, and once gave forty grains in twenty-four hours by mistake; that he never saw any harm result; and that vomiting or diarrhœa was seldom produced, and never after the first day. The power of endurance he found to diminish, but not, as Rasori alleges, to cease altogether, when the fever ceases; for some of his patients took six, twelve, or eighteen grains daily when in full convalescence.[1146] My own observations correspond with Laennec’s, except as to the effects of large doses during convalescence, of which effects I have had no experience. I have seen from six to twenty grains, given daily in several doses of one or two grains, check bad cases of pneumonia and bronchitis, without causing vomiting or diarrhœa after the first day, and also without increasing the perspiration. At the same time I have twice seen the first two or three doses excite so violent a purging and pain in the stomach and whole bowels, that I was deterred from persevering with the remedy. In continued fever too I have repeatedly found that the doses mentioned above did not cause any symptoms of irritation in the stomach or intestines.
The large quantities now mentioned have even been sometimes given in a single dose with nearly the same results. Dr. Christie mentions in his Treatise on Cholera that he sometimes gave a scruple in one dose with the effect of exciting merely some vomiting and several watery stools. But he admits that in one instance symptoms were induced like those of a case of violent cholera.[1147]
The same large doses have been given by some in delirium tremens without any poisonous effect being produced. A correspondent of the Lancet has even mentioned that on one occasion, after gradually increasing the dose, he at last wound up the treatment, successfully as regarded the disease, and without any injury to the patient, by giving four doses of twenty grains each, in the course of twenty minutes.[1148]
These facts are sufficiently perplexing, when viewed along with what were previously quoted in support of the poisonous effects of tartar-emetic. On a full consideration of the whole circumstances, however, I conceive the conclusion which will be drawn is, that this substance is not so active a poison as was till lately supposed;—that in the dose of four, six, or ten grains, it may cause severe symptoms, but is uncertain in its action,—and that although there appears to be some uncertainty in the effects of even much larger doses, such as a scruple, yet in general violent irritation will then be induced, and sometimes death itself.
An instance is related in the Journal Universel of a man who, while in a state of health, swallowed seventeen grains, and then tried to suffocate himself with the fumes of burning charcoal. He recovered, though not without suffering severely from the charcoal fumes; but he could hardly be said to have been affected at all by the tartar-emetic.[1149] Here the inactivity of the poison was probably owing to the narcotic effects of the fumes.
The effects of tartar-emetic on the skin are worthy of notice; but they have not yet been carefully studied. Some facts tend to show that even its constitutional action may be developed through the sound skin. Mr. Sherwen attempted to prove by experiments on himself and two pupils, that five or seven grains in solution will, when rubbed on the palms, produce in a few hours nausea and copious perspiration.[1150] His observations have been confirmed by Mr. Hutchinson.[1151] But Savary, a French physician, on repeating these experiments, could remark nothing more than a faint flat taste and slight salivation;[1152] and Mr. Gaitskell could not remark any constitutional effect at all.[1153] Sometimes it has appeared to cause severe symptoms of irritant poisoning when used in the form of ointment to excite a pustular eruption. An instance of this has been described in a late French Journal.[1154] Nay, in the Medical Repository there is a case, in which the external use of tartar-emetic ointment is supposed to have been the cause of death. The subject was an infant, two years old, who, soon after having the spine rubbed with this ointment, was seized with great sickness and frequent fainting, which in forty-eight hours proved fatal.[1155] Considering the numerous opportunities which medical men have had of witnessing the effects of tartar-emetic applied in the same manner, and that these are solitary cases, doubts may be entertained whether the irritant symptoms in the one case, or the child’s death in the other, were occasioned in the way supposed.
Although the constitutional action of tartar-emetic is not easily developed through the sound skin, its local effects are severe and unequivocal. When applied to the skin it does not corrode, but excites inflammation, on which account it is much used instead of cantharides. It does not blister; but after being a few days applied, it brings out a number of painful pustules; if it be persevered in, the skin ulcerates; and if it be applied to an ulcerated surface it causes profuse suppuration, or sometimes even sloughing.
