I have already shown, Part I. Chap. IX. that oxygen does not always part with the whole of the caloric it contained in the state of gas when it enters into combination with other bodies. It carries almost the whole of its caloric alongst with it in entering into the combinations which form nitric acid and oxygenated muriatic acid; so that in nitrats, and more especially in oxygenated muriats, the oxygen is, in a certain degree, in the state of oxygen gas, condensed, and reduced to the smallest volume it is capable of occupying.
In these combinations, the caloric exerts a constant action upon the oxygen to bring it back to the state of gas; hence the oxygen adheres but very slightly, and the smallest additional force is capable of setting it free; and, when such force is applied, it often recovers the state of gas instantaneously. This rapid passage from the solid to the aëriform state is called detonation, or fulmination, because it is usually accompanied with noise and explosion. Deflagrations are commonly produced by means of combinations of charcoal either with nitre or oxygenated muriat of potash; sometimes, to assist the inflammation, sulphur is added; and, upon the just proportion of these ingredients, and the proper manipulation of the mixture, depends the art of making gun-powder.
As oxygen is changed, by deflagration with charcoal, into carbonic acid, instead of oxygen gas, carbonic acid gas is disengaged, at least when the mixture has been made in just proportions. In deflagration with nitre, azotic gas is likewise disengaged, because azote is one of the constituent elements of nitric acid.
The sudden and instantaneous disengagement and expansion of these gasses is not, however, sufficient for explaining all the phenomena of deflagration; because, if this were the sole operating power, gun powder would always be so much the stronger in proportion as the quantity of gas disengaged in a given time was the more considerable, which does not always accord with experiment. I have tried some kinds which produced almost double the effect of ordinary gun powder, although they gave out a sixth part less of gas during deflagration. It would appear that the quantity of caloric disengaged at the moment of detonation contributes considerably to the expansive effects produced; for, although caloric penetrates freely through the pores of every body in nature, it can only do so progressively, and in a given time; hence, when the quantity disengaged at once is too large to get through the pores of the surrounding bodies, it must necessarily act in the same way with ordinary elastic fluids, and overturn every thing that opposes its passage. This must, at least in part, take place when gun-powder is set on fire in a cannon; as, although the metal is permeable to caloric, the quantity disengaged at once is too large to find its way through the pores of the metal, it must therefore make an effort to escape on every side; and, as the resistance all around, excepting towards the muzzle, is too great to be overcome, this effort is employed for expelling the bullet.
The caloric produces a second effect, by means of the repulsive force exerted between its particles; it causes the gasses, disengaged at the moment of deflagration, to expand with a degree of force proportioned to the temperature produced.
It is very probable that water is decomposed during the deflagration of gun-powder, and that part of the oxygen furnished to the nascent carbonic acid gas is produced from it. If so, a considerable quantity of hydrogen gas must be disengaged in the instant of deflagration, which expands, and contributes to the force of the explosion. It may readily be conceived how greatly this circumstance must increase the effect of powder, if we consider that a pint of hydrogen gas weighs only one grain and two thirds; hence a very small quantity in weight must occupy a very large space, and it must exert a prodigious expansive force in passing from the liquid to the aëriform state of existence.
In the last place, as a portion of undecomposed water is reduced to vapour during the deflagration of gun-powder, and as water, in the state of gas, occupies seventeen or eighteen hundred times more space than in its liquid state, this circumstance must likewise contribute largely to the explosive force of the powder.
I have already made a considerable series of experiments upon the nature of the elastic fluids disengaged during the deflagration of nitre with charcoal and sulphur; and have made some, likewise, with the oxygenated muriat of potash. This method of investigation leads to tollerably accurate conclusions with respect to the constituent elements of these salts. Some of the principal results of these experiments, and of the consequences drawn from them respecting the analysis of nitric acid, are reported in the collection of memoirs presented to the Academy by foreign philosophers, vol. xi. p. 625. Since then I have procured more convenient instruments, and I intend to repeat these experiments upon a larger scale, by which I shall procure more accurate precision in their results; the following, however, is the process I have hitherto employed. I would very earnestly advise such as intend to repeat some of these experiments, to be very much upon their guard in operating upon any mixture which contains nitre, charcoal, and sulphur, and more especially with those in which oxygenated muriat of potash is mixed with these two materials.
I make use of pistol barrels, about six inches long, and of five or six lines diameter, having the touch-hole spiked up with an iron nail strongly driven in, and broken in the hole, and a little tin-smith's solder run in to prevent any possible issue for the air. These are charged with a mixture of known quantities of nitre and charcoal, or any other mixture capable of deflagration, reduced to an impalpable powder, and formed into a paste with a moderate quantity of water. Every portion of the materials introduced must be rammed down with a rammer nearly of the same caliber with the barrel, four or five lines at the muzzle must be left empty, and about two inches of quick match are added at the end of the charge. The only difficulty in this experiment, especially when sulphur is contained in the mixture, is to discover the proper degree of moistening; for, if the paste be too much wetted, it will not take fire, and if too dry, the deflagration is apt to become too rapid, and even dangerous.
When the experiment is not intended to be rigorously exact, we set fire to the match, and, when it is just about to communicate with the charge, we plunge the pistol below a large bell-glass full of water, in the pneumato chemical apparatus. The deflagration begins, and continues in the water, and gas is disengaged with less or more rapidity, in proportion as the mixture is more or less dry. So long as the deflagration continues, the muzzle of the pistol must be kept somewhat inclined downwards, to prevent the water from getting into its barrel. In this manner I have sometimes collected the gas produced from the deflagration of an ounce and half, or two ounces, of nitre.
In this manner of operating it is impossible to determine the quantity of carbonic acid gas disengaged, because a part of it is absorbed by the water while passing through it; but, when the carbonic acid is absorbed, the azotic gas remains; and, if it be agitated for a few minutes in caustic alkaline solution, we obtain it pure, and can easily determine its volume and weight. We may even, in this way, acquire a tollerably exact knowledge of the quantity of carbonic acid by repeating the experiment a great many times, and varying the proportions of charcoal, till we find the exact quantity requisite to deflagrate the whole nitre employed. Hence, by means of the weight of charcoal employed, we determine the weight of oxygen necessary for saturation, and deduce the quantity of oxygen contained in a given weight of nitre.
I have used another process, by which the results of this experiment are considerably more accurate, which consists in receiving the disengaged gasses in bell-glasses filled with mercury. The mercurial apparatus I employ is large enough to contain jars of from twelve to fifteen pints in capacity, which are not very readily managed when full of mercury, and even require to be filled by a particular method. When the jar is placed in the cistern of mercury, a glass syphon is introduced, connected with a small air-pump, by means of which the air is exhausted, and the mercury rises so as to fill the jar. After this, the gas of the deflagration is made to pass into the jar in the same manner as directed when water is employed.
I must again repeat, that this species of experiment requires to be performed with the greatest possible precautions. I have sometimes seen, when the disengagement of gas proceeded with too great rapidity, jars filled with more than an hundred and fifty pounds of mercury driven off by the force of the explosion, and broken to pieces, while the mercury was scattered about in great quantities.
When the experiment has succeeded, and the gas is collected under the jar, its quantity in general, and the nature and quantities of the several species of gasses of which the mixture is composed, are accurately ascertained by the methods already pointed out in the second chapter of this part of my work. I have been prevented from putting the last hand to the experiments I had begun upon deflagration, from their connection with the objects I am at present engaged in; and I am in hopes they will throw considerable light upon the operations belonging to the manufacture of gun-powder.
