ACTION OF SULPHUR UPON THE PENTACHLORIDE OF PHOSPHORUS. 5 Dec. 17 1849. The PRESIDENT in the Chair. The following presents were announced cc The Pharmaceutical Journal,” for December from the Editor. ‘c The Journal of the Franklin Institute,” for October from the Insti- tute. A. Volker Ph. I). was duly elected a Fellow of the Society. The following Papers were read ‘‘ On Titanium,” by Professor Wohler (Vol. 11. p. 352). II.-On the Action of Sutphur upon the Pentachloride of Phosphorus. BY J. H. GLADSTONE, YH. D F.C.S. The object of the present communication is to describe a substance which was first noticed by me during my researches upon the com- pounds of the halogens with phosphorus but on account of its very distinct character was reserved for separate consideration.found that when sulphur and pentachloride of phosphorus are mixed together and heat applied combination takes place; a mass of colourless crystals is formed which if the heat be continued are converted into a yellow liquid that may be distilled and obtained pure by repeating the distillation This liquid contains phosphorus chlorine and sulphur but differs from the sulphochlorides of phos- phorus already known both in physical and chemical properties. Attempts to analyze the new substance by oxidizing it with nitric acid failed because the heat evolved during the reaction volatilized part of the liquid. The results however appeared to indicate that the sulphur and phosphorus were in the proportion of 4 to 1 ; and this led me to the best method of preparing the compound which is as follows.Three parts of pentachloride of phosphorus are mixed in a small retort with 1 part of sulphur; that is 1 equiv. of the former to rather more than 4 equivs. of the latter and combination is deter- DR. GLADSTONE ON THE ACFlON OF mined by heating the mixture till it begins to fuse. There are then formed in the retort a yellow liquid and a mass of trans- parent colourless crystals differing in appearance from the penta- chloride of phosphorus. A gentle heat must be maintained until this transformation has taken place throughout the whole mass when the crystalline body will be found gradually to disappear and the liquid to increase in quantity. Qn cooling the crystals are repro- duced; but if the liquid be briskly boiled a distillate will be o5tained from which only a small quantity of crystals separates.A transformation has thus been effected; for the whole liquid may be distilled over the thermometer which at first indicated about llOo C. (230OF.) gradually rising; and nothing remains in the retort except perhaps a small quantity of a pecdiar dark-coloured viscid matter which will be immediately described. If a smaller proportion of sulphur be employed the same products result; but unaltered pentachloride of phosphorus is found in the retort after distillation. If on the contrary a larger proportion of sulphur be mixed with the pentachloride of phosphorus both substances are likewise pro-duced; but during the distillation of the yellow liquid it assumes a deep colour and there remains *in the retort a dark brown mass.This is a mixture of sulphur with another substance which may be distilled by the heat of a spirit-lamp. It is of a viscid consistence; water has no effect upon it but alkalis appear to separate some chlorine. I believe it to be a secondary product resulting from the action of sulphur upon the new liquid itself at an elevated temperature. Under no circumstances have I remarked the least trace of dichlo-ride of sulphur free chlorine or any other product accompanying the reaction just described. The crystalline and the liquid body are found in various proportions and sometimes there remains scarcely any amount of crystals. Thus it would appear that the liquid at least is formed by the direct combination of sulphur with the penta- chloride of phosphorus.LIQUID COMPOUND. No method of rectifying the liquid compound with perfect accu-racy has presented itself to me. The crystalline body will rise in vapour along with it ; but an approximate separation may be effected by decanting the liquid from the crystals and submitting it to gentlc SULPHUR UPON THE PENTACHLORIDE OF PHOSPHORUS. distillation. That which passes over first must be redistilled until a product is obtained which boils uniformly at a temperature not exceeding 125O C. (257O F.). The substance thus prepared is a clear mobile liquid of rather high refracting power heavier than water of a pale yellow colour and possessing an odour somewhat acid but not powerful.It evapo- rates at ordinary temperatures and shows great disposition to rise in vapour when heated. This and other causes have combined to prevent my determining its boiling point within a degree or two but it is about 118O C. (244~4~ F.). It showed no disposition to fuse when immersed in a mixture of ice and common salt at a tempera- ture of -17O C. (1*4O F.). It is capable of dissolving a large amount of sulphur when hot which it deposits again in crystals of the form of rhomboidal octohedrons or sometimes in needles. It also dissolves phosphorus alunost to an unlimited extent when hot and deposits that substance also on cooling in a crystalline form. The same may be said of the peiitachloride of phosphorus.The new liquid under consideration dissolves iodine imparting a deep red colour to the solution as is the case with most of these liquid com- pounds of phosphorus and the halogens. It mixes with bisulphide of carbon. Strong sulphuric acid has no action upon it at least in the cold ; and instead of dissolving in ether alcohol or oil of turpen-tine it violently attacks these organic solvents. The new liquid is not affected by hydrogen gas either at the ordinary or boiling temperature; but if a stream of hydrosulphuric acid be passed over it sulphur separates bubbles of gas rise through the liquid and another liquid compound remains. Metals decompose the substance under consideration in some cases with in other cases without the assistance of heat.It is violently oxidized by nitric acid. When it is brought into contact with water decomposition instantly commences ; the characteristic odour of sulphochloride of phosphorus is perceptible; and after a few hours there remains a quantity of sulphur contaminated with some sulpliide of phosphorus and in solution hydrochloric sulphuric phosphoric and perhaps phos- phorous acid together with another acid containing both phos-phorus and sulphur and giving a brown precipitate with nitrate of silvcr not soluble in dilute nitric acid but slightly so in ammonia. I believe this to be the sulphoxyphosphoric acid described by Wurt z,* notwithstanding the remark of that chemist that the silver-salt is * Ann. Chim. Ph!s. [3] XX 372. s DR.GLADSTONE OW THE ACTION OF too unstable to be prepared. The same decomposition results only more rapidly wheu solutions of the alkalis are employed; in that case however the liquid before being entirely destroyed assumes a dark red coloui* and the sulphur which separates is mixed at first with flocculent masses of an orange tint. A remarkable circumstance attending this reaction is the total absence of hydrosulphuric acid among the numerous resulting compounds unless the solution be boiled in which case it probably arises from decomposition of the sulphoxyphosphoric acid. It appeared to me that this decomposition by water might be taken advantage of for the ultimate analysis of the compound provided means could be devised for completely separating the phos- phorus sulphur and chlorine existing under so many different forms.The following process I found effectual :-The liquid having been weighed was decomposed by a dilute solution of ammonia in a corked flask so as to prevent loss of the liquid by evaporation. When the decompositiou was complete nitrate of silver was added which produced a dark brown precipitate and rendered the ammo- niacal solution of an inky appearance. This was boiled briskly for some minutes until the precipitate completely separated leaving a clear supernatant liquid. The black precipitate was then collected well washed with ammonia and afterwards oxidized by means of strong nitric acid. If pure sulphur separated it was collected by itself. The nitric acid solution thus obtained was added to the previous ammoniacal solution ; the chloride of silver was recovered by completely acidifying the liquid by additional nitric acid if neces- sary and the sulphuric and phosphoric acids were estimated by baryta.It was found necessary to continue the boiling of the ammoniacal solution for several minutes or the whole amount of chlorine was not converted into silver-salt. I. 0.3765 grm. of the new liquid yielded 0.988 grm. of chloride of silver 0.059 grni. of free sulphur 0.222grm. of sulphate of baryta and 0.1047grm. of phosphoric acid. 11. 0.1882grm of a separate preparation yielded 0.253 grm. of sulphate of baryta and 0.0494 grm. of phosphoric acid besides 0-010grm of free sulphur. 111. 09"78grm. of a separate preparation having a somewhat higher boiling-point yielded 2.041 grnis.of chloride of silver 1*001of snlphate of bnryta and 0,068 grm. of phosphoric acid hesides 0.130 gnu. of free sulphur which proved however to con-tain phosphorus. SULPHUR UPON THE PENTACHLORIDE OP FHOSPHORUS. 9 IV 0.254 grm. of the new liquid was analyzed in a totally different manner. It was poured into a flask containing reduced copper which was corked up until the odour of the liquid had entirely disappeared The resulting mass was exhausted with hot water and afterwards oxidized by nitric acid. Owing to the formation I imagine of dichloride of copper the chlorine was in a great measure contained in that portion which was subjected to the action of nitric acid ;hence an almost inevitable loss.However it yielded 0.6265 grm. of chloride of silver equivalent to 60.84 per cent of chlorine. The sulphate of baryta obtained was 0.451 grm. V. 0.4175 grm. was analyzed in the same manner as the last iron being employed in place of copper. The application of heat was necessary to effect the decomposition. 0.521 grm of sulphate of baryta wqs obtained and 0.031 grm. of free sulphur. These results reckoned to 100 parts are I. 11. 111. IV. V. Phosphorus . . 12.3 11.7 I Sulphur . . . . 23.8 23.8 { 37'8 } 24.5 24*6 Chlorine . . . 64.7 -63.9 -These numbers accord sufficiently with these deduced from the formula PS C15. Phosphorus . . . 11.70 Sulphur . . 23.40 Chlorine . . 64-90 1oo*oo Several views may be taken of the rational constitution of this new liquid compound.It may be considered as a double chloride of phosphorus and sulphur; thus P Cl, 2 (S Cl) ;but the action of water upon the substance appears to assimilate it to those compounds in which phosphorus is combined with five atoms of halogen two of them being easily replaceable by sulphur or oxygen. We may regard it therefore as P C1 S, 2 (S Cl) and suppose the sulpho- chloride set free by the decomposition of the chloride of sulphur ;-or as pentachloride of phosphoriis in direct combination with four atoms of sulphur ;P C1 S,. This is the view I prefer and I shall accord- ingly designate the new liquid as sulpho-perchloride of phosphorus. The manner in which water acts upon this compound will then appear DIt.GLADSTONE ON THE ACTION OF analogous to its mode of action upon the pentachloride of phos- phorus itself; that is two atoms of hydrogen remove two of the five atonis of chlorine ;but the two atoms of oxygen thus liberated instead of entering into the composition of the new substance combine in this case with two of the atoms of sulphur leaving the other two still to form part of the phosphorus compound. P Clj+2HO=2HCl+PC1 0, and P CZ S,+2 HO=2 H Cl+P Cl S,+S 0,. The existence of hyposulphurous acid in the solution is hypo-thetical ;and I must remark that where a considerable amount of water was employed I never observed sulphurous acid among the products even when the decomposition was effected by means of dilute acid.But unless in large quantity the odour would be masked by that of the sulphochloride and there are many conceivable ways in which the sulphurous acid might be immediately reduced or oxidized. Yet upon adding a very small quantity of water to a portion of the liquid in a corked tube a strong pungent odour was observed when the cork was removed and the gas prodnced a blue colour when suffered to fall upon a mixture of starch and solution of iodate of potash. We may therefore conclude that sulphurous acid was evolved. I may here observe that sulphochloride of phosphorus prepared in the manner described by Serullas and decomposed by water or solu- tions of alkalis without the aid of beat gives the acid formerly referred to which yields a brown silver-salt and not a trace of hydro- sulphuric acid.The view which regards the liquid just examined as a direct com- pound of sulphur with the pentachloride of phosphorus receives additional support from the discovery of Kremers who has recently shown* that sulphurous acid combines directly with pentachloride of phosphorus Fiving rise to two liquids each resolvable by water into sulphurous acid with phosphoric and hydrochloric acids. These he terms sulphites of the pentachloride of phosphorus with the formulze P Cl, 2 SO, and P Cl, 3 SO,. Rose’s sulphate of the pentachloride of phosphorus is a substance about which too little is accurately known to warrant us in drawing any deductions from it. * Am. Cli. l’harm JLIII~, 18-19.SULPHUR UPON THE PENTACHLORIDE OF PHOSPHORUS f 1 In order to ascertain whether another compound of different formula could be obtained from the liquid under examination by merely collecting that which rose first in vapour I subjected a portion for some time to a temperature not exceeding looo C. The portion which evaporated condensed into a clear yellow liquid apparently identical with that formerly examined. 0.385 grm. analyzed as above yielded 1-020grms. of chloride of silver ;the estimation of sulphur and phosphorus was unfortunately lost. This number reckoned to 100 parts gives. Chlorine = 65.35 per cent; a result sufficient to prove the identity of this liquid with the previously- described sulpho-perchloridc of phosphorus. Through the kindness of Messrs.Watts and Russell I am enabled to add a determination of the specific gravity of the vapour of sulpho-perchloride of phosphorus. The details of the experiment are as follows Weight of globe filled with air at temp. 1405~ C. 944.10 grs. (58~1~ F.) ;bar. press. 29-64inches. 