Tartar-emetic is one of the substances which appear to possess the property of acting on the infant through the medium of its nurse’s milk. I do not know, indeed, what may be the general experience on this point; but a French physician, M. Minaret, has published a clear case of the kind, in the instance of a young woman who was taking tartar-emetic for pleurisy, and whose infant was attacked with a fit of vomiting immediately after every attempt to suck the breast.[1156]
There is some reason to suppose, that the vapours of antimony may prove injurious when inhaled. Four persons, constantly exposed in preparing antimonial compounds to the vapour of antimonious acid and chloride of antimony, were attacked with headache, difficult breathing, stitches in the back and sides, difficult expectoration of viscid mucus, want of sleep and appetite, mucous discharge from the urethra, loss of sexual propensity, atrophy of the testicles, and a pustular eruption on various parts, but especially on the scrotum. They all recovered.[1157]
The morbid appearances caused by tartar-emetic have not been often witnessed in man.
In M. Récamier’s case there were some equivocal signs of reaction in the brain. The organs in the chest were healthy. The villous coat of the stomach, except near the gullet, where it was healthy, was everywhere red, thickened, and covered with tough mucus. The whole intestines were completely empty. The duodenum was in the same state as the stomach; but the other intestines were in their natural condition.
M. Jules Cloquet observed in the body of a man who died of apoplexy, and who in the course of five days had taken forty grains of tartar-emetic, without vomiting or purging,—that the villous coat of the stomach had a deep reddish-violet colour, with cherry-red spots interspersed; and that the whole small intestines were of a rose-red tint spotted with cherry-red.[1158]
The only other dissection I have seen noticed is one by Hoffmann. He says that in a woman poisoned by tartar-emetic he found the stomach gangrenous, and the lungs, diaphragm, and spleen as it were in a state of putrefaction.[1159] Little credit can be given to this description.
In animals Schloepfer found the blood always fluid.[1160]
The treatment of poisoning with tartar-emetic is simple. If the poison be not already discharged, large draughts of warm water should be given and the throat tickled, to bring on vomiting. At the same time some vegetable decoction should be prepared, which possesses the power of decomposing the poison; and none is better or more likely to be at hand than a decoction of cinchona-bark, particularly yellow-bark. The tincture is also a good form for giving this antidote. The administration of bark has been found useful even after vomiting had continued for some length of time, probably because a part of the poison nevertheless remained undischarged. Before the decoction is ready, it is useful to administer the bark in powder. It is alleged, however, by M. Toulmouche that decoction of cinchona is not nearly so serviceable as infusion of galls, and that powder of galls is better still.[1161] When there is reason to believe that the patient has vomited enough, and that a sufficient quantity of the antidote has been taken, opium is evidently indicated and has been found useful; but venesection may be previously necessary if the signs of inflammation in the stomach are obstinate.
The following case related by M. Serres was probably cured by cinchona. At all events, the effect of the antidote was striking. A man purchased half a drachm in divided doses at different shops, and swallowed the whole in a cup of coffee. Very soon afterwards he was attacked with burning pain in the stomach, convulsive tremors, and impaired sensibility,—afterwards with cold clamminess of the skin, hiccup, and some swelling of the epigastrium, but not with vomiting. Decoction of cinchona was given freely. From the first moment almost of its administration he felt relief, and began to sweat and purge. Next morning, however, he vomited, and for some days there were evident signs of slight inflammation in the stomach; nay, for a month afterwards he had occasional pricking pains in that region; but he eventually recovered.[1162] Another and more pointed case has been related by Dr. Sauveton of Lyons. A lady swallowed by mistake for whey a solution of sixty grains of tartar emetic. In ten minutes she was seen by her physician, and at this time vomiting had not commenced. Tincture of bark was immediately given in large doses. No unpleasant symptom occurred except nausea and slight colic.[1163]
Orfila considers that the diuretic plan of treatment recommended by him for arsenic [p. 288] is equally applicable in the case of antimony. Having ascertained that a grain and a half of tartar-emetic applied to a wound constantly killed dogs in a period varying from seventeen to thirty-six hours, if no treatment was employed,—he administered to them in this way a dose varying from a grain and a half to three grains, and by then giving diuretics effected a cure in four out of five instances.[1164]
The chloride of antimony [sesquichloride, muriate, or butter of antimony] being now put to little use and seldom seen except as an intermediate product obtained in the preparation of other compounds of antimony, it is rarely met with as the cause of poisoning, and therefore scarcely deserves notice here, were it not that its effects differ widely from those of tartar-emetic and other antimonials.
