Analysis of Atmospheric Air, and its Division into two Elastic Fluids; the one fit for Respiration, the other incapable of being respired.

From what has been premised, it follows, that our atmosphere is composed of a mixture of every substance capable of retaining the gasseous or aËriform state in the common temperature, and under the usual pressure which it experiences. These fluids constitute a mass, in some measure homogeneous, extending from the surface of the earth to the greatest height hitherto attained, of which the density continually decreases in the inverse ratio of the superincumbent weight. But, as I have before observed, it is possible that this first stratum is surmounted by several others consisting of very different fluids.

Our business, in this place, is to endeavour to determine, by experiments, the nature of the elastic fluids which compose the inferior stratum of air which we inhabit. Modern chemistry has made great advances in this research; and it will appear by the following details that the analysis of atmospherical air has been more rigorously determined than that of any other substance of the class. Chemistry affords two general methods of determining the constituent principles of bodies, the method of analysis, and that of synthesis. When, for instance, by combining water with alkohol, we form the species of liquor called, in commercial language, brandy or spirit of wine, we certainly have a right to conclude, that brandy, or spirit of wine, is composed of alkohol combined with water. We can produce the same result by the analytical method; and in general it ought to be considered as a principle in chemical science, never to rest satisfied without both these species of proofs.

We have this advantage in the analysis of atmospherical air, being able both to decompound it, and to form it a new in the most satisfactory manner. I shall, however, at present confine myself to recount such experiments as are most conclusive upon this head; and I may consider most of these as my own, having either first invented them, or having repeated those of others, with the intention of analysing atmospherical air, in perfectly new points of view.

I took a matrass (A, fig. 14. plate II.) of about 36 cubical inches capacity, having a long neck B C D E, of six or seven lines internal diameter, and having bent the neck as in Plate IV. Fig. 2. so as to allow of its being placed in the furnace M M N N, in such a manner that the extremity of its neck E might be inserted under a bell-glass F G, placed in a trough of quicksilver R R S S; I introduced four ounces of pure mercury into the matrass, and, by means of a syphon, exhausted the air in the receiver F G, so as to raise the quicksilver to L L, and I carefully marked the height at which it stood by pasting on a slip of paper. Having accurately noted the height of the thermometer and barometer, I lighted a fire in the furnace M M N N, which I kept up almost continually during twelve days, so as to keep the quicksilver always almost at its boiling point. Nothing remarkable took place during the first day: The Mercury, though not boiling, was continually evaporating, and covered the interior surface of the vessels with small drops, at first very minute, which gradually augmenting to a sufficient size, fell back into the mass at the bottom of the vessel. On the second day, small red particles began to appear on the surface of the mercury, which, during the four or five following days, gradually increased in size and number; after which they ceased to increase in either respect. At the end of twelve days, seeing that the calcination of the mercury did not at all increase, I extinguished the fire, and allowed the vessels to cool. The bulk of air in the body and neck of the matrass, and in the bell-glass, reduced to a medium of 28 inches of the barometer and 10° (54.5°) of the thermometer, at the commencement of the experiment was about 50 cubical inches. At the end of the experiment the remaining air, reduced to the same medium pressure and temperature, was only between 42 and 43 cubical inches; consequently it had lost about 1/6 of its bulk. Afterwards, having collected all the red particles, formed during the experiment, from the running mercury in which they floated, I found these to amount to 45 grains.

I was obliged to repeat this experiment several times, as it is difficult in one experiment both to preserve the whole air upon which we operate, and to collect the whole of the red particles, or calx of mercury, which is formed during the calcination. It will often happen in the sequel, that I shall, in this manner, give in one detail the results of two or three experiments of the same nature.

The air which remained after the calcination of the mercury in this experiment, and which was reduced to 5/6 of its former bulk, was no longer fit either for respiration or for combustion; animals being introduced into it were suffocated in a few seconds, and when a taper was plunged into it, it was extinguished as if it had been immersed into water.