1 Weight of globe filled with vapour at temp. 203O C. 951,60 grs. (39744O I?.) ;bar. press. 29-87inches. I Capacity of globe . . 29.15 cub. in. Volume of residual air at temp. 13O C. (55*4OF.) ;} 9.82 bar. press. 29.77 inches. in. The specific gravity of the vapour calculated from these numbers is 5.5. Now if we suppose 6 voluines of the vapour of pentachloride of phosphorus to unite with 4 volumes of sulphur vapour without condensation we obtain the theoretical density 5.552.This would therefore appear to be the specific gravity of the vapour in question. CRYSTALLINE COMPOUND. It has already been observed that the first distillates in the prepa- ration of sulpho-perchloride of phosphorus deposit crystals on cooling. These will often not appear till after the lapse of several hours or even days. In such a case they are usually perfectly transparent and well dcfincd having the forrn of two octagonal pyramids placed base to base and the projecting angle at the point of juncture truncated SO as to form hcsagons. The crystals thus obtained unquestionably 12 ACTION OF SULPHUR UPON THE PENTACHLORIDE OF PHOSPHORUS. sometimes contain pentachloride of phosphorus ;but they comport themselves in contact with water in a manner similar to the liquid compound just described.I. 0.2945 grm. of well-defined crystals drained and exposed for awhile to a current of dry air having been analyzed according to the process formerly described yielded 0.964 grm. of chloride of silver and 0.110 grm. of sulphate of baryta. 11. 0.1945 grm. of a separate crystallization also well-defined and uniform which was drained and dried by means of asbestos yielded 0.6415 grm. of chloride of silver and 0.058 grm. of sulphate of baryta. These numbers reckoned to 100 parts are I 11. Phosphorus (by difference) 14.1 14.6 Chlorine . 80.7 81-3 Sulphur . 5.2 4-1 The proportion between the phosphorus and chlorine is evidently as 1:5 which would require r.rr. Phosphorus . . 14.6 14-7 Chlorine . 80.7 81.3 We can scarcely suppose these crystals to be anything else than pentachloride of phosphorus contaminated with a small quantity of the sulpho-perchloride (P C1 S,) which could not be easily removed. Yet in other analyses where the crystals were so well defined I have found a larger amount of sulphur; in one instance as much as 16.6 per cent. This leads me to believe either that a crystalline compound of sulphur with the pentachloride of phosphorus does exist or that the sulpho-perchloride has itself a great tendency to cohere to the pentachloride of phosphorus. It is on this account alone that I have specially described the crystalline body. EXPERIMENT ON THE GASES GENEEATED IN A SEWER.13 Remarks on the use of the AZkaZine Carbonates for the preventiofi of Incrustation in Steam Boilers. By MR. ALFRED ANDERSON. The author gave the results of his experience that the addition of carbonates of soda and potash prevent incrustations in boilers as Kuhlmann and others had previously observed. He states that the addition of organic matters such as rice-meal was also found advantageous. Detail of some Experiments on the Gases generated in a Sewer. MAURICESCANLAN By MESSRS. AND ALFRED ANDERSON The experiments by the authors were made upon the sewer in Friar Street Southwark. The sewer was in a very foul state being 5 feet from the floor to the roof and containing between 3 and 4 feet of deposit which evolved a gas of a most powerful and filthy odour.To collect it the authors used a circular funnel of tin-plate which was inverted in the sewage matter of the sewer and there kept floating at the surface by a board ; to the top of this funnel was connected a gutta-percha delivering tube from which the gas was obtained. The pressure of the gas was capable of overcoming that of 4 inches of water. The greatest amount collected in 24 hours amounted to 34 cubic inches from an area of one square foot. The chief circumstance of chemical interest connected with this subject upon which very little has as yet been done is the probable existence of the bisulphide of carbon in this sewer at the time of the experiments. Being however a very difficult substance to detect at any time and more particularly when mixed with so many other compounds the observations as to its positive existence are not to be considered as conclusive.At times its peculiar odour was strongly developed. Alcohol through which the gas had passed acquired a peculiar odour resembling that of onions. In distilling this solution results were obtained confirming to a certain extent the existence of sulphide of carbon. The mixture of gas was found to consist of sulphuretted hydrogen carbiiretted hydrogen carbonic acid and phosphuretted hydrogen ; of the two latter a considerable proportion. A few minutes’ exposure to the gas was sufficient to produce headache and nausea. The quantitative examination of the gases was not made.