It is easily known by the characters mentioned above. It has not yet been made the subject of investigation by experiments on the lower animals. Mr. Taylor has collected three cases of poisoning with it, which show that it is a powerful corrosive and irritant, and that its effects, as hitherto witnessed, seem to depend entirely on this action. In one instance, that of a boy, twelve years old, who swallowed four or five drachms of the solution by mistake for ginger-beer, the symptoms were vomiting in half an hour, then faintness and extreme feebleness, and next day heat in the mouth and throat, difficulty in swallowing, slight abrasions of the lining membrane of the mouth, and general fever; but he got quite well in eight days. In the case of another boy, ten years old, who got about the same quantity by mistake for antimonial wine, there was an immediate sense of choking and inability to speak, then vomiting and pain in the throat, next a general state of collapse, with dilated pupils and a tendency to stupor, and on the subsequent day bright scarlet patches on the throat, with difficulty of swallowing. This patient also recovered completely in a few days. The third was the case of a surgeon who took intentionally between two and three fluid ounces, and was found in an hour by his medical attendant in a state of great prostration, and affected with severe efforts to vomit, violent griping, and urgent tenesmus. Reaction soon ensued, the pain abated, and the pulse rose to 120; a strong tendency to doze succeeded; and in ten hours and a half he expired. The whole inside of the alimentary canal, from the mouth to the jejunum, was black as if charred; the mucous membrane seemed to have been removed along the whole of this extent of the canal; and the submucous and peritoneal coats were so soft as to be easily torn with the finger.[1165]
Several other metallic compounds produce effects analogous to those of the preparations of arsenic, copper, mercury, and antimony. But they may be passed over shortly; because they are little known as poisons, and it is therefore only necessary that their leading properties be mentioned. They are the compounds of tin, silver, gold, bismuth, chrome, zinc, and iron.
The chlorides of tin are used in the arts of colour-making and dyeing, and the oxide of tin forms part of the putty-powder used for staining glass and polishing silver plate.
There are two chlorides, the protochloride and bichloride. They both form acicular crystals, which are very soluble. It is needless to notice their tests or chemical history; but in order that the following account of their effects on man and animals may be understood, it is necessary to mention, that they are decomposed by almost all vegetable infusions and animal fluids.
Orfila found, that a solution of six grains of the protochloride injected into the jugular vein of a dog killed it in one minute,—that two grains caused death by tetanus in fifteen minutes,—and that so small a quantity as half a grain caused death in twelve hours, the only symptoms being somnolency and catalepsy or fixedness of position.
To these dreadful effects when introduced into the blood, its effects when swallowed are not nearly proportionate. From eighteen to forty-four grains killed dogs in one, two, or three days, efforts to vomit and great depression being the only symptoms; and after death the stomach was found excessively inflamed, and sometimes ulcerated. Its effects when applied externally are still less violent. Two drachms applied to a wound merely caused violent inflammation and sloughing of the part, and death in twelve days, without any internal symptom during life or appearance after death.[1166]
These phenomena, considered along with the violent symptoms excited when the poison is injected into the veins, show that, when swallowed or applied outwardly, it acts only as a local irritant.
