DR. SHERIDAN MUSPRATT ON THE IDENTITY OF W,-On the identity of ~ i ~ ~with~~~~~ ~ to ~~~ Acids and of Bisulphimethylic with Hyposulphamethylic acids. Bg SHERIDAN Ph. D. F.C.S. MUSPRATT In my paper on the ‘<Action of Nitric Acid upon the Sulpho-cyanides of Ethyl and Methyl,’’ I described acids containing no nitrogen which is interesting as they are produced by the action of one nitrogeneous body upon another. The following were the formuh given for the two acids.* Hyposulphethylic acid HO C 13 S 0,. Hyposulphamethylic acid HO. C HI S 0;. Since my results were published others have entered upon a similar field of research aniong whom I may mention Mr. Medlock who was induced to undertake the preparation of acids in the amyl series. By the action of nitric acid upon the sulphocyanide of amyl * Chem.SOC.Qu. Journ. 11 116. f-Chem. SOC.Qu. Journ. I 45. BISULPHETHYLIC WITH HYPOSULPHETHYLIC ACIDS. he procured a compound analogous in every respect to those above- mentioned. Appended to his paper is a note by Dr. Hofmann stating that the acid prepared by Xlr. XIedlock is evidently identical with the compound which &M.Gerathewohl and Erdmann ob- tained as a product of the decomposition of the bisulphide of amyl by means of nitric acid although these chernists adopt a different formula for that compound. The formula which they give for the baryta-salt of their acid is Ba. C, H, S 0 HO = Ba. C, EIp3 S O, differing from Mr. &ledlock’s formula Ba C, H, S O, by one equivalent of hydrogen.In four hydrogen determinations however a deficiency was found oscillating between 0.2 and 0.4 per cent while Meillock’s analysis generally gave a slight excess. A similar objection may be made to the analysis of several salts of the acid obtained by the ection of nitric acid on the bisulphide of ethyl. It would be interesting to repeat the analysis of the baryta-salt on which the formula H. C H R 0, assigned to this acid is principally founded. I have intended for some time to recur to the bisulphethylic acid considering that its description and properties correspond very closely with those of my acid; yet I have not until now had an opportunity to decide the question as to their identity moreover the repulsive qualities of bisulphide of ethyl are almost a sufficient reason to debar any one from preparing the compound.It is extremely difficult with acids containing a small per centage of hydrogen to arrive at its exact amount even when the greatest accuracy is exercised; consequently I was determined to prepare the baryta-salt of Lowig’s acid and to ascertain the exact amount of baryta; and if that amount corresponded with the quantity of baryta in the salt obtained by the action of nitric acid upon the sulphocyanide of ethyl the identity of the two would be proved and the correctness of my formula established. PREPARATION OF BISULPHIDE OF ETHYL. It is extremely difficult to obtain this body in large quantities and unless the materials employed are well prepared the stench is insuffer- able my clothes have retained it for weeks.The best mode of procedure appears to be to distil equal portions of concentrated solutions of sulphovinate of lime and tersulphide of potassium in a retort having a capacity ten times the volume of the mixture to prevent any of the solution passing over into the receiver which it is apt to do owing to violent intumescence that occurs. As c2 DR. SHERIDAN MUSPRATT ON THE IDENTITY OF the mass becomes viscid the oil that drops over must be repeatedly washed with distilled water and then rectified several times over chloride of calcium. It has a most disgusting smell when crude but after rectification the smell is only slightly alliaceous. It is sparingly soluble in water but is copiously dissolved by alcohol and ether it burns with a blue flame giving sulphurous acid.In the air it is unchanged but potash slowly decomposes it. PREPARATION OF THE ACID. Equal parts of bisulphide of ethyl and tolerably strong nitric acid were introduced into a retort adapted to a Liebig’s condenser. A gentle heat was applied during the process. The action was most violent nitrogen carbonic acid and nitrous acid passing off sul-phuric acid was also produced during the operation but I found the quantity depended upon the strength of the acid employed. The distillate was repeatedly returned to the retort to decompose all the oil. When the elimination of gas had ceased the liquid was evaporated over a water bath to expel the least trace of nitric acid.A fluid like oil of vitriol remained possessing a slight alliaceous odour. This was dissolved in water saturated with pure carbonate of baryta and filtered to remove the excess of carbonate and any sulphate of baryta. The filtrate on slow evaporation afforded large rhom-bohedral crystals of hyposulphethylate of baryta. These crystals were dissolved in water and precipitated by an excess of absolute alcohol and recrystallized. Tbe following is an analysis of the salt dried at loo0C. 0.1212grms. of substance gave 0.0797 grrns. of sulphate o€balyta = 0*0524grms. of baryta = 43.23 per cent. From a pretty considerable quantity of the salt I precipitated the baryta by sulphuric acid and filtered. I digested the filtrate with carefully prepared carbonate of lead refiltered and decomposed the lead solution by sulphide of hydrogen separated the sulphide of lead and evaporated the filtrate on a water bath.A portion of it left in a cold place over sulphuric acid in vucau afforded colourless needles extremely deliquescent and having a feeble odour of garlic. The deliquescent mass was mixed with water and carbonate of baryta filtered and the filtrate evaporated. Very fine crystals of the rhombohedra1 system settled down which were dried over sulphuric acid. BISULPHETHYLIC WITH HYPOSULPHETHYLIC ACIDS. ANALYSIS OF THESE CRYSTALS. 0*801grms. of the crystals dried at loooC. gave -0386 grms. of water. These results agree exactly with the annexed formula BaO. C H S 0 + aq.Centesimally represented Theory. Found. Hyposulphethylate of baryta . . . Water . . . . . . . . . . 178 9 95-19 4.81 >> 4% 1 100.00 This salt when dried at loooC. yielded the following numbers 0.410 grms. of salt burnt with chromate of lead gave 0.204 grms. of carbonic acid and 0.111 grms. of water. 0.1701 grms. of salt treated with potash and nitrate of potash gave 0.2210 grms. of sulphate of baryta = 0.0302 grms. of sulphur. 0,2399 salt dried at looo C. gave 0.1580 grms. of sulphate of baryta = 0,1039 grms. of baryta. Centesimally represented Theory. Pound. I---the Ba- ofAnd1ysls ryta-salt of the acid produced by the ac- tion of nitric acid ryta-salt of the acid produced by the dC-tion of nitric acid on the Ilisulphide of Ethyl.on the Sulphocy-anide of Ethyl. 4 eq. Carbon . . 24 13-49 13.53 13.16 5 , Hydrogen . 5 2.82 3-00 3.06 2 , Sulphur . . 5 ’ Oxygen . . 32 40 17.97 22.47 17.75 22-42 17.56 22.9‘7 1 , Baryta . . 77- 43.25 43.30 - 43.26- c_- 178 100.00 100*00 100*00 On referring to the preceding analysis there is every ground for asserting that the baryta-salt of the acid produced by the action of nitric acid on the bisulphide of ethyl is identical with the baryta-salt of the acid produced by the action of nitric acid on the sulphocyanide of ethyl. Lowig’s baryta-salt yields theoretically 3-36per cent of hydrogen; mine gives 2.82per cent. Analysis gives me 3.00and 3.05 per cent. Kopp found in the baryta-salt of the acid produced by DR. SHERIDAN MUSPRATT O’u’ THE IDENTITY OF the action of nitric acid upon the bisrilphide of ethyl 43.66 per cent of baryta while Lowig gives 44.83 per cent of baryta in the same salt a difference sufficiently accounting for the formula which the latter assumed.Appended are the four determinations that have been made Baryta in the acid from the bisulphide of ethyl . . 43.66 per cent-Kopp*. Baryta in the acid from the same source 43.23 , , -Muspratt. Second determination . . 43.30 , , -Ditto. Baryta in the acid produced from the sulphocyanide of ethyl by the action of nitric acid. . . 43.26 , , -Muspratt. PREPARATION OF THE ACID FROM BISULPHIDE OF METHYL. The bisulphide of methyl was treated similarly to the ethyl com-pound. I remarked on evaporating the decomposed bisulphide on the water bath that a most stifling vapour passed off which excited a flow of tears.This however was not the case when the purified bisulphide of methyl was employed. PREPARATION OF THE BARYTA-SALT. The acid was mixed with an excess of carbonate of baryta filtered and the filtrate precipitated by absolute alcohol. Very fine splendent needles were deposited which when dried at looo C. gave the annexed quantities of baryta First determination; 0.2140 grms. of salt gave 0.1520 grms. of sulphate of baryta equivalent to 0*1000grms. of baryta = 46.72 per cent. Second determination; 0.2310 grms of salt gave 0.1650 grms. of sulphate of baryta equivalent 0.2085 grms. of baryta = 46.97 per cent. f shall append the above two determinations collaterally with the one I previously made with the baryta-salt obtained from the acid produced by the action of nitric acid on the sulphocyanide of methyl.Baryta-salt of the acid obtained by the action of nitric acid on the bisulphide of methyl. * Lowig’s Chemie der organischen Verbindungen. TI. Rand S. 427. BISULPHETHYLIC WITH HYPOSULPHETHYLIC ACIDS. Centesimally represented I. . 46.72 baryta. I1 . . 46.97 , Baryta-salt of the acid obtained by the action of nitric acid on the sulphocyanide of methyl I. . . 46.74 per cent of baryta. The following formula agrees perfectly with the above BaO. C H S 0, and yields 46.95 per cent-baryta by theory ; a sufficient proof of the identity of the two methyl-acids.Having obtained such satisfactory results with regard to the identity of the two ethyl acids with each other and of the two methyl acids with each other I did not think it necessary to prepare the bisulphide of amyl so as to ascertain whether the acids of Erdmann and Medlock were identical. When identity is proved in the ethyl series with regard to two acids we may with a degree of certainty assume identity in corresponding series such as those of methyl and aniyl; and although the latter series are not so extended as the former still the analogues of all the sulphur and oxygen compounds of the ethyl combinations will I am convinced be disco- vered long before. When this is the case mom decided conclusions may be drawn with regard to the basyles and salt radicals upon which the whole fabric of chemical theory is at present based.Although the number of compounds in Organic Chemistry is very great yet I feel convinced that a repetition of old investigations by skilful hands will tend to reduce their number ; for with regard to the accurate determination of a formula very much depends upon the perfection of the apparatus employed and the accuracy of the manipulator. I shall in conclusion give the formulE for the two acids which have been discussed Hyposulphethylic acid H. C H S O, or HO. C H S 0, Hyposulphamethylic acid H. C H S O, or HO. C H S 0,.