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THE LABORATORY PREPARATION OF HYDROGEN SULFIDE: A HISTORICAL SURVEY E. E. AYNSLEY and W. A. CAMPBELL King's College, Newcastle upon Tyne 1, England
T o VAN HELMONT collecting gas sylvestre and gas pingue, to Stephen Hales writing "Vegetable Staticks" in his Middlesex vicarage, to the millionaire Cavendish and to scholarly dissenting Priestley, gases other than common air were objects of curiosity which were prepared only in order that their properties might be studied. Although hydrogen sulfide had long been known under the name of hepatic air, it was not until the end of the eighteenth century that i t came to be used as an analytical reagent, and that the need arose for some means of preparing a gas for continuous use in the laboratory. Scheele's "Essay on Fire and Air" (1777) contained a paragraph headed "Stinking Sulphur-air," and here the various ways of preparing the gas were examined, the conclusion being reached that the best results were obtained by treating iron sulfide with acids. His quaint description of the synthesis of iron sulfide is worth recording.
. . . man sehmelze drey Unzen zarte Eisen feile mit Unzen Schwefel in einer Retorte eusammen: man unterhalte die Hitze so lange, bis kein Schwefel mehr in den Hals steigen will: wenn alles erkaltet, zerschlage man die Retorte: man wird finden dass das Eisen cine Unze am Gewiehte zugenommen. Dieses geschwefelte Eisen nolnret sioh mit starken Gahrung in den Sauren, und man erhdt lauter stinkende sohwefelluft. (I) The new demand for this gas as a reagent required that the preparation might be started and stopped as required, and the smell precluded the simple expedient of pouring off the acid when sufficient gas had been generated. But for t.his requirement hydrogen sulfide would no doubt have continued to be made, as hydrogen is frequently made in school laboratories, in the twonecked bottle fitted with a thistle funnel which has
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come to he known as Woulfe's bottle, but which was in fact invented not by Woulfe but by Glanber. Several early attempts were made to solve the problem of providing hydrogen sulfide "on tap"; that they were not completely successful is shown by the fact that Rose and Fresenius preferred to use a solution of the gas, which they called liquid hydrogen sulfide. Berzelius used an ordinary aspirator bottle with its funnel graduated so that the required amount of acid could be added. The volume of acid was of course calculated on an empirical basis. Several pieces of apparatus were introduced by J. J. Griffin, a learned chemist who translated Rose's analytical textbook into English and founded the firm of scientific instrument makers now known as Griffin and George Ltd. Griffin's gas bottle (Fig. 1) used excess of acid, the pressure of gas forcing the liquid into the bulb, but it was obviously impossible to free the solid reactant from all traces of acid. A later Griffin apparatus (Fig. 2) overcame this difficulty by allowing the-acid to drain from the sulfide when the vessel was inverted. Only the size of the lump prevented the iron sulfide's falling through the orifice between the chambers, and small pieces must often have become detached in use. Based on the same principle, and subject to the same disadvantage, was the apparatus of von Babo (Fig. 3). An arrangement of bottles described by Dr. Phipson in 1865 certainly overcame the difficulty of preventing the sulfide from falling into the acid (Fig. 4). When in use, the acid container stood on three bricks and was lowered to bench level when sufficient gas had been generated. Phipson said that he saw this apparatus "in the laboratory of Professor Pisani, in Paris (f?)," but it was probably devised by Deville. It may be noted
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Kipp an idea for the external features of his own apparatus. This was a three chambered vessel designed by Kooth for saturating water r i t h carbon dioxide (Fig. 5) (5). Priestley had, of course, already described the preparation of "soda vater" in his essay "On different kinds of air" (6). Nooth's apparatus must have been a fearsome object to use, considering that it involves generating the gas in a closed system. The heavy stopper at the top was supposed to jump up and down as required, acting as a safety valve. The non-return at the junction between the two lower chambers, consisting of a plano-convex lens moving in a metal cylinder separating two capillary tubes, very frequently jammed. Faraday said of this: It may be prudent to warn those r h o possess it against gene* ating gas afresh in the l a w x vessel without first ascertaining tlint the valve between that and the second is in the right order. From inattention to this circumstance, an apparatus of the lund has in two or three cases been b h m to pieces.
Dr. Ure also had this caution to give: The valve is the most defective part of this apparatus, for the cqdlitry tube does not admit air through, unless there is a considerahle quantity condensed in the lower vessel; and the condensation has in some instances burst the vessel (8).
It is perhaps not surprising that the txro copies of this
P.J. Kipp (1808-1864)
that these methods of regulating the production of gas by moving some part of the apparatus imply the existence of good flexible tubing. This was not obtainable much before 1850, as Goodyear's process for vulcanizing rubber, though invented in 1839, was not patented until 1844. Famday, for instance, gave directions for making out of sheet lubber connecting pieces which were only fit for glass-to-glass joints (8). Thomson in 1836 described how he made rubber joints out of a ribbon of rubber: I besmear one side of such x ribbon with-&varnish composed of caoutchouc disaolwd in naphtha, wrap it tightly round the place and then tie it firmly \r-ith a:pieeqof twine.
...
apparatus listed in Daubeny's inventory of 1823 have not survived to be included in the Dauheny collection, now in the Museum of the History of Science in Oxford. This was the background against which Kipp's apparatus was developed. P. J . K i p p founded his firm of scientific instrument dealers in the year 1830; the firm is still in business in.Delft and has very kindly supplied the photograph of the founder and of the early form of apparatus. The actual date of it,s invention is not known, nor is the place of its manufacture, though the first apparatus appears to have been made for Kipp by a German glassblower (Fig. 6). The apparatus was offered for sale in England in 1866, two years after the death of Kipp. A n early catalogue of Griffin's gives the price of the largest size in Bohemian glass as tmentyfive shillings, and the smallest size in German glass as eight shillings. A short biography of Kipp appearedin the year of the firm's centenary. (0).
Thus one development in chemical manipulation waits upon another. Meanwhile there had appeared an apparatus which, though designed for a different purpose must have given
Figure 6.
Oi-igind Form of Apparmtnm Made for P. J . Kipp
JOURNAL OF CHEMICAL EDUCATION
Very many modifications to Kipp's apparatus have appeared and are appearing, ~h~~ have been designed mainly to increase the life of a filling, or to allow the spent acid t o be removed without disturbing the rest of the equipment. LITERATURE CITED (1) "Abhmdlung von den Luft und dem Feuer," Ostwald's Klsssiker der Exakten Wissenschaften No. 58, Engelmann, Leipeig, 1894.
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(2) PHIPSON, T. L., J. Chem. Soc., 17, 152 (1865). (3) F ~ R ~ D AM., Y ,"Chemical Manipulation," W. Phillips, London, 1827, p. 206. (4) T ~ ~ T., M"Outlines ~ ~ of Mineralom, ~ , Geology and Mineral Andysis," Baldwin and Craddock, London, 1836, Vol. 2, p. 358 (in footnote). (5) Noom, J. M., Phrl. Trans. Roy. Soc. London, 6 5 , 59 (1775). (6) PRIESTLEY, J., Phtl. Trans. Roy. So?. Ladon, 62, 151 (1772). (7) Ref. (5), p. 367. (8) URE, A,, "A Dictionary of Chemistrv," 2nd ed., Thomas Tegg, London, 1824, p. 538. (9) GIBSON,C. S., Chem. & Ind., 49, 509 (1930)