Tin is absorbed in the course of its action, and may be detected in the liver, spleen, and urine, by boiling them in water acidulated with hydrochloric acid, evaporating the decoction to dryness, charring the residue by means of nitric acid as directed for copper, treating the carbonaceous mass with a mixture of twenty parts of hydrochloric acid and one of nitric acid, evaporating the solution to dryness so as to expel any excess of acid, dissolving what is left in hydrochloric acid diluted with twice its volume of water, and then transmitting hydrosulphuric acid gas. If the precipitated sulphuret of tin has not a fine yellow colour, it must be heated with a little strong nitric acid; after which, if the residuum be again dissolved in diluted hydrochloric acid, a characteristic yellow bisulphuret will be thrown down by hydrosulphuric acid gas. This process may be applied to all organic mixtures containing tin.[1167]
The oxide of tin, according to Schubarth, is quite inactive; for he gave an entire drachm to a dog without being able to observe any effect from it whatever.[1168] This is what would be expected from its extreme insolubility. Yet Orfila has stated in the early editions of his Toxicology, and repeats in that of 1843, but without noticing the contradictory observations of Schubarth, that one or two drachms of the oxide occasion in dogs all the phenomena of irritant poisoning, and prove invariably fatal.[1169]
The metal has been proved by Bayen and Charlard to be inactive.[1170] It has been given expressly to dogs without any effect being observed; and it is given in large doses to man for worms, without detriment. No importance therefore can be attached to some alleged cases of poisoning with this metal.[1171]
Cases of poisoning with the preparations of tin are rare. Orfila briefly notices a set of cases which occurred to M. Guersent. Several persons in a family took the protochloride, in consequence of the cook having mistaken a packet of it for salt and dressed their dinner with it. They had all colic, some of them diarrhœa; none vomited; and all recovered in a few days.[1172] A case is related in the Medical Times of death apparently caused by so small a quantity as half a tea-spoonful of a solution of protochloride. The effects were vomiting, acute pain in the stomach, anxiety, restlessness, thirst, and a frequent, hard, small pulse. These symptoms increased next day; and on the third day death took place, preceded by delirium.[1173] As this was a case of suicide, it is probable that some other poison, or a larger dose of the chloride of tin was taken.
Little need be said of the morbid appearances. Besides the signs of violent irritation caused by the poisons of tin in common with other irritants, Orfila always found in dogs a peculiar tanned appearance of the villous coat of the stomach. In the case from the Medical Times the gullet was red, the stomach inflamed externally, and internally thickened, vascular, and pulpy.
Of the preparations of silver, the only one which requires notice is the nitrate or lunar caustic.
It exists in two forms,—crystallized in broad, transparent, colourless tables,—and fused into cylindrical, crystalline, grayish pencils. Both forms are essentially the same in chemical nature.—The most convenient tests are, 1, Hydrochloric acid, or any hydrochlorate, which even in a state of extreme dilution causes with it a dense white precipitate, passing, under exposure to light, into dark brown; and 2, Ammonia, followed by the solution of oxide of arsenic; if the nitrate of silver is not too much diluted it gives a dark brown precipitate with ammonia, soluble, however, in an excess of that alkali; and when the solution has thus been restored, arsenic throws down a lively yellow precipitate, passing rapidly to brown, if left exposed to the light.
Most organic substances, but in particular all animal fluids, with the exception of gelatin, decompose nitrate of silver.
It appears from the experiments of Orfila, that, like the chlorides of tin, the nitrate of silver is a deadly poison when introduced into the veins; but that, by reason of its facility of decomposition, it cannot enter the blood through ordinary channels in a quantity sufficient to develope any remote action. When two grains in solution were injected into the jugular vein of a dog it died in six minutes, difficult respiration being the chief symptom; the third part of a grain caused death in four hours and a half, violent tetanus having preceded death; and in both animals the blood in the heart was found very black and the lungs gorged, or vivid red. According to Mr. Blake, the salts of silver when directly introduced into the blood, do not act on the heart, but operate by causing obstruction of the capillary system. If they are injected into the aorta, the systemic capillaries are obstructed, the nervous system is consequently oppressed, respiration is arrested through the medium of this nervous oppression, and death takes place by asphyxia, the heart continuing to beat vigorously. If again they are injected into a great vein, immediate obstruction of the pulmonary capillaries takes place, so that the blood ceases to be transmitted to the left side of the heart.[1174]
To the violent action exerted by nitrate of silver when directly admitted into the blood, its effects through the medium of the stomach bear no proportion or resemblance. Thus, when twelve grains of the salt were introduced into the stomach in the solid state, its effects were so slight as not to be distinguishable from those of the ligature on the gullet practised to prevent its discharge by vomiting. When introduced in a state of solution, however, and in a larger dose, in the dose of 36 grains, for example, it is more energetic. Death ensued in thirty-six hours, but without any particular symptoms; and in the dead body the villous coat of the stomach was found generally softened, and corroded near the pylorus by little grayish eschars like those formed by this poison on the skin.[1175]
Hence it appears that nitrate of silver does not act remotely, but simply as a local irritant and corrosive. The corrosion it produces is incompatible with its absorption in large quantity. This inference is confirmed by the experiments of Schloepfer, on its effects when introduced into the trachea. He found that it caused inflammation of the windpipe, and pneumonia passing on to hepatization of the lungs, but no symptom referrible to a remote action.[1176] Its pure corrosive properties have long pointed it out to the surgeon as the most convenient of all escharotics.