In the next place, I took the 45 grains of red matter formed during this experiment, which I put into a small glass retort, having a proper apparatus for receiving such liquid, or gasseous product, as might be extracted: Having applied a fire to the retort in a furnace, I observed that, in proportion as the red matter became heated, the intensity of its colour augmented. When the retort was almost red hot, the red matter began gradually to decrease in bulk, and in a few minutes after it disappeared altogether; at the same time 41-1/2 grains of running mercury were collected in the recipient, and 7 or 8 cubical inches of elastic fluid, greatly more capable of supporting both respiration and combustion than atmospherical air, were collected in the bell-glass.

A part of this air being put into a glass tube of about an inch diameter, showed the following properties: A taper burned in it with a dazzling splendour, and charcoal, instead of consuming quietly as it does in common air, burnt with a flame, attended with a decrepitating noise, like phosphorus, and threw out such a brilliant light that the eyes could hardly endure it. This species of air was discovered almost at the same time by Mr Priestley, Mr Scheele, and myself. Mr Priestley gave it the name of dephlogisticated air, Mr Scheele called it empyreal air. At first I named it highly respirable air, to which has since been substituted the term of vital air. We shall presently see what we ought to think of these denominations.

In reflecting upon the circumstances of this experiment, we readily perceive, that the mercury, during its calcination, absorbs the salubrious and respirable part of the air, or, to speak more strictly, the base of this respirable part; that the remaining air is a species of mephitis, incapable of supporting combustion or respiration; and consequently that atmospheric air is composed of two elastic fluids of different and opposite qualities. As a proof of this important truth, if we recombine these two elastic fluids, which we have separately obtained in the above experiment, viz. the 42 cubical inches of mephitis, with the 8 cubical inches of respirable air, we reproduce an air precisely similar to that of the atmosphere, and possessing nearly the same power of supporting combustion and respiration, and of contributing to the calcination of metals.

Although this experiment furnishes us with a very simple means of obtaining the two principal elastic fluids which compose our atmosphere, separate from each other, yet it does not give us an exact idea of the proportion in which these two enter into its composition: For the attraction of mercury to the respirable part of the air, or rather to its base, is not sufficiently strong to overcome all the circumstances which oppose this union. These obstacles are the mutual adhesion of the two constituent parts of the atmosphere for each other, and the elective attraction which unites the base of vital air with caloric; in consequence of these, when the calcination ends, or is at least carried as far as is possible, in a determinate quantity of atmospheric air, there still remains a portion of respirable air united to the mephitis, which the mercury cannot separate. I shall afterwards show, that, at least in our climate, the atmospheric air is composed of respirable and mephitic airs, in the proportion of 27 and 73; and I shall then discuss the causes of the uncertainty which still exists with respect to the exactness of that proportion.

Since, during the calcination of mercury, air is decomposed, and the base of its respirable part is fixed and combined with the mercury, it follows, from the principles already established, that caloric and light must be disengaged during the process: But the two following causes prevent us from being sensible of this taking place: As the calcination lasts during several days, the disengagement of caloric and light, spread out in a considerable space of time, becomes extremely small for each particular moment of that time, so as not to be perceptible; and, in the next place, the operation being carried on by means of fire in a furnace, the heat produced by the calcination itself becomes confounded with that proceeding from the furnace. I might add the respirable part of the air, or rather its base, in entering into combination with the mercury, does not part with all the caloric which it contained, but still retains a part of it after forming the new compound; but the discussion of this point, and its proofs from experiment, do not belong to this part of our subject.

