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Early preparation and analytical use of hydrogen sulphide
Tahttta.
1959. Vol. 2, pp. 156 to 157.
EARLY
Pergamon
Press Ltd.
Printed
in Northern
Ireland
PREPARATION AND ANALYTICAL OF HYDROGEN SULPHIDE
USE
F. SZABADV~RY Institute of General Chemistry, Technical University Budapest, Hungary (Received 13 December 1958)
Summary-Robert Boyle obtained hydrogen sulphide and applied it as an analytical reagent in 1685 for the detection of mercury, tin, lead and copper.
THE “sulphur-liver” test has been known for a long time. Treated with acids hydrogen sulphide is developed. Even the alchemists must have met this phenomenon but, having no knowledge about gases at that time, they probably paid no attention to it. According to KoppZ it was F. Hoffmans who first mentioned hydrogen sulphide, writing about a gas smelling of rotten eggs and obtained by the acidification of caustic sulphur solutions. Hydrogen sulphide was more fully studied by Rouelle3 in 1774. It was stated by Bergman,4 that hydrogen sulphide water gave precipitates of different colour with many metal-salt solutions. These reactions were fully studied by him. It is interesting that this great analyst did not think of the analytical utilization of these reactions. Until now it has been held in the literature that Fourcroy5, and at the same time Hahnemann6 both recommended hydrogen sulphide as an analytical reagent for the detection of lead. Robert Boyle, however, long before that, obtained hydrogen sulphide and applied it as analytical reagent. This appears from his Memoirs for a Natural History of Mineral Waters published in 1685. Dealing with the use of the long known metal-reagent, tincture of galls, he states that its use is not so certain as it is believed to be. Some of the metals in water, like arsenic or lead may not give a colour with it. “But, probably, the sulphureous spirit we shall presently describe, wou’d have shewn that water to be impregnated with a body of the nature of vitriol, but not the common sort. For the’ galls give no very blackish colour to a solution of Sacharum Saturni, that is, the vitriol of lead, in distill’d or rain-water yet I found this volatile sulphur wou’d soon manifestly do it: which expedient I made use of, because I had not then at hand the ores of lead, copper, etc. For the same reason I contented myselfwith the solutions of the several metals in their proper menstrua; for ‘tis probable, that the metalline parts of the ores, wou’d have afforded either the same, or similar solutions, in the same menstrua; which consisting of nitre, sea-salt, and vitriol, bodies that abound in several parts of the earth thro’ which springs flow, their several impregnated waters might exhibit phenomena of the same kind. We made then, among others, a solution of fine gold in Aqua regis; another of common running mercury in Aqua fortis; and a clear one of tin, in a peculiar solvent that readily acts upon it, and keeps it permanently dissolv’d. To these solutions I put galls, without obtaining any blackish colour, except from that which contained gold; but with our sulphureous liquor, we obtained notable changes of colour, tho’ ‘twas dark in all of them, except one, or tending to blackness. And tho’ 156
Early preparation
and analytical use of hydrogen sulphide
157
for that reason a careless eye might judge them indifferently blackish, yet, since the degrees, or some other modification of the same dark colour, seemed plainly not to be the same in them all; ‘tis possible, that a very careful view may discern some little differences between those obscure colours, from whence to form a conjecture, what metalline substance is contained, or at least predominates in the respective liquors. And I particularly remember, that the colour which arose from our sulphureous liquor, and the solution of tin, was manifestly distinguishable from those produced in any of the other solutions; being not black or blackish, nor so much as purple; but of a kind of brownish yellow.“’ Later Boyle also describes the production of the “sulphureous spirit”: “. . . take equal parts of pure salt of tartar (K&O,), flowers of sulphur, and good sal-ammoniac (NH&l), reduce the first and the last to powder separately, melt the sulphur, over a gentle fire, and, by degrees, put to it the salt of tartar; stirring them well, that they may incorporate and grow reddish; then put the mixture, pulverized, into a glassretort, pour on it the sal-ammoniac dissolv’d in fair water; and closing well the junctures, distil all in sand, by degrees of a moderate fire; shifting the receiver once or twice, because the liquors will be differently ting’d and strong, and that which ascends last, may bring over but very little of the sulphur, whose volatile tincture is yet the chief thing we aim at in this operation.“6 Repeating Boyle’s experiment I have found that hydrogen sulphide is in fact developed. Boyle also used his reagent for the detection of copper: “. . . yet common English vitriol, as also that of Dantzick, which is of the copper kind, will presently turn it of a black or very dark colour.“g But it is worth observing that he did not get any precipitate with arsenic: “. . . and to another portion of the same liquor (arsenic) we put some of our volatile sulphureous spirit, but no precipitation ensued.“lO The solution was probably alkaline. Zusammenfassung-Robert Boyle erzeugte schon im Jahre 1685 Schwefelwasserstoff bei Wasseranalysen zum Nachweis von Quecksilber, Zinn, Blei turd Kupfer. R&rum&-Robert Boyle a prepare de l’acide sulfhydrique et l’a utilise comme rbctif 1685 pour la caracterisation du mercure, etain, plomb et cuivre. REFERENCES l H. Kopp, Geschichte der Chemie, Braunschweig, 1845, Vol. 3, 317. * F. Hoffman, Obserontiones chym. phys., Halle, 1772, 305. a H. M. Rouelle, Journal de Mkdecine, 1773,39,454. 4 T. Bergman, Opuscula Phys. et chym. Uppsala, 1779, Vol. 3, 239. 6 A. F. Fourcroy, M&n. Acad. Franc., 1787, 250. BS. Hahnemamr, Crells Annalen, 1788, I, 291. ’ R. Boyle, Philosophical Works, London 1725, Vol. 3, 506-7. 8 ibid., 508. s ibid., 509. lo ibid., 510.
turd bentitzte es
analytique en
1959. Vol. 2, pp. 156 to 157.
EARLY
Pergamon
Press Ltd.
Printed
in Northern
Ireland
PREPARATION AND ANALYTICAL OF HYDROGEN SULPHIDE
USE
F. SZABADV~RY Institute of General Chemistry, Technical University Budapest, Hungary (Received 13 December 1958)
Summary-Robert Boyle obtained hydrogen sulphide and applied it as an analytical reagent in 1685 for the detection of mercury, tin, lead and copper.
THE “sulphur-liver” test has been known for a long time. Treated with acids hydrogen sulphide is developed. Even the alchemists must have met this phenomenon but, having no knowledge about gases at that time, they probably paid no attention to it. According to KoppZ it was F. Hoffmans who first mentioned hydrogen sulphide, writing about a gas smelling of rotten eggs and obtained by the acidification of caustic sulphur solutions. Hydrogen sulphide was more fully studied by Rouelle3 in 1774. It was stated by Bergman,4 that hydrogen sulphide water gave precipitates of different colour with many metal-salt solutions. These reactions were fully studied by him. It is interesting that this great analyst did not think of the analytical utilization of these reactions. Until now it has been held in the literature that Fourcroy5, and at the same time Hahnemann6 both recommended hydrogen sulphide as an analytical reagent for the detection of lead. Robert Boyle, however, long before that, obtained hydrogen sulphide and applied it as analytical reagent. This appears from his Memoirs for a Natural History of Mineral Waters published in 1685. Dealing with the use of the long known metal-reagent, tincture of galls, he states that its use is not so certain as it is believed to be. Some of the metals in water, like arsenic or lead may not give a colour with it. “But, probably, the sulphureous spirit we shall presently describe, wou’d have shewn that water to be impregnated with a body of the nature of vitriol, but not the common sort. For the’ galls give no very blackish colour to a solution of Sacharum Saturni, that is, the vitriol of lead, in distill’d or rain-water yet I found this volatile sulphur wou’d soon manifestly do it: which expedient I made use of, because I had not then at hand the ores of lead, copper, etc. For the same reason I contented myselfwith the solutions of the several metals in their proper menstrua; for ‘tis probable, that the metalline parts of the ores, wou’d have afforded either the same, or similar solutions, in the same menstrua; which consisting of nitre, sea-salt, and vitriol, bodies that abound in several parts of the earth thro’ which springs flow, their several impregnated waters might exhibit phenomena of the same kind. We made then, among others, a solution of fine gold in Aqua regis; another of common running mercury in Aqua fortis; and a clear one of tin, in a peculiar solvent that readily acts upon it, and keeps it permanently dissolv’d. To these solutions I put galls, without obtaining any blackish colour, except from that which contained gold; but with our sulphureous liquor, we obtained notable changes of colour, tho’ ‘twas dark in all of them, except one, or tending to blackness. And tho’ 156
Early preparation
and analytical use of hydrogen sulphide
157
for that reason a careless eye might judge them indifferently blackish, yet, since the degrees, or some other modification of the same dark colour, seemed plainly not to be the same in them all; ‘tis possible, that a very careful view may discern some little differences between those obscure colours, from whence to form a conjecture, what metalline substance is contained, or at least predominates in the respective liquors. And I particularly remember, that the colour which arose from our sulphureous liquor, and the solution of tin, was manifestly distinguishable from those produced in any of the other solutions; being not black or blackish, nor so much as purple; but of a kind of brownish yellow.“’ Later Boyle also describes the production of the “sulphureous spirit”: “. . . take equal parts of pure salt of tartar (K&O,), flowers of sulphur, and good sal-ammoniac (NH&l), reduce the first and the last to powder separately, melt the sulphur, over a gentle fire, and, by degrees, put to it the salt of tartar; stirring them well, that they may incorporate and grow reddish; then put the mixture, pulverized, into a glassretort, pour on it the sal-ammoniac dissolv’d in fair water; and closing well the junctures, distil all in sand, by degrees of a moderate fire; shifting the receiver once or twice, because the liquors will be differently ting’d and strong, and that which ascends last, may bring over but very little of the sulphur, whose volatile tincture is yet the chief thing we aim at in this operation.“6 Repeating Boyle’s experiment I have found that hydrogen sulphide is in fact developed. Boyle also used his reagent for the detection of copper: “. . . yet common English vitriol, as also that of Dantzick, which is of the copper kind, will presently turn it of a black or very dark colour.“g But it is worth observing that he did not get any precipitate with arsenic: “. . . and to another portion of the same liquor (arsenic) we put some of our volatile sulphureous spirit, but no precipitation ensued.“lO The solution was probably alkaline. Zusammenfassung-Robert Boyle erzeugte schon im Jahre 1685 Schwefelwasserstoff bei Wasseranalysen zum Nachweis von Quecksilber, Zinn, Blei turd Kupfer. R&rum&-Robert Boyle a prepare de l’acide sulfhydrique et l’a utilise comme rbctif 1685 pour la caracterisation du mercure, etain, plomb et cuivre. REFERENCES l H. Kopp, Geschichte der Chemie, Braunschweig, 1845, Vol. 3, 317. * F. Hoffman, Obserontiones chym. phys., Halle, 1772, 305. a H. M. Rouelle, Journal de Mkdecine, 1773,39,454. 4 T. Bergman, Opuscula Phys. et chym. Uppsala, 1779, Vol. 3, 239. 6 A. F. Fourcroy, M&n. Acad. Franc., 1787, 250. BS. Hahnemamr, Crells Annalen, 1788, I, 291. ’ R. Boyle, Philosophical Works, London 1725, Vol. 3, 506-7. 8 ibid., 508. s ibid., 509. lo ibid., 510.
turd bentitzte es
analytique en