Nitrate of silver is absorbed, however, in the course of its action. It would seem to be absorbed when it is taken medicinally in frequent small doses. It is not easy to account otherwise for the singular blueness of the skin, sometimes observed after the protracted use of lunar caustic as a remedy for epilepsy and other diseases.[1177] The effects of the poison on the constitution in such cases are not very well known. It appears, however, that considerable doses may be taken for a great length of time without injury, and that the first and only unpleasant effects produced by its too free administration are such as indicate simply an injury of the stomach. The only exception to this general statement I have met with is a case by Wedemeyer, where, after the remedy had been taken for six months on account of epilepsy, that disease disappeared, and dropsy, with diseased liver at the same time commenced, and soon proved fatal. It is probable, however, that the nitrate of silver had no share in the ultimate event. In this instance the whole internal organs were more or less blue; and metallic silver, it is said, was found in the pancreas, and in the choroid plexus of the brain.[1178] Silver has been found in the urine of persons who were taking it medicinally. A young man who had used the nitrate for some time observed that his urine became muddy soon after being passed, and that the sediment became black if exposed to the light; and when the sediment was digested in ammonia, chloride of silver was detached by neutralizing the ammoniacal liquor.[1179]
But it also appears that some nitrate of silver is absorbed when it is given in a single large dose. For in animals poisoned with it Orfila found that silver may be detected in the liver and spleen by charring these organs with nitric acid as in the instance of poisoning with copper, and then treating the residue with boiling diluted nitric acid, and adding hydrochloric acid to the solution. He also found silver in the urine by charring the extract with heat, acting on the charcoal with ammonia, and saturating the filtered ammoniacal solution,—chloride of silver being then detached.[1180] These results have been confirmed by the experiments of Drs. Panizza and Kramer of Milan,[1181] who found silver in the blood after the administration both of the nitrate and chloride.
Boerhaave has noticed a case of poisoning with this substance, but in very brief terms. He says it caused gangrene. Schloepfer in his thesis notices a case by Dr. Albers of Bremen in which croup was brought on by a bit of lunar caustic dropping into the windpipe. M. Poumarede has related an instance of poisoning with an ounce of nitrate of silver in solution. A few hours afterwards the individual was found insensible, with the eyes turned up, the pupils dilated, the jaws locked, and the arms and face agitated with convulsions. A solution of common salt was immediately given as an antidote. In two hours there was some return of consciousness, and abatement of the convulsions, but still complete insensibility of the limbs, with redness of the features, and pain in the stomach. In eleven hours he could articulate. For thirty-six hours he continued subject to fits of protracted coma; but he eventually recovered. Sixteen hours after taking the poison he vomited a large quantity of chloride of silver.[1182]
The treatment of poisoning with the nitrate of silver is obvious. The muriate of soda by decomposing it will act as an antidote; and any signs of irritation left will be subdued by opium.
Gold in various states of combination was at one time much used in medicine, and an attempt has been lately made to revive its employment.
Its poisonous properties are powerful, and closely allied to those of the chlorides of tin and nitrate of silver. In the state of chloride it occasions death in three or four minutes when injected into the veins, even in very minute doses; and the lungs are found after death so turgid as to sink in water. But if swallowed, corrosion takes place; the salt is so rapidly decomposed, that none is taken up by the absorbents; and death ensues simply from the local injury.[1183] It has been of late used in medicine in France as an antisyphilitic; but even doses so small as a tenth of a grain have been known to produce an unpleasant degree of irritation in the stomach.[1184]
In the state of fulminating gold, this metal has given rise to alarming poisoning in former times, when it was used medicinally. Plenck in his Toxicologia says it excites griping, diarrhœa, vomiting, convulsions, fainting, salivation; and sometimes has proved fatal.[1185] Hoffmann likewise repeatedly saw it prove fatal, and the most remarkable symptoms were vomiting, great anxiety and fainting. In one of his cases the dose was only six grains.[1186] These compounds are now so little met with that they need not be noticed in greater detail.
Bismuth, in its saline combinations, is also an active poison. One of its compounds, the trisnitrate, white bismuth, or magistery of bismuth, is a good deal used in medicine and the arts; and pearl white, one of the paints used in the cosmetic art, is the tartrate of this metal.
The former substance is an active poison. It is got by dissolving bismuth in nitric acid, and pouring hot water over the crystals; a supernitrate being left in solution, and the trisnitrate thrown down in the form of a white powder.
Orfila found that the soluble part of fifteen grains of the nitrate, when injected into the jugular vein of a dog, caused immediate giddiness and staggering, and death in eight minutes. He also remarked that forty grains mixed with water and introduced into the stomach, caused all the customary signs of irritation, and death in twenty-four hours; and that a great part of the villous coat of the stomach was reduced to a pulpy mass, and likewise exhibited several ulcers.[1187]
Similar effects were produced by the trisnitrate; but a larger dose was required. Two drachms and a half killed a dog in twenty-four hours; and redness and eroded spots were found in the stomach.
In some more recent researches Orfila found that the poison is absorbed, and may be detected, like other metallic poisons, in the liver, spleen, and urine. The process for this purpose, applicable also to all organic mixtures, consists in boiling the solids in water acidulated with a twentieth of nitric acid, evaporating the solution to dryness, charring the residue with nitric acid, as directed for copper, boiling the charcoal in diluted nitric acid, and thus obtaining an acid solution of nitrate of bismuth, which may be known by the effects of water and of hydrosulphuric acid.[1188]
Orfila remarks, that Camerarius of Tübingen once detected the adulteration of wine with the oxide of bismuth, and that the bakers in some parts of England used to render their bread white and heavy by mixing the trisnitrate with flour; but he has not stated his authority for this accusation. It may be discovered in any such mixture by calcining the suspected substance in a crucible, and then separating the metallic bismuth by means of nitric acid. But the adulteration of bread with bismuth is very questionable, as there are many cheaper methods for effecting the purpose, without adding any thing positively deleterious.
The following is the only case with which I am acquainted of poisoning with the preparations of bismuth in the human subject. A man subject to water-brash took two drachms of the trisnitrate with a little cream of tartar by mistake for a mixture of chalk and magnesia. He was immediately attacked with burning in the throat, brown vomiting, watery purging, cramps, and coldness of the limbs, and intermitting pulse, and then with inflammation of the throat, difficult swallowing, dryness of the membrane of the nose, and a constant nauseous metallic taste. On the third day he had hiccup, laborious breathing, and swelling of the hands and face; and suppression of urine was then discovered to have existed from the first. On the fourth day swelling and tension of the belly were added to the pre-existing symptoms, on the fifth day salivation, on the sixth delirium, on the seventh, swelling of the tongue and enormous enlargement of the belly; and on the ninth he expired. The urine continued suppressed till the eighth day.—On inspection of the body it was found that from the back of the mouth to the rectum there were but few points of the alimentary canal free of disease. The tonsils, uvula, pharynx, and epiglottis, were gangrenous, the larynx spotted black, the gullet livid, the stomach very red, with numerous purple pimples, the whole intestinal canal red, and here and there gangrenous, especially at the rectum. The inner surface of the heart was bright red. The kidneys and brain were healthy.[1189]
The next metal whose properties deserve notice is chrome. As it is now extensively used in the art of dyeing it is necessary to mention its effects, more especially as they are singular. They have been ascertained experimentally with great care by Professor Gmelin of Tübingen. He found that in the dose of a grain the chromate of potass had no effect when injected into the jugular vein of a dog,—that four grains produced constant vomiting, and death in six days without any other striking symptom,—and that ten grains caused instant death by paralysing the heart. Its effects, when introduced under the skin, are still more remarkable. It seems to cause general inflammation of the lining membrane of the air-passages. When a drachm was thrust in the state of powder under the skin of the neck of a dog, the first symptoms were weariness and a disinclination to eat. But on the second day the animal vomited, and a purulent matter was discharged from the eyes. On the third day it became palsied in the hind legs; on the fourth it could not breathe or swallow but with great difficulty; and on the sixth it died. The wound was not much inflamed; but the larynx, bronchi, and minute ramifications of the air tubes contained fragments of fibrinous effusion, the nostrils were full of similar matter, and the conjunctiva of the eyes was covered with mucus. In another dog, an eruption appeared on the back, and the hair fell off.[1190]
The effects of the salts of chrome on man have not been well ascertained, but seem to be peculiar. Dr. Schindler of Greifenberg relates the following case of fatal poisoning with bichromate of potash. A colourman having swallowed a solution of it, vomiting was brought on by warm water, soap and oil, and kept up until the discharges ceased to be yellow. The man got apparently well and passed a quiet night; but next morning he felt excessively weary, had stitches in his back and kidneys, passed no urine, and was affected with purging. A restless night followed. On the subsequent morning, he lay motionless and like one fatigued to the extremest degree; in which state he died, fifty-four hours after swallowing the poison. The stomach was healthy, the intestines reddish, the kidneys gorged with blood and marbled internally with dark-red patches, and the bladder empty.[1191]—Mr. Wilson of Leeds has described the case of an elderly man who took the poison in the evening, and was found dead about twelve hours afterwards, without any sign of vomiting, purging, or convulsions; and no morbid appearance was found but redness of the villous coat of the stomach, and an inky-like fluid in it, containing a large quantity of bichromate of potash.[1192]
To these facts may be added another not less singular, which my late colleague Dr. Duncan informed me has been observed by the workmen in Glasgow, who use the bichromate of potass in dyeing. When this salt was first introduced into the art of dyeing, the workmen who had their hands often immersed in its solution were attacked with troublesome sores on the parts touched by it; and the sores gradually extended deeper and deeper, without spreading, till they sometimes actually made their way through the arm or hand altogether.[1193]
The compounds of zinc, which have been long used in considerable doses in medicine, have sometimes occasioned serious and even fatal effects. Partly on this account, and partly because one of them, the sulphate of zinc, being the emetic most commonly used in the treatment of poisoning, is apt to complicate various medico-legal analyses, it will be proper to notice both its physiological properties and the mode of detecting it by chemical means.
The only important compound of this metal is the sulphate or white vitriol. As usually sold in the shops, it forms small, prismatic crystals, transparent, colourless, of a very styptic metallic taste, and exceedingly soluble in water. That which is kept by the apothecary is tolerably pure; but there is a salt sometimes met with in commerce which contains an admixture of sulphate of iron, and with which the natural action of the tests for zinc is materially modified.
The solution of the pure salt is precipitated white by the caustic alkalis, an oxide being thrown down, which is soluble in an excess of ammonia. The alkaline carbonates also precipitate it white, the carbonate of ammonia being the most delicate of these reagents. The precipitate is soluble in an excess of carbonate of ammonia, and is not thrown down again by boiling. The precipitate produced both by the alkalis and by their carbonates becomes yellow, when heated nearly to redness; and on cooling it becomes again white. This is a characteristic property, by which the oxide of zinc may be known from most white powders. But oxide of antimony is similarly affected. The ferro-cyanate of potass also causes a white precipitate. A stream of sulphuretted-hydrogen likewise causes a white precipitate, the sulphuret of zinc, the colour of which distinguishes the present genus of poisons from all those previously mentioned, as well as from the poisons of lead. The precipitate is apt to be suspended till the excess of gas is expelled by ebullition. The action of this test will not distinguish sulphate of zinc from the salts of peroxide of iron, by which white sulphur is disengaged from the gas in consequence of the peroxide of iron being reduced to the state of protoxide. The same decomposition takes place wherever there is free chlorine, as in impure samples of muriatic or nitric acid.
When the sulphate of zinc contains iron, the alkalis throw down a greenish-white precipitate, the alkaline carbonates a grayish or reddish-white, the ferro-cyanate of potass a light-blue, but sulphuretted-hydrogen the usual white precipitate. Tincture of galls, which merely renders the pure salt hazy, causes a deep violet coagulum if there is any ferruginous impurity.
The sulphate of zinc is acted on by albumen and milk precisely in the same manner as the sulphate of copper. The salt is decomposed, and the metallic oxide forms an insoluble compound with the animal matter.
When the sulphate of zinc has been mixed with vegetable and animal substances, the action of the tests mentioned above is modified. In such circumstances I have found the following process convenient.