It is, however, easy to render this disengagement of caloric and light evident to the senses, by causing the decomposition of air to take place in a more rapid manner. And for this purpose, iron is excellently adapted, as it possesses a much stronger affinity for the base of respirable air than mercury. The elegant experiment of Mr Ingenhouz, upon the combustion of iron, is well known. Take a piece of fine iron wire, twisted into a spiral, (BC, Plate IV. Fig. 17.) fix one of its extremities B into the cork A, adapted to the neck of the bottle DEFG, and fix to the other extremity of the wire C, a small morsel of tinder. Matters being thus prepared, fill the bottle DEFG with air deprived of its mephitic part; then light the tinder, and introduce it quickly with the wire upon which it is fixed, into the bottle which you stop up with the cork A, as is shown in the figure (17 Plate IV.) The instant the tinder comes into contact with the vital air it begins to burn with great intensity; and, communicating the inflammation to the iron-wire, it too takes fire, and burns rapidly, throwing out brilliant sparks, which fall to the bottom of the vessel in rounded globules, which become black in cooling, but retain a degree of metallic splendour. The iron thus burnt is more brittle even than glass, and is easily reduced into powder, and is still attractable by the magnet, though not so powerfully as it was before combustion. As Mr Ingenhouz has neither examined the change produced on iron, nor upon the air by this operation, I have repeated the experiment under different circumstances, in an apparatus adapted to answer my particular views, as follows.

Having filled a bell-glass (A, Plate IV. Fig. 3.) of about six pints measure, with pure air, or the highly respirable part of air, I transported this jar by means of a very flat vessel, into a quicksilver bath in the bason BC, and I took care to render the surface of the mercury perfectly dry both within and without the jar with blotting paper. I then provided a small capsule of china-ware D, very flat and open, in which I placed some small pieces of iron, turned spirally, and arranged in such a way as seemed most favourable for the combustion being communicated to every part. To the end of one of these pieces of iron was fixed a small morsel of tinder, to which was added about the sixteenth part of a grain of phosphorus, and, by raising the bell-glass a little, the china capsule, with its contents, were introduced into the pure air. I know that, by this means, some common air must mix with the pure air in the glass; but this, when it is done dexterously, is so very trifling, as not to injure the success of the experiment. This being done, a part of the air is sucked out from the bell-glass, by means of a syphon GHI, so as to raise the mercury within the glass to EF; and, to prevent the mercury from getting into the syphon, a small piece of paper is twisted round its extremity. In sucking out the air, if the motion of the lungs only be used, we cannot make the mercury rise above an inch or an inch and a half; but, by properly using the muscles of the mouth, we can, without difficulty, cause it to rise six or seven inches.

I next took an iron wire, (MN, Plate IV. Fig. 16.) properly bent for the purpose, and making it red hot in the fire, passed it through the mercury into the receiver, and brought it in contact with the small piece of phosphorus attached to the tinder. The phosphorus instantly takes fire, which communicates to the tinder, and from that to the iron. When the pieces have been properly arranged, the whole iron burns, even to the last particle, throwing out a white brilliant light similar to that of Chinese fireworks. The great heat produced by this combustion melts the iron into round globules of different sizes, most of which fall into the China cup; but some are thrown out of it, and swim upon the surface of the mercury. At the beginning of the combustion, there is a slight augmentation in the volume of the air in the bell-glass, from the dilatation caused by the heat; but, presently afterwards, a rapid diminution of the air takes place, and the mercury rises in the glass; insomuch that, when the quantity of iron is sufficient, and the air operated upon is very pure, almost the whole air employed is absorbed.

It is proper to remark in this place, that, unless in making experiments for the purpose of discovery, it is better to be contented with burning a moderate quantity of iron; for, when this experiment is pushed too far, so as to absorb much of the air, the cup D, which floats upon the quicksilver, approaches too near the bottom of the bell-glass; and the great heat produced, which is followed by a very sudden cooling, occasioned by the contact of the cold mercury, is apt to break the glass. In which case, the sudden fall of the column of mercury, which happens the moment the least flaw is produced in the glass, causes such a wave, as throws a great part of the quicksilver from the bason. To avoid this inconvenience, and to ensure success to the experiment, one gross and a half of iron is sufficient to burn in a bell-glass, which holds about eight pints of air. The glass ought likewise to be strong, that it may be able to bear the weight of the column of mercury which it has to support.

By this experiment, it is not possible to determine, at one time, both the additional weight acquired by the iron, and the changes which have taken place in the air. If it is wished to ascertain what additional weight has been gained by the iron, and the proportion between that and the air absorbed, we must carefully mark upon the bell-glass, with a diamond, the height of the mercury, both before and after the experiment[9]. After this, the syphon (GH, Pl. IV. fig. 3.) guarded, as before, with a bit of paper, to prevent its filling with mercury, is to be introduced under the bell-glass, having the thumb placed upon the extremity, G, of the syphon, to regulate the passage of the air; and by this means the air is gradually admitted, so as to let the mercury fall to its level. This being done, the bell-glass is to be carefully removed, the globules of melted iron contained in the cup, and those which have been scattered about, and swim upon the mercury, are to be accurately collected, and the whole is to be weighed. The iron will be found in that state called martial ethiops by the old chemists, possessing a degree of metallic brilliancy, very friable, and readily reducible into powder, under the hammer, or with a pestle and mortar. If the experiment has succeeded well, from 100 grains of iron will be obtained 135 or 136 grains of ethiops, which is an augmentation of 35 per cent.

If all the attention has been paid to this experiment which it deserves, the air will be found diminished in weight exactly equal to what the iron has gained. Having therefore burnt 100 grains of iron, which has acquired an additional weight of 35 grains, the diminution of air will be found exactly 70 cubical inches; and it will be found, in the sequel, that the weight of vital air is pretty nearly half a grain for each cubical inch; so that, in effect, the augmentation of weight in the one exactly coincides with the loss of it in the other.

I shall observe here, once for all, that, in every experiment of this kind, the pressure and temperature of the air, both before and after the experiment, must be reduced, by calculation, to a common standard of 10° (54.5°) of the thermometer, and 28 inches of the barometer. Towards the end of this work, the manner of performing this very necessary reduction will be found accurately detailed.

If it be required to examine the nature of the air which remains after this experiment, we must operate in a somewhat different manner. After the combustion is finished, and the vessels have cooled, we first take out the cup, and the burnt iron, by introducing the hand through the quicksilver, under the bell-glass; we next introduce some solution of potash, or caustic alkali, or of the sulphuret of potash, or such other substance as is judged proper for examining their action upon the residuum of air. I shall, in the sequel, give an account of these methods of analysing air, when I have explained the nature of these different substances, which are only here in a manner accidentally mentioned. After this examination, so much water must be let into the glass as will displace the quicksilver, and then, by means of a shallow dish placed below the bell-glass, it is to be removed into the common water pneumato-chemical apparatus, where the air remaining may be examined at large, and with great facility.

When very soft and very pure iron has been employed in this experiment, and, if the combustion has been performed in the purest respirable or vital air, free from all admixture of the noxious or mephitic part, the air which remains after the combustion will be found as pure as it was before; but it is difficult to find iron entirely free from a small portion of charry matter, which is chiefly abundant in steel. It is likewise exceedingly difficult to procure the pure air perfectly free from some admixture of mephitis, with which it is almost always contaminated; but this species of noxious air does not, in the smallest degree, disturb the result of the experiment, as it is always found at the end exactly in the same proportion as at the beginning.

I mentioned before, that we have two ways of determining the constituent parts of atmospheric air, the method of analysis, and that by synthesis. The calcination of mercury has furnished us with an example of each of these methods, since, after having robbed the respirable part of its base, by means of the mercury, we have restored it, so as to recompose an air precisely similar to that of the atmosphere. But we can equally accomplish this synthetic composition of atmospheric air, by borrowing the materials of which it is composed from different kingdoms of nature. We shall see hereafter that, when animal substances are dissolved in the nitric acid, a great quantity of gas is disengaged, which extinguishes light, and is unfit for animal respiration, being exactly similar to the noxious or mephitic part of atmospheric air. And, if we take 73 parts, by weight, of this elastic fluid, and mix it with 27 parts of highly respirable air, procured from calcined mercury, we will form an elastic fluid precisely similar to atmospheric air in all its properties.

There are many other methods of separating the respirable from the noxious part of the atmospheric air, which cannot be taken notