The absorption of this gas by water, has been stated variously. In 1799 M. Raymond found that water absorbs rather less than ¼ of its volume of this gas: in 1802, Dr. Henry rates its absorption at ¹/₄₇ only; in 1810 I found it ¹/₂₇; in 1812, Davy found it (hydrophosphoric gas) to be ⅛; in 1816, Dr. Thomson found it to be ¹/₄₇; I now estimate it as stated above at ⅛. These enormous differences may be partly accounted for by varieties in the gas; and partly from the theory of the absorption not being understood; but these are scarcely sufficient excuses in all the cases. I find that my early experiments on the absorption of phosphuretted hydrogen by water, were made prior to the discovery of the method of analysing the gas by electric combustion; consequently they were deficient in regard to the quality of the gas, both before and after agitation; the best gas that ever I had, was such as took 150 oxygen per cent. for its combustion, exclusive of any common air; and it was often such as to require considerably less. The bottle which I used for the purpose in 1810 contains 2700 grains of water; at first I charged water with hydrogen: into this 120 grain measures of phosphuretted hydrogen were put, and the whole well agitated: there were left 98 measures;—this proved that the gas was more absorbable than hydrogen: into the same water were put 98 more phosphuretted hydrogen and agitated; out, 80; this confirmed the proof: Into the same water were put 97 hydrogen and agitated well; out 105: This shewed that the hydrogen had expelled a part of the gas again, and was less absorbable of the two. As the phenomena were much the same as if oxygen had been used instead of phosphuretted hydrogen, it was concluded to have the same absorbability.
In the present instance, however, I have been more circumstantial; after repeatedly agitating water with pure azotic gas, so as to saturate it and expel the oxygen, I then put in 110 grain measures of phosphuretted hydrogen composed of 100 pure gas, 5 hydrogen, and 5 azotic gas or rather atmospheric air. After due agitation, all was absorbed but 35; this was mixed with a known portion of oxygen and exploded; the diminution was 19 measures; the oxygen remaining was determined by hydrogen; from which it appeared that 10 combustible gas had taken 9 oxygen. Now 10 being ²/₇ of 35, we may consider the water as ²/₇ impregnated with the phosphuretted hydrogen, and ⁵/₇ with azote; but as there were 105 combustible gas and only 10 left, 95 must have entered the water and caused it to be ²/⁷ charged with the gas; whence we may infer that 332 gas would have been a full charge for 2700 water, which is almost exactly ⅛, as stated above. Other experiments gave corresponding results. On admitting 51 azotic gas to the water, and agitating it a good deal for 4 or 5 minutes, there came out 51 measures or the same volume: this was found in the same way to consist of 43 azote and 8 combustible, which took 10 oxygen. Again 51 azote was agitated in the water, and there came out 51, of which 5 + were combustible and took 9 oxygen. After this the bottle of water was put into a pan of water which was raised to the boiling heat, a bent tube filled with water being adapted to the water bottle, and having its end immersed in water: by this operation gas was expelled from the water, and caught in the neck of the bottle; when it amounted to 22 grain measures it was transferred and was found to consist of 17 azote + 5 + combustible, which took 10 oxygen. By these experiments we see that the gas is expelled again from the water, both by ebullition and by other gases, nearly the same in quality, but much diminished in quantity, the reason of which is not very obvious. The liquid now required 30 measures of oxymuriate of lime, equivalent to 100 measures of oxygen, before it was saturated; that is, there appeared to be 50 phosphuretted hydrogen remaining in the water. Adding a little lime water threw down a very sensible quantity of phosphate of lime.
The expansion of phosphuretted hydrogen by electricity is a subject on which there has been as much diversity as on its absorption. In 1797, Dr. Henry found that it expanded “equally with carbonated hydrogen.” (Philos. Trans.). In 1800, Davy states that phosphuretted hydrogen was not altered in volume by electricity. (Researches, page 303.) In 1810, my experiments led me to adopt the same conclusion. In 1811, Gay Lussac found (Recherches, page 214), that potassium heated in phosphuretted hydrogen gas, expanded 100 volumes to 146; he infers that the true expansion ought to have been to 150. In 1812, Davy observes, that when electric sparks are passed through gases of this kind, “usually there is no change of volume.” (Elements of Chem. Philos. p. 294.) But he adds that when a gas (sp. gr. 6, hyd. being 1) was heated with zinc filings over mercury, there was an expansion of volume of more than ⅓. Also potassium heated in it, made 2 parts become 3 or 3, parts rather more than 4, (1810); the residual gas in these cases was pure hydrogen. Hydrophosphoric gas (sp. gr. 12) yielded 2 volumes of hydrogen, by heating potassium in it. In 1816, Dr. Thomson found that by electric sparks phosphorus was deposited, and hydrogen remained “exactly equal to the original bulk of the phosphuretted hydrogen.” Lastly, in 1817, I found by two experiments, that by electrifying 30 grain measures of phosphuretted hydrogen in a tube over water, uninterruptedly for nearly 2 hours, I produced an expansion of ⅕, or the gas became 36 measures; originally the gas contained 2½ common air, and the rest was combustible so that 100 measures took 190 oxygen. By exploding the residue with oxygen, I found that ¹/₁₅ or ¹/₂₀ of the phosphuretted hydrogen still remained undecomposed. Taking these observations into consideration along with the fact, that 1 volume of the purest gas requires 2 of oxygen for its combustion, I conclude that the true expansion should be ⅓, or 3 volumes of gas should become 4, and then it will be found that ⅓ of the oxygen is joined to the hydrogen and ⅔ to the phosphorus, which accords with what appears to me the only correct view of the constitution of phosphoric acid, namely, 2 atoms of oxygen to 1 of phosphorus.
The action of oxymuriatic acid, whether free or combined, on phosphuretted hydrogen, is curious and interesting; in both cases it effects a complete and instantaneous combustion of both phosphorus and hydrogen; when the acid is put to in the state of gas, it not only burns the phosphuretted hydrogen, but any free hydrogen that may be present; but this has a limit: if the phosphuretted hydrogen be largely diluted (90 per cent.) with hydrogen, this last is wholly left; the reason seems to be, the phosphuretted hydrogen burns at a lower temperature; and hence probably it is, that liquid oxymuriate of lime burns the phosphuretted hydrogen, but not the hydrogen gas.
The quantity of oxygen necessary to saturate a given volume of phosphuretted hydrogen is easily found. Oxygen gas containing a known per centage of azotic gas, must be used in some excess, mixed with a due portion of the gas. After exploding the mixture, the loss must be observed, and then the remaining oxygen must be found by exploding it with hydrogen. Hence the true volume of oxygen spent by the first explosion, and that of the combustible gas are both determined. The due proportion of oxygen is so nearly 2 to 1, that I have not been able to determine on which side the truth lies. Dr. Thomson says that when phosphuretted hydrogen and oxygen are mixed, two volumes to one, a white smoke takes place, the volume of oxygen gradually disappears, and there remains behind a quantity of hydrogen exactly equal to the original volume of the phosphuretted hydrogen. I have observed nothing at all like this. A mixture of phosphuretted hydrogen and oxygen stood 24 hours without sensible diminution, and afterwards being exploded, 2 volumes of oxygen disappeared for 1 of phosphuretted hydrogen, the same as would have done at the moment of mixing. Perhaps the temperature may have some influence; mine was about 55°.
I have tried the minimum of oxygen that will consume or dissipate phosphuretted hydrogen gas. It may be exploded with about ¼ of its volume of oxygen, with the same phenomena as Davy observed of the hydrophosphoric gas. Phosphorus is thrown down and a volume of combustible gas is left about 10 per cent. greater than the original volume of phosphuretted hydrogen. This gas is nearly pure hydrogen. Hence the whole gas may be dissipated at 2 successive explosions, by rather less than an equal volume of oxygen. If phosphuretted hydrogen be exploded with an equal volume of oxygen, phosphorous acid, water and a little phosphoric acid are formed, and some hydrogen remains.
One of the most remarkable properties of phosphuretted hydrogen, is that announced by Dr. Thomson, namely, its combustion with nitrous gas by electricity; and the slow combustion by the same gas, which I have mentioned above is a fact still more difficult to explain. I tried the combustion of phosphuretted hydrogen by nitrous gas and electricity in 1810, but did not succeed. The reason was, the gas was not sufficiently pure. No phosphuretted hydrogen that is not 70 or 80 per cent. pure, can, I imagine, be exploded by nitrous gas; even the purest requires sometimes more than one spark, when mixed in the most favourable proportions; and I have known instances in which the mixture has exploded after electrification for a few minutes. An excess or defect of nitrous gas, occasions oxygen or hydrogen to be found in the residual gas, just as when we explode with oxygen. One volume of phosphuretted hydrogen requires, as nearly as I can find, 3½ of nitrous gas for mutual saturation. The azote developed amounts to 1¾ volumes or rather less, (due allowances in all such cases being made for that already existing in the two gases.)
The mutual action of nitrous gas and phosphuretted hydrogen without electricity exhibits one of the most singular phenomena we have in chemistry. Nitrous gas seems constantly to be decomposed, one part producing nitrous oxide and another part azote, even though an excess of nitrous gas remain undecomposed in the mixture, and both the phosphorus and hydrogen are completely burnt; but if the nitrous gas be deficient, then nitrous oxide, azote, and some of the phosphuretted hydrogen are found in the residue, and the rest of the phosphuretted hydrogen is completely burnt or converted into phosphoric acid and water; here appears no preference of phosphorus to hydrogen in this case, nor any partial combustion. From an attentive consideration of the results of several experiments, I am inclined to offer the following solution of this remarkable case: One atom of phosphuretted hydrogen attacks 5 of nitrous gas at the same instant; the atom of phosphorus takes 2 of oxygen, and gives the corresponding 2 of azote to the two of nitrous gas, and thus makes two atoms of nitrous oxide, while the hydrogen takes 1 of oxygen from the fifth atom and liberates the azote; thus 2 measures of nitrous oxide are formed along with 1 of azote; and they are generally found in the residue in that ratio. The azote does not seem to pass through the intermediate state of nitrous oxide; for, as soon as the nitrous gas ceases to exist, there is an end of the combustion.
It may be proper to advert more particularly to the hydrophosphoric gas of Davy. That this gas is the same as that we have been describing, can hardly admit of a doubt. Their near agreement in sp. gr., in their absorbability by water, in the quantity of oxygen requisite for their combustion, in their moderate expansion by burning with a minimum of oxygen and in their combustibility by oxymuriatic acid, are circumstances sufficient to warrant their identity. It is said that by heating potassium in this gas, one volume yields two of hydrogen; but it has not been found to yield two volumes by electricity, the more accurate criterion. Besides, both Davy and Gay Lussac find that potassium heated in the more common phosphuretted hydrogen expands it from 1 to 1⅓ or 1½ volume, which common electricity will not do; it is presumed therefore that the potassium in some way conduces to the production of a portion of the hydrogen. Spontaneous ignition or explosion is, I believe, no distinctive mark of variety in phosphuretted hydrogen; when this gas is produced, it is usually explosive from the uncombined phosphorus which it elevates; but the best and purest phosphuretted hydrogen loses the property wholly or partially by standing a while over water, though it loses no sensible part of its phosphorus.
It is commonly stated that phosphuretted hydrogen deposits phosphorus by long standing. This seems to be true; but the deposition is slower than I imagined. Seven years ago I set aside a bottle of impure phosphuretted hydrogen which I then labeled, 10 combustible take 14.6 oxygen; this bottle has not been preserved with special care to seclude the atmosphere; notwithstanding that, it is now such, that 10 combustible take 6.7 oxygen, and hence it still contains some genuine phosphuretted hydrogen.