The mixture being strained through gauze, it is to be acidulated with acetic acid, and filtered through paper. The acetic acid dissolves any oxide of zinc that may have been thrown down in union with animal matter. The filtered fluid is then to be evaporated to a convenient extent, and treated when cool with sulphuretted-hydrogen gas,—upon which a grayish or white milkiness or precipitate will be formed. The excess of gas must now be expelled by boiling, and the precipitate washed by the process of subsidence and affusion, and collected on a filter. It is then to be dried and heated to redness in a tube. When it has cooled, it is to be acted on by strong nitric acid, which dissolves the zinc and leaves the sulphur. The nitrous solution should next be diluted, and neutralized with carbonate of ammonia; after which the liquid tests formerly mentioned will act characteristically. The effect of carbonate of ammonia, and that of heat on the carbonate of zinc which is thrown down, ought to be particularly relied on.
I have tried this process with the matter vomited after the administration of sulphate of zinc, in a case of pretended poisoning, and found it to answer exceedingly well.
Orfila has lately suggested the following method. Boil the suspected substance in water, evaporate the filtered decoction to dryness, char the residuum with nitric acid as directed for copper in similar circumstances, digest the charcoal in diluted muriatic acid, and subject the filtered solution to hydrosulphuric acid. If the sulphuret be not white, but yellowish from iron, heat it with strong nitric acid, dry the product, and heat it to redness; dissolve it in weak nitric acid; throw down the oxide of iron by an excess of ammonia, which retains the oxide of zinc; and then having filtered the fluid, separate the oxide of zinc by neutralizing the ammonia.[1194]
Orfila has furnished the only accurate information hitherto possessed regarding the effects of sulphate of zinc on the animal system.[1195] He found that dogs might be made to swallow 7½ drachms without any permanent harm being sustained, provided they were allowed to vomit; for in a few seconds the whole poison was invariably discharged, and the animals, after appearing to suffer for four or five hours, gradually recovered their usual liveliness. But the result is different if the gullet be tied: violent efforts to vomit ensue, and death follows in three days, the intermediate phenomena being those of local irritation chiefly, and the appearances in the dead body those of incipient inflammation of the stomach, without corrosion.—When injected into the veins, the effect of sulphate of zinc is much more violent, in an inferior dose. Forty-eight grains occasioned almost instant death; and half the quantity proved fatal in three minutes. Orfila does not appear to have ascertained the cause of death in the last two experiments. But Mr. Blake found that when this salt is injected into the veins in the dose of three grains, it causes some depression of the heart; that thirty grains arrest the action of the heart in eight seconds, leaving that organ exhausted of irritability and full of florid blood in its left cavities; and that when injected into the arterial system in the dose of sixteen grains, it seemed not to cause any obstruction of the capillaries, but to act on the nervous system, producing extreme prostration, without insensibility or convulsions.[1196] These experiments, when taken together, show that sulphate of zinc, though a moderately active irritant, is more indebted for its activity to a remote operation on some vital organ.
Sulphate of zinc is absorbed in the course of its action; for Orfila has lately found it by his process for complex mixtures in the spleen, liver, and urine of animals.[1197]
The effects of the preparations of zinc on man in large doses have not been particularly studied. In the dose of a scruple or a drachm, the sulphate is the most immediate emetic known; and it is to be inferred, that if larger doses are rejected, as is the fact, with equal rapidity, they will in general cause no more harm than the medicinal dose.
Nevertheless, some people have suffered severely from over-doses of sulphate of zinc, and a few have even perished. Instead of presenting here a general view of the symptoms, it will be preferable to relate the heads of such cases as have been published.
The first to be mentioned is related by Foderé, who, in consequence of the violent symptoms produced, assigns to the present poison very active properties. “A patient of mine,” says he, “a custom-house officer, having got from a druggist six grains of sulphate of zinc to cure a gonorrhœa, was attacked with inflammation in the lower belly, attended by retraction of the navel and severe colic, which yielded only to repeated blood-letting, general as well as local, oleaginous emollients, opiates, and the warm bath.”[1198] This case is noticed here chiefly to prevent any one from being misled by it, as it has been quoted by other medico-legal authors. For assuredly some other cause must have co-operated before such symptoms could arise; since I have in many cases given the same dose thrice daily for several days, without ever observing more than slight sickness; and Dr. Babington once gave thirty-six grains thrice a day for some weeks with as little effect.[1199]