The Discovery of Carbonic Acid Gas, "Fixed Air"
Joseph Black
Hoffman, in one of his observations, gives the history of a powder called Magnesia Alba, which had been long used, and esteemed as a mild and tasteless purgative; but the method of preparing it was not generally known before he made it public. [p.273]
It was originally obtained from a liquor called the Mother of nitre, which is produced in the following manner:
Salt-petre is separated from the brine which first affords it, or from the water with which it is washed out of nitrous earths, by the process commonly used in crystallizing salts. In this process, the brine is gradually diminished, and at length reduced to a small quantity of an unctuous bitter saline liquor, affording no more salt-petre by evaporation, but, if urged with a brisk fire, drying up into a confused mass, which attracts water strongly, and becomes fluid again when exposed to the open air.
To this liquor the workmen have given the name of the Mother of nitre; and Hoffman, finding it composed of the magnesia united to an acid, obtained a separation of these, either by exposing the compound to a strong fire, in which the acid was dissipated, and the magnesia remained behind, or by the addition of an alkali, which attracted the acid to itself: and this last method he recommends as the best. He likewise makes an inquiry into the nature and virtues of the powder thus prepared; and observes, that it is an absorbent earth, which joins readily with all acids, and must necessarily destroy any acidity it meets in the stomach; but that its purgative power is uncertain, for sometimes it has not the least effect of that kind. As it is a mere insipid earth, he rationally concludes it to be a purgative only when converted into a sort of neutral salt by an acid in the stomach, and that its effect is therefore proportional to the quantity of this acid.
Although magnesia appears from this history of it, to be a very innocent medicine; yet, having observed that some hypochondriacs, who used it frequently, were subject to flatulencies and spasms, he seems to have suspected it of some noxious quality. The circumstances, however, which gave rise to his suspicion, may very possibly have proceeded from the imprudence of his patients; who, trusting too much to magnesia (which is properly a palliative in that disease) and neglecting the assistance of other remedies, allowed their disorder to increase upon them. It may, indeed, be alleged that magnesia, as a purgative, is not the most eligible medicine for such constitutions, as they agree best with those that strengthen, stimulate, and warm; which the saline purges, commonly used, are not observed to do. But there seems at least to be no objection to its use, when children are troubled with an acid in their stomach: for, gentle purging, in this case, is very proper; and it is often more conveniently procured by means of magnesia, than of any other medicine, on account of its being entirely insipid.
The above-mentioned Author, observing, some time after, that a bitter saline liquor, similar to that obtained from the brine of salt-petre, was likewise produced by the evaporation of those waters which contain common salt, had the curiosity to try if this would also yield a magnesia. The experiment succeeded: And he thus found out another process for obtaining this powder; and at the same time assured himself, by experiments, that the product from both was exactly the same.
My curiosity led me, some time ago, to inquire more particularly into the nature of magnesia, and especially to compare its properties with those of the other absorbent earths, of which there plainly appeared to me to be very different kinds, although commonly confounded together under one name. I was indeed led to this examination of the absorbent earths, partly by the hope of discovering a new sort of lime and lime-water, which might possibly be a more powerful solvent of the stone, than that commonly used; but was disappointed in my expectations.
I have had no opportunity of seeing Hoffman’s first magnesia, or the liquor from which it is prepared, and have therefore been obliged to make my experiments upon the second.
In order to prepare it, I at first employed the bitter saline liquor called bittern, which remains in the pans after the evaporation of sea-water. But as that liquor is not always easily procured, I afterwards made use of a salt called Epsom salt, which is separated from the bittern by crystallization, and is evidently composed of magnesia and the vitriolic acid.
There is likewise a spurious kind of Glauber salt, which yields plenty of magnesia, and seems to be no other than Epsom salt, of sea-water reduced to crystals of a larger size. And common salt also affords a small quantity of this powder; because, being separated from the bittern by one hasty crystallization only, it necessarily contains a portion of that liquor.
Those who would prepare a magnesia from Epsom salt, may use the following process:
Dissolve equal quantities of Epsom salt, and of pearl ashes, separately, in a sufficient quantity of water; purify each solution from its dregs, and mix them accurately together by violent agitation. Then make them just to boil over a brisk fire.
Add now to the mixture, three or four times its quantity of hot water; after a little agitation, allow the magnesia to settle to the bottom, and decant off as much of the water as possible. Pour on the same quantity of cold water; and, after settling, decant it off in the same manner. Repeat this washing with the cold water ten or twelve times, or even oftener, if the magnesia be required perfectly pure for chemical experiments.
When it is sufficiently washed, the water may be strained and squeezed from it in a linen cloth; for very little of the magnesia passes through.
The alkali in the mixture, uniting with the acid, separates it from the magnesia; which, not being of itself soluble in water, must consequently appear immediately under a solid form. But the powder which thus appears is not entirely magnesia; part of it, is the neutral salt formed from the union of the acid and alkali. This neutral salt is found, upon examination, to agree in all respects with vitriolated tartar, and requires a large quantity of hot water to dissolve it. As much of it is therefore dissolved as the water can take up; the rest is dispersed through the mixture, in the form of a powder. Hence the necessity of washing the magnesia with so much trouble; for the first effusion of hot water is intended to dissolve the whole of the salt, and the subsequent additions of cold water to wash away this solution.
The caution given, of boiling the mixture, is not unnecessary: if it be neglected, the whole of the magnesia is not accurately separated at once; and, by allowing it to rest for some time, that powder concretes into minute grains, which, when viewed with the microscope, appear to be assemblages of needles diverging from a point. This happens more especially when the solution of the Epsom salt, and of the alkali, are diluted with too much water before they are mixed together. Thus, if a dram of Epsom salt, and of salt of tartar, be dissolved each in four ounces of water, and be mixed, and then allowed to rest three or four days, the whole of the magnesia will be formed into these grains. Or, if we filtrate the mixture soon after it is made, and heat the clear liquor which passes through, it will become turbid, and deposit a magnesia.
An ounce of magnesia was exposed in a crucible, for about an hour, to such a heat as is sufficient to melt copper. When taken out, it weighed three drams and one scruple, or had lost 7–12 of its former weight.
I repeated, with the magnesia prepared in this manner, most of those experiments I had already made upon it before calcination, and the result was as follows:—
It dissolves in all the acids, and with these composes salts exactly similar to those described in the first set of experiments: But, what is particularly to be remarked, it is dissolved without any the least degree of effervescence. [p.276]
It slowly precipitates the corrosive sublimate of mercury, in the form of a black powder.
It separates the volatile alkali in salt-ammoniac from the acid, when it is mixed with a warm solution of that salt. But it does not separate an acid from a calcareous earth, nor does it introduce the least change upon lime-water.
Lastly, when a dram of it is digested with an ounce of water in a bottle for some hours, it does not make any the least change in the water. The magnesia, when dried, is found to have gained ten grains; but it neither effervesces with acids, nor does it sensibly affect lime-water.
Observing magnesia to lose such a remarkable proportion of its weight in the fire, my next attempts were directed to the investigation of this volatile part; and, among other experiments, the following seemed to throw some light upon it:—
Three ounces of magnesia were distilled in a glass retort and receiver, the fire being gradually increased until the magnesia was obscurely red hot. When all was cool, I found only five drams of a whitish water in the receiver, which had a faint smell of the spirit of hartshorn, gave a green colour to the juice of violets, and rendered the solutions of corrosive sublimate, and of silver, very slightly turbid. But it did not sensibly effervesce with acids.
The magnesia, when taken out of the retort, weighed an ounce, three drams, and thirty grains, or had lost more than half of its weight. It still effervesced pretty briskly with acids, though not so strongly as before this operation.
The fire should have been raised here to the degree requisite for the perfect calcination of magnesia. But, even from this imperfect experiment, it is evident, that, of the volatile parts contained in that powder, a small proportion only is water; the rest cannot, it seems, be retained in vessels, under a visible form. Chemists have often observed, in their distillations, that part of a body has vanished from their senses, notwithstanding the utmost care to retain it; and they have always found, upon further inquiry, that subtle part to be air, which having been imprisoned in the body, under a solid form, was set free, and rendered fluid and elastic by the fire. We may therefore safely conclude, that the volatile matter lost in the calcination of magnesia, is mostly air; and hence the calcined magnesia does not emit air, or make an effervescence when mixed with acids.
The water, from its properties, seems to contain a small portion of volatile alkali, which was probably formed from the earth, air and water, or from some of these combined together; and perhaps also from a small quantity of inflammable matter, which adhered accidentally to the magnesia. Whenever chemists meet with this salt, they are inclined to ascribe its origin to some animal or putrid vegetable substance; and this they have always done, when they obtained it from the calcareous earths, all of which afford a small quantity of it. There is, however, no doubt, that it can sometimes be produced independently of any such mixture, since many fresh vegetables, and tartar, afford a considerable quantity of it. And how can it, in the present instance, be supposed, that any animal or vegetable matter adhered to the magnesia, while it was dissolved by an acid, separated from this by an alkali, and washed with so much water?
Two drams of magnesia were calcined in a crucible, in the manner described above, and thus reduced to two scruples and twelve grains. This calcined magnesia was dissolved in a sufficient quantity of spirit of vitriol, and then again separated from the acid by the addition of an alkali, of which a large quantity is necessary for this purpose. The magnesia being very well washed and dried, weighed one dram and fifty grains. It effervesced violently, or emitted a large quantity of air, when thrown into acids; formed a red powder, when mixed with a solution of sublimate; separated the calcareous earths from an acid, and sweetened lime-water; and had thus recovered all those properties which it had but just now lost by calcination. Nor had it only recovered its original properties, but acquired besides an addition of weight, nearly equal to what had been lost in the fire; and as it is found to effervesce with acids, part of the addition must certainly be air.
This air seems to have been furnished by the alkali, from which it was separated by the acid; for Dr. Hales has clearly proved, that alkaline salts contain a large quantity of fixed air, which they emit in great abundance when joined to a pure acid. In the present case, the alkali is really joined to an acid, but without any visible emission of air; and yet the air is not retained in it; for the neutral salt, into which it is converted, is the same in quantity, and in every other respect, as if the acid employed had not been previously saturated with magnesia, but offered to the alkali in its pure state, and had driven the air out of it in their conflict. It seems therefore evident, that the air was forced from the alkali by the acid, and lodged itself in the magnesia.
These considerations led me to try a few experiments, whereby I might know what quantity of air is expelled from an alkali, or from magnesia, by acids.
Two drams of a pure fixed alkaline salt, and an ounce of water, were put into a Florentine flask, which, together with its contents, weighed two ounces and two drams. Some oil of vitriol diluted with water was dropped in, until the salt was exactly saturated; which it was found to be, when two drams, two scruples and three grains of this acid had been added. The phial with its contents now weighed two ounces, four drams and fifteen grains. One scruple, therefore, and eight grains, were lost during the ebullition; of which a trifling portion may be water, or something of the same kind; the rest is air.