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V.—A Contribution to the Chemistry of Nitroglycerine

Published online by Cambridge University Press:  06 July 2012

Matthew Hay
Affiliation:
Assistant to the Professor of Materia Medica in the University of Edinburgh

Extract

Introductory.—In the course of an inquiry into the physiological and therapeutical action of alkaline nitrites, and allied substances, I was struck with the strong resemblance which the action of nitroglycerine bears to that of the nitrites. The resemblance is, indeed, so well marked, that the action of the one may be held to be identical with that of the other, unless in respect of intensity. The suggestion, therefore, naturally occurred to me, that nitroglycerine is not a nitrate of glyceryl, as it is always represented, but a nitrite. For no ordinary nitrate, as an alkaline nitrate or nitrate of ethyl, nor any compound of glyceryl with another acid, as sulphuric acid, produces an action on the body at all resembling that of nitroglycerine. On referring to the various investigations which had been made for the purpose of ascertaining the chemical constitution of nitroglycerine, I found that none of them was sufficiently extended and exact to place beyond doubt its precise nature. The danger in manipulating so explosive a body had evidently prevented the various chemists from making a thorough examination of its composition. I at first thought that nitroglycerine might be a nitrite of glyceryl, having its nitrous acid so intimately combined with the glyceryl, that the acid did not exhibit its reactions when tested for in the usual way ; just as the acids of other ethereal compounds will not yield their usual reactions, unless special means are taken to forcibly dissociate the acid from the base ; for example, the acid of acetate of ethyl, or of chloride of ethyl. Certainly nitroglycerine gives no blue colour with a solution of starch and iodide of potassium and sulphuric acid, a very delicate test for the presence of nitrous acid. In order, however, to apply the test to the separated acid of nitroglycerine, I mixed an alcoholic solution of nitroglycerine with an alcoholic solution of pure caustic potash. The potash was ascertained to be free from nitrite, which I have frequently found present in small quantity in various specimens of ordinary potash. Decomposition of the nitroglycerine quickly occurred, and the fluid, when now tested for nitrous acid, was found to contain the acid in abundance, and so much of it, that for the moment I believed that nitroglycerine was, in reality, a nitrite of glyceryl; and hence the nature of its physiological action. Some estimations, however, of the quantity of the nitrous acid proved to me that whilst the larger portion of the nitrogen of the nitroglycerine appeared as nitrous acid in the decomposed products, yet a considerable portion was present in some other form.

Type
Transactions
Copyright
Copyright © Royal Society of Edinburgh 1883

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References

page 67 note * Hay, Matthew, Practitioner, March, and June 1883Google Scholar.

page 68 note * Müller, und De la Rue, , Liebig's Annalen. d. Chemie., CIX. 122Google Scholar.

page 68 note † Hess, und Schwab, , Berichte d. deutsch. chem: Gesellschft. Bd. XI. (1878), S. 192Google Scholar.

page 68 note ‡ Railton, , QU. Journ. of Chem. Soc., vol. vii. p. 222Google Scholar.

page 68 note § Williamson, , Proc. Roy. Soc. Lond., vol. vii. p. 130Google Scholar.

page 72 note * Masson, , Journ. Chem. Soc., August 1883Google Scholar.

page 72 note † Vide accompanying communication on “ The Elementary Composition of Nitroglycerine.”

page 76 note * Dumas, et Stas, , Ann. Chim. Phys., lxxiii., 148Google Scholar.

page 78 note * Beckerhinn, , Sitzungsb. d. Wien. Akad., Bd. lxxiii. (1876), Abth. 2, S. 235Google Scholar.

page 78 note † Hess u. Schwab, Sitzungsb. d. Wien. Akad.., Bd. lxxv. (1877), Abth. 1, S. 702.

page 79 note * It is somewhat remarkable that the yield of nitrous acid was as great as when a fixed alkali was used ; since it is well known that a solution of nitrite of ammonia readily undergoes decomposition when heated ; and it was to be expected that the estimated yield of nitrous acid would have been diminished by the occurrence of such a decomposition in the heated fluid. In order to make certain that the result obtained was correct, and that under the conditions of the experiment such a decomposition did not occur, or occurred only to a limited extent, I have, since the paper was read, repeated the experiment. This I have done on two occasions, and with separate quantities of pure nitroglycerine. On the first occasion only 29 6 per cent, of nitrous anhydride was obtained, but, on the second, 34.1 per cent., or very nearly what was obtained in the experiment recorded in the text. The nitrite of ammonia formed by the splitting up of the nitroglycerine would appear, therefore, to undergo very little decomposition under the conditions in which it is placed. This may be due to. The excess of free ammonia always maintained in the decomposing mixture, or to the low degree of heat applied, as, in order to prevent the rapid escape of gaseous ammonia, heat was appliéd short of ebullition of the fluid, or, more properly, of the escape of ammonia in the form of bubbles of gas ; or it may be that the highly concentrated alcohol in which the nitroglycerine was dissolved hindered the decomposition of the nitrite.

page 81 note * De Vrij, , Journ. Pharm. [3], xxviii., 3Google Scholar; and Gmelin's, Handbook of Chemistry, x. p. 562Google Scholar.

page 84 note * Vide Hay and Masson's Paper on “The Elementary Composition of Nitroglycerine.”

page 85 note * Bd. iii. 1878.

page 85 note † S. 529, 1881.

page 86 note * Op. cit.