GLADSTONE ON SOYE COSEPOUNDS OF PHOSPHORITS ETC. 15 11.-On Some Compounds of Pliosplmrus containing Nitrogem By J. H. GLADSTONE, Ph.D. F.R.S. THREEseries of acid bodies all phosphoric amides have been described in previous papers. They are respectively The Pyrophosplioric Amides." Pyrophesphamic acid .................. P,(NH,)H3OGI Pyrophosphodiarnic acid ................ Y,(NH,),H,O,. Pyrophosph otriamic acid. ............... P,(NH,) ,H 0,. The T etraphosphoric Amides.? Tetraphospho-t etramic acid ........... P (NH,),H,O,. Terammoniated tetrap hosphodinmic acid. . P4(NH,) ,N,H,,O, Tetraphospho-pent'azotic acid .......... P,N,H,O,. The Thio-phosphoric Amides.$ Thio-phosphamic acid .................. P(NH,)H,SO,. Thio-phosphodiamic acid ..............P(NH,) ,HSO. During the investigation a number of other compounds have * Quart. Journ. Chem. Sac. February 1868 et. al. + Ibid. July 1868 et. al. $ Ihid. January 1865. GLADSTONE ON SOME COMPOUNDS been noticed and more or less fully examined,-and I now propose to group together these miscellaneous observations. Amidated Oxychlorides of Plzospl~o~~us. When oxychloride of phosphorus is exposed to a slow current of ammonia gas at a temperature of 0" centigrade it combines to form a solid white body and in so doing increases in weight about 22 per cent. This indicates the absorption of two mole- cules of ammonia; but on standing at the ordinary temperature the smell of the oxychloride always reappears and the con- tinuous passage of ammonia even at zero will cause a further increase of weight.At a higher temperature the combination proceeds much more rapidly and the increase through absorp- tion amounts to about 44 per cent. In either case the solid mass cakes together and it is necessary to break it up frequently in order to insure the saturation of the oxychloride. The most natural supposition is that the ammonia removes one or two equivalents of the chlorine their place being filled by amidogen thus PC1,O + 2NH = PCT,(NH,)O + NH,Cl. PC1,O + 4NH = PCl(NH,),O + ZNH,Cl. The increase in weight in the first case should be 22-15 per cent. in the second 44.3 per cent. That this is really the case is a matter of which there can be little doubt though all my efforts to separate either amidated compound from the chloride of ammonium have been fruitless.Water decomposes them at once giving rise to pyro-or tetra-phosphoric amides and absolute alcohol decomposes them in some other manner while no other solvent presented itself which was capable of dissolving the one and not the other sub- stance. Still zt mixture of alcohol and water warnsfound to effect a partial separation. Thus when a portion of PC1,O com-bined with 4NH was washed with small quantities of ordinary methylated spirit a great deal of chloride of ammonium was diesolved at once but for a long time the insoluble portion continued to yield some chloride of ammonium leading to the conviction that it was slowly formed; the long washed sub- stance was divided iiito two portions; one was heated per se and gave off ammonia and.cldoride of ammonium while the OF PHOSPHORUS CONTAINING NITROGEN. other was treated with water which decomposed it at once wit11 the evolution of heat and the production of the usual amidated acids together with chloride of ammonium. Some of the sub- stance resulting from the action of ammonia and oxychloride of phosphorus was washed with absolute alcohol ; a portion dis- solved with evolution of heat while there remained what proved to be almost pure chloride of ammonium. The alco- holic solution evaporated to dryness in vacuo and re-dissolved in water showed that some compound ether of an aromatic odour had been formed and it gave no inclications of either ortho-or pyrophosphoric acid or the amides of the latter but rather of nietaphosplioric acid ; chlorine mas also present.It has already been stated that when the -compound of oxychloride of phosphorus and four equivalents of ammonia is heated at or above 200' centigrade its constitution is so altered that it gives a different acid amide on the addition of water. Some of thin was washed with absolute aleohol till the chloride of ammonium was gradually but completely removed ;there remained a white powder which when treated with water gave the tetrsphospho- pentazotic acid while the solution gave some indication of pyro-diamic and hydrochloric acids. These three experiments all show a separation of the white powder into chloride oi ammonium and some other chlorinated body but in no case was the amide obtained in a state fit for analysis; in