MANGANESE-SALT.-Chloride of manganese gives a yellowish salt of this acid. CHROMIUM-SALT.-A green compound may be produced by means of acetate of chromium. MAGNESIUM-SALT.-This was produced by warming the acid with an ammoniacal solution of magnesia, and washing with water containing a little ammonia, and afterwards with pure water. On analysis, it appeared to be a mixture of monometallic and dimetallic salts. POTASSIUM-SALT.-Monometallic.-Pyrophosphotriamic acid decomposes carbonate of potassium without dissolving. The white, almost insoluble salt is readily decomposed by acids. The following determinations were made : I. 0.312 grm. of salt gave 0.356 grm. of potassio-chloride of platinum. II. 0329 grm. gave 0.3402 grm. of pyrophosphate of mag nesium. III. 0·2985 grm. gave 0.3355 grm. of potassio-chloride of platinum. This agrees with the numbers deduced from the formula P2N H KO AMMONIUM-SALT.-The acid forms a similar sparingly soluble ammonium-compound, which cakes together in small white lumps, and readily parts with the base when treated with dilute acids in the cold. I. 0.129 grm. of salt gave 0-5945 grm. of ammonio-chloride of platinum. IL. 0-2095 grm. gave 0-9805 grm. of ammonio-chloride of platinum. III. 0-3423 grm. gave 0-3995 grm. of pyrophosphate of magnesium. IV. 0-220 grm. gave 1014 grm. of ammonio-chloride of platinum. This indicates the compound P2N,Hε(NHI)04. Phosphorus 2 3 .... 56 62 32.29 32.61 .... 64 33.33 192 100.00 MERCURY-SALT.-Tetrametallic.-It was observed early in the investigation that if pyrophosphotriamic acid be boiled with oxide of mercury, the oxide loses its colour and forms a white compound which is insoluble in dilute nitric or hydrochloric acid. This mercury-salt may be also prepared by diffusing the acid through a solution of corrosive sublimate, but Mr. Holmes seems always to have employed a slightly acid solution of the double chloride of mercury and ammonium. It is a heavy, white, granular powder, which becomes yellowish, and eventually dark-coloured, when exposed to light. Iodide of potassium first turns it scarlet, and then dissolves out the mercury. The following analyses were made: I. 0.4175 grm. of salt gave 0.3405 grm. of sulphide of mercury. II. 0.5405 grm. gave 0·4405 grm. of sulphide of mercury. III. 0-276 grm. gave 0.224 grm. of sulphide of mercury, and 0.3305 grm. of ammonio-chloride of platinum. IV. 0-3415 grm. gave 0.277 grm. of sulphide of mercury, and 0.1305 grm. of pyrophosphate of magnesium. These numbers require the formula P2N2H2Hg. 3 PLATINUM-SALT.-When pyrophosphotriamic acid is treated with a strong aqueous solution of platinic chloride, a bulky, yellowish compound is formed. This is entirely decomposed when washed with water, in presence of the liberated acid; but it may be safely washed with alcohol, and then water has not the same effect upon it. 0.097 grm. of the original acid gave 0·207 grm. of this platinum-compound, which shows that two equivalents of the metal must have entered into combination, displacing, no doubt, four equivalents of hydrogen; the formula being P2N2H ̧Pt24. Calculated. Platinum .. 53.7 per cent. Found. 54.1 per cent. An attempt to prepare a salt of gold in a similar manner was unsuccessful. The rational formula P2(NH2),HQ4 has been given above for this pyrophosphotriamic acid, but the elements are susceptible of another arrangement, which brings them more closely in accordance with the formula of pyrophosphoric acid, and indicates four equivalents of hydrogen as in a different position to the remaining three. Pyrophosphoric acid The following table exhibits at a glance the number of hydrogen atoms displaced by different metals, as far as the salts have been hitherto examined quantitatively : II. On the Action of Carbonic Oxide on Sodium-ethyl. By J. ALFRED WANKLYN. (Preliminary Notice.) WHEN the compound containing sodium-ethyl and zinc-ethyl, which I have described on a former occasion,* is placed in contact with carbonic oxide, it becomes black. The darkening takes place slowly at ordinary temperatures, but very quickly, almost instantaneously, at temperatures approaching 100° C. The black deposit is not carbonaceous, for it dissolves in hydrochloric acid. It is metallic, consisting of metallic zinc, and most probably also of metallic sodium. Absorption of the gas and formation of an oily product, accompany this deposit of metal. The most convenient way of exhibiting the oil is to wash out with water the vessel in which the experiment has been performed, and then to distil the wash-water. The oil distils over with the first portions of the distillate. In one experiment nearly 2 grm. of oil were yielded by 1 grm. of sodium employed in the state of sodium-ethyl. The oil was dried and rectified. The greater portion boiled at about 105° C., and gave the following result on analysis : I. 2076 grm. gave 5218 CO2 and 2300 grm. H2O. In another experiment a quantity of oil having about the same boiling point was obtained. II. 1029 grm. gave 2597 grm. CO2, and 1155 grm. H2O. The numbers approximate to those required by a compound containing one atom of carbonic oxide and two atoms of ethyl, These details leave no doubt of the reaction which takes place between carbonic oxide and the compound containing sodiumethyl. We have : (1) Disappearance of carbonic oxide. (2) Precipitation of metal. (3) Formation of an oil of pretty constant boiling-point, and commensurate in quantity with the sodium-ethyl taken, and approximating sufficiently in composition to CO(CH)2. Furthermore, the wash-water from which the oil distilled over was strongly alkaline. The reaction may, therefore, be represented by the equation : An experiment showed that zinc-ethyl alone is not attacked by carbonic oxide. The precipitation of zinc is obviously a secondary action. Sodium on being set free would instantly attack the zinc-ethyl, liberating zinc, and forming fresh sodium-ethyl. The oil, CO(C2H5)2, is probably identical with propione (ethylpropionyl). I am at present engaged in preparing a quantity sufficient to admit of purification and of an examination of its physical properties and reactions. Among the latter I propose to study its oxidation products, and to inquire whether it is capable of uniting with hydrogen so as to form a pseudo-amylic alcohol. It may be remarked that it is by no means impossible that on adding water to the black mass containing finely divided metal saturated with the oil CO(C2H)2 addition of hydrogen may have taken place, and, indeed, both the boiling point of the oil and the analyses point in this direction. Propione boils at 101° C. Amylene-hydrate boils at 108° C.; whilst our oil boiled at 105° C. The analytical numbers given by the oil are also intermediate between those required by propione and amylene-hydrate. |