Philosophical Transactions of the Royal Society
vol. 101, pp. 155-162 (1811)
Read February 21, 1811
I shall beg permission to lay before the Society the account of some experiments on a compound of oxymuriatic gas and oxygene gas, which, I trust, will be found to illustrate an interesting branch of chemical enquiry, and which offer some extraordinary and novel results.
I was led to make these experiments in consequence of the difference between the properties of oxymuriatic gas prepared in different modes; it would occupy a great length of time to state the whole progress of this investigation. It will, I conceive, be more interesting that I should immediately refer to the facts; most of which have been witnessed by Members of this Body, belonging to the Committee of Chemistry of the Royal Institution.
The oxymuriatic gas prepared from manganese, either by mixing it with a muriate and acting upon it by sulphuric acid, or by mixing it with muriatic acid, is when the oxide of manganese is pure, and, whether collected over water or mercury, uniform in its properties; its colour is a pale yellowish green; water takes up about twice its volume; and scarcely gains any colour; the metals burn in it readily; it combines with hydrogene without any deposition of moisture: it does not act on nitrous gas or muriatic acid, or carbonic oxide, or sulphureous gasses, when they have been carefully dried. It is the substance which I employed in all the experiments on the combinations of oxymuriatic gas described in my last two papers.
The gas produced by the action of muriatic acid on the salts which have been called hyperoxymuriates, on the contrary, differs very much in its properties, according as the manner in which it is prepared and collected is different.
When much acid is employed to a small quantity of salt, and the gas is collected over water, the water becomes tinged of a lemon colour; but the gas collected is the same as that procured from manganese.
When the gas is collected over mercury, and is procured form a weak acid, and from a great excess of salt by a low heat, its colour is a dense tint of brilliant yellow green, and it possesses properties entirely different from the gas collected over water.
It sometimes explodes during the time of its transfer from one vessel to another, producing heat and light, with an expansion of volume; and it may be always made to explode by a very gentle heat, often by that of the hand.*
*My brother, Mr. J. Davy, from whom I receive constant and able assistance in all my chemical enquiries, has several times observed explosions, in transferring the gas from hyperoxymuriate of potash, over mercury, and he was inclined to attribute the phaenomenon to th combustion of a thin film of mercury, in contact with a globule of gas. I several times endeavoured toproduce the effect, but withut success, till an acid was employed for the preparation of the gas, so diluted as not to afford it without the assistance of heat. The change of colour and expansion of volume, when the effect took place, immediately convinced me, that it was owing to a decomposition of the gas.
It is a compound of oxymuriatic gas and oxygene, mixed with some oxymuriatic gas. This is proved by the results of its spontaneous explosion. It gives off, in this process, from 1/6 to 2/5 its volume of oxygen, loses its vivid colour, and becomes common oxymuriatic gas.
I attempted to obtain the explosive gas in a pure form, by applying heat to a solution of it in water; but in this case, there was a partial decomposition; and some oxygene was disengaged, and some oxymuriatic gas formed. Finding that in the cases when it was most pure, it scarcely acted upon mercury, I attempted to separate the oxymuriatic gas with which it is mixed, by agitation in a tube with this metal; corrosive sublimate formed, and an elastic fluid was obtained, which was almost entirely absorbed by 1/4 of its volume of water.
This gas in its pure form is so easily decomposable that it is dangerous to operate upon considerable quantities.
In one set of experiments upon it, a jar of strong glass, containing 40 cubical inches, exploded in my hands with a loud report, producing light; the vessel was broken, and fragments of it were thrown to a considerable distance.
I analysed a portion of this gas, by causing it to explode over mercury in a curved glass tube, by the heat of a spirit lamp.
The oxymuriasitc gas formed, was absorbed by water; the oxygene was found to be pure, by the rest of nitrous gas.
50 parts of the detonating gas, by decomposition, expanded so as to become 60 parts. The oxygene, remaining after the absorption of the oxymuriatic gas, was about 20 parts. Several other experiments were made, with similar results. So that it may be inferred, that it consists of 2 in volume of oxymuriatic gas, and 1 in volume of oxygene; and the oxygene in the gas is condensed to half its volume. Circumstances conformable to the laws of combination of gaseous fluids, so ably illustrated by M. GAY LUSSAC, and to the theory of definite proportions.
I have stated on a former occasion, that approximations to the numbers representing the proportions in which oxygene and oxymuriatic gas combine, are found in 7-5 and 32.9. And this compound gas contains nearly these quantities.*
* In page 245 of the Phil. Tans. for 1810, I have mentioned that the specific gravity of oxymuriatic gas, is between 74 and 75 grains per 100 cubical inches. The gas that I weighed, was collected over water and procured from hyperoxymuriate of potash, and at that time I conceived, that this elastic fluid did not differ from the oxymuriatic gas from manganese, except in being purer. It probably contained some of the new gas; for I find that the specific gravity of pure oxymuriatic gas from manganese, and muriatic acid is to that of common air, as 244 to 100. Taking this extimation, the specific gravity of the new gas will be about 238, and the number representing the proportion in which oxymuriatic gas combines, from this estimation, will be rather higher than is stated above.
The smell of the pure explosive gas somewhat resembles that of burnt sugar, mixed with the peculiar smell of oxymuriatic gas. Water appeared to take up eight or ten times its volume ; but the experiment was made over mercury, which might occasion an error, though it did not seem to act on the fluid. The water became of a tint approaching to orange.
When the explosive gas was detonated with hydrogens, equal to twice its volume, there was a great absorption, to more than 1/3, and solution of muriatic acid was formed; when the explosive gas was in excess, oxygene was always expelled, a fact demonstrating the stronger attraction of hydrogene for oxymuriatic gas than for oxygene.
I have said that mercury has no action upon this gas in its purest form at common temperatures. Copper and antimony, which so readily burn in oxymuriatic gas, did not act upon the explosive gas in the cold: and when they were introduced into it, being heated, it was instantly decomposed, and its oxygene set free; and the metals burnt in the oxymuriatic gas.
When sulphur was introduce into it, there was at first no action, but an explosion soon took place: and the peculiar smell of oxymuriate of sulphur was perceived.
Phosphours produced a brilliant explosion, by contact with it in the cold, and there was produced phosphoric acid and solid oxymuriate of phosphorus.
Arsenic introduced into it did not inflame; the gas was made to explode, when the metal burnt with great brilliancy in the oxymuriatic gas.
Iron wire introduced into it did not burn, till it was heated so as to produce an explosion, when it burnt with a most brilliant light in the decomposed gas.
Charcoal introduced in it ignited, produced a brilliant flash of light, and burnt with a dull red light, doubtless owing to its action upon the oxygene mixed with the oxymuriatic gas.
It produced dense red fumes when mixed with nitrous gas, and there was no absorption of volume.
When it was mixed with muriatic acid gas, there was a gradual diminution of volume. By the application of heat the absorption was rapid, oxymuriatic gas was formed, and a dew appeared on the sides of the vessel.
These experiments enable us to explain the contradictory accounts that have been given by different authors of the properties of oxymuriatic gas.
That the explosive compound has not been collected before, is owing to the circumstance of water having been used for receiving the products from hyperoxymuriate of potash, and unless the water is highly saturated with the explosive gas, nothing but oxymuriatic gas is obtained; or to the circumstance of too dense an acid having been employed.
This substance produce the phaenomena which Mr. CHENEVIX. in his able paper on oxymuriatic acid, referred to the hyperoxygenised muriatic acid; and they prove the truth of his ideas respecting the possible existence of a compound of oxymuriatic gas, and oxygene in a separate state.
The explosions produced in a attempts to procure the products of hyperoxymuriate of potash by acids are evidently owing to the decomposition of this new and extraordinary substance.
All the conclusions which I have ventured to make respecting the undecompounded nature of oxymuriatic gas, are, I conceive, entirely confirmed by these new facts.
If oxymuriatic gas contained oxygene, it is not easy to conceive, why oxygene should be afforded by this new compound to muriatic gas, which must already contain oxygene in intimate union. Though on the idea of muriatic acid being a compound of hydrogene and oxymuriatic gas, the phaenomena are such as might be expected.
If the power of bodies to burn in oxymuriatic gas depended upon the presence of oxygene, they all ought to burn with much more energy in the new compound; but copper and antimony, and mercury, and arsenic, and iron, and sulphur have no action upon it, till it is decompsed; and they act then according to their relative attractions on the oxygene, or on the oxymuriatic gas.
There is a simple experiment which illustrates this idea; Let a glass vessel containing brass foil be exhausted, and the new gas admitted, no action will take place; throw in a little nitrous gas, a rapid decomposition occurs, and the metal burns with great brilliancy.
Supposing oxygene and oxymuriatic gas to belong to the same class of bodies; the attraction between them might be conceived very weak, as it is found to be, and they are easily separated form each other, and made repulsive by a very low degree of heat.
The most vivid effects of combustion known, are those produced by the condensation of oxygene or oxymuriatic gas; but in this instance, a violent explosion with heat and light are produced by their separation, and expansion, a perfectly novel circumstance in chemical philosophy.
This compound destroys dry vegetable colours, but first gives them a tint of red. This and its considerable absorbability by water would incline one to adopt Mr. CHENEVIX"s idea that it approaches to an acid in its nature. It is probably combined with the peroxide of potassium in the hyperoxymuriate.
That oxymuriatic gas and oxygene combine and separate from each other with such peculiar phaenomena, appears strongly in favor of the idea of their being distinct, though analogous species of matter. It is certainly possible to defend the hypothesis that oxymuriatic gas consists of oxygene united to an unknown basis; but it would be possible likewise to defend the speculation that it contains hydrogene.
Like oxygene it has not yet been decomposed; and I sometime ago made an experiment, which like most of the others I have brought forward, is very adverse to the idea of its containing oxygene.
I passed the solid oxymuriate of phosphorus in vapour, and oxygene gas together through a green glass tube heated to redness.
A decomposition took place,a and phosphoric acid was formed, and oxymuriatic gas was expelled.
Now, if oxygene existed in the oxymuriate of phosphorus, there is no reason why this change should take place. On the idea of oxymuriatic gas being undecompounded, it is easily explained. Oxygene is known to have a stronger attraction for phosphorus than oxymuriatic gas has, and consequently ought to expel it from this combination.
As the new compound in its purest form is possessed of a bright yellow green colour, it may be expedient to designate it by a name expressive of this circumstance, and its relation to oxymuriatic gas. As I have named that elastic fluid Chlorine, so I venture to propose for this substance the name Euchlorine, or Euchloric gas from eu and clwroV. The point of Nomenclature I am not, however, inclined to dwell upon. I shall be content to adopt any name that may be considered as most appropriate by the able chemical philosophers attached to this Society.
In page 48, it is stated that magnesia is not decomposed by oxymuriatic gas at a red heat. From some experiments of M. M. GAY LUSSAC, and THENARD, Bullet. de la Societ. Phil. Mai. 1810, it appears that oxygene is procured by passing oxymuriatic gas over magnesia, at a high temperature, and that a muriate indecomposable by heat is proved. They attribute the presence of this oxygene to the decomposition of the acid, but according to all analogies, it must arise from the decomposition of the earth.