the last instance the small amount of chlorine (6.67 per cent.) showed that the transformation into an acid amide had been partially effected during the washing with alcohol.The transformations of these amidated oxycldorides under the influence of Tyater have been describccl iu previous papers. If the white powder produced by the treatment of osychlo- ride of phosphorus with more than two and less than four equivalents of ammonia be allowed to stand for some time the amell of the oxychloride develops itself and if it be heated the reproduction of this substance is still more evident. It would seem probable therefore that the lower compound is capable of transforming itself slowly into the higher compound and the original oxychloride 2(PC12NH,0) = PCl(NH,),O + PC1,O.The last atom of chlorine cannot be replaced by treating the VOL. XXII. c GLADSTONE ON SOME COMPOUNDS powder with gaReous ammonia at any temperature short of that at which the substance itself is decomposed,-above 300" centi-grade. Indeed I have never succeeded in preparing such a substance as Schiff 'B phospho-triamide. If the mixtiires of amidated oxychloride of phosphorus and chloride of ammonium above described be strongly heated they give up all their chloi-ine and hydrogen and part of their nitrogen leaving behind a white amorphous substance fusing at a bright red heat incapable of combining with either acids or bases and difficult of decomposition.This is the substance which has been described by various names and has the corn- position PNO. That it was really this substance has been proved both directly and indirectly. A portion of the mixture PC12(NH,)0 + NH,Cl when heated gave off chloride of ammonium and hydrochloric acid and lost 32-45 per cent.; the theoretical loss should have been 32.36 per cent. 0.289 gramme of the residue fused with nitre and carbonate of sodium gave 0.525 grm. of pyrophosphate of magnesium. This agrees with the calculated amount. Calculated. Found. Phosphorus . 5042 Nitrogen ...... 22.95 50.73 - Oxygen ...... 26-23 100*00 The decomposition will be as follows :- PC1,NH20 = 2HC1 + PNO. The same substance is produced when tfhe higher amide is decomposed by heat in which case the decomposition will be- PC1(NH2),0 = NH,Cl + PNO.As Gerhardt's original name bi-phosphamide will be gene- rally considered inapplicable to a substance of such a coni-position I suggegt the name phosphonitryle. PNO mrtp be OF PHOSPHORUS CONTATNT?;G ?;ITROQES. theoretically derived froni the ammonium salt of my variety of phosphoric acid by tJhe subtraction of all the hydrogen in the form of water P(NH,)H,O = PNO + 3H,O. P(NH,)O = PNO + 2H20. P,(NH,),H,O,= Z(PN0) + 5H,O. An attempt to prepare it by heating the pyrophosphate of ammonium gave a negative result. According to the notes of my assistant the late J. D. Holm es a series of bodies having the coinposition of pyrophosphonitry- lates may be prepared by heating pyro-triamates His aiialyses were very satisfactory but in repeating the experiments I have never succeeded in obtaining the same results ; at any rate the substances prepared by me have never been pure.The follow- ing account therefore must be understood as restiiig on the authority of his notes. ‘(PJ-rophosphotriamateof potassium when ignited evolves two equivalents of ammonia P,N,H6K0 = P,NKO + 2NH, leaving a residue which may be considered as the potassium salt of a new acid pyrophosphonitrylic (P,NHO,). This salt is a fused transparent glass quite insoluble in water; when ground to a very fine powder in an agate mortar and diffused through .cvat,er it is deconiposed by a solntion of AgNO beiiig deposited as a white heavy precipitate which becomes converted on standing into microscopic crystals.” In his experiment 0.684 grm.lost 0.073 that is 10.6 per ceut. In my experinient 0.892 grm. lost 0.097 that is 10.8 per cent. This is not in accordance with the formula given above which will require a loss of 15.9 per cent. Mr. Holnies gives the analysis of the silver salt and an nnalo gous copper salt. I. 0.4325 of the silver salt gave 0-2445 of chloride of silver and 0-4295of the ammoniochloride of platinum. 11. 0.4055 gave 0.2305 of chloride of silver. These results give numbera not very different from those of the formula P,NAgO,- c2 GLADSTONE ON SOXE COMPOUNDS Calculated. Found.-\ I. 11. -Phosphorus. . 25.00 -c Nitrogen. ... 5-65 6.22 Silver ...... 43-55 42.54 42-78 Oxygen .... 25-50 -100*00 0.345 grm. of the copper salt gave 09785.of oxide of copper and 0.4405 of aimnionioc'thride of platinum wliich agrees well with the formula P2NCu04-Calctdated. Found. Phosphorus. ... 36-13 -Nitrogen ...... 8.16 8900 Copper.. ..,. 18.41 18.15 Oxygen ...... 37-30 -7-100~00 If pyrophospho-triamic acid itself be heated at a low redness it gives off ammonia without any water. Mr. Holines found t,hat 0.6585 grm. lost 0.065 that is 9.87 per cent. In my experiment 1.555 grm. lost 0.145 that is 9-3 per cent. P,N,H,O -NH requires 9.71 per cent. loss. The residue was a semi-fused grey mass insoluble in water but gradually decomposed bv that substance even by the moisture of the air which resolves it into a mixture of acid amides and ammonium salts in which pyrophosphamic acid is most prominent but in which may also be detected the tetra- phosphoric compounds precipitsble by alcohol.Mr. H olm e s gives the following analysis of the residue I. 0.275 grm. gzve 0.7715 of mnmoniochloride of platinum. 11. 0.312 grm. gave 0.4375 of pyrophosphate of magnesium. Which agree with the formula P,N,H,O,. Calculated. Found. -I. II. Phosphorus. 39.24 39.15 I Nitrogen. ... 17-72 17-55 -Hydrogen .. 2.53 -c Oxygen , . . 40.51 -I 100-00 OF PHOSPHORUS CONTAINING NITROGEN. This may be considered as the pyrophospho-nitrplate of ammonium P,N(NH,jO, but I did not succeed in decomposing it by hydrochloric acid into NH,Cl and P2NH0 as I hoped.Ita resolution irito pyrophosphamic acid is what might be anticipated of a nitrylste P,N(NH,)O + 2H20 = P,NH,OG 3-NH,. If this semi-fluid acid be heated per se at 100' C. it gradnally gives off ammonia and something which has a smell resembling nicotine and beconies a white brittle solid dissolving in water from which alcohol throws down no precipitate. The result seems to be principtilly pyrophosphamate of ammonium. If it be heated at a higher temperature some yyrophosplio-trinmic acidis also produced. If however the experiment be con-ducted at a temperature of about 220' C. ammonia is given off as before and the resulting solid white mass is resolvable by cold water into two portions ; in the solution are found pyro- phospho-diamic and perhaps tetraphospho-tetramic acids ; undissolved is an amorphous solid which is very sparingly soluble in cold water but is instantly dissolved by warm water or by cold dilute solutions of mineral acids giving rise to pyro-phospho-diamic acid.0.252 grm. of the substance not diseolved by cold water gave 0.57 of ammoiiiochloride of platinum and 0.292 of pyrophos- phate of magnesium. This agrees best with the simple formula PNH,O Calculated. Found. Phosphorus.. .. 31.96 32-36 Nitrogen ...... 14.43 14-18 Hydrogen .... 4-12 -Oxygen ...... 49.49 I 100~00 but as this substance is most easily resolvable into P2N2H60 and H,O it seems necessary to double if not quadruple the above formula.If we allow ourselves to speculate we may imagine it P4N4Hl4Ol1, that is the semi-fluid acid P4N5Hl,OI1 from which NH has been driven by heat. CHURCH'S MINERALOGIOAL NOTICES. ~etrapliospho-tetrinzicAcid. It has been previously shown in describing the reactions of tetraphospho-pentazotic acid that under the influence of ni6rate of silver it is broken up with formation of tetrqhosphotetri-mate of silver. It has since occurred to me that this reaction might have a further bearing on the rational constitution of this body than was seen at first. If the silver salt merely trailsforins it from P,N,H,O to P,N,H,Ag,O by the eliniiiiation of NH as well as the bssic hydrogen the pale yellow salt should be to the original compound in the ratio of 315 to 512 or as 100 to 162.5.But if the tetrimic acid P,(NH),II,O pre-exists in the compound in combination with P,N6H120,,only about half that amount of silver salt will be produced and t'he solution mill contain the soluble products of decomposition of the hexamide. On performing the experiment the silver salt actually obtained showed an increase of 50.1 per cent. on the origiiial compound. This falls little short of the theoretical 62.5 and indicates that the reaction must Zmve been of the character described in the first instance. On removing the excess of silver from the solution it did give the usual reactions of tetraphospho-tetramic and pyrophospho-diamic acids as well as ammonia but these were probably secoiidary products of decomposition due to the slight excess of nitric acid.If the views already given of the tetraphosphoric amides be correct other bodies of a sirnilar character might doubtless be prepared ;indeed during the progress of the resesrcli indications of such have been met with but their reproduction and separation fkom one another are attended with extreme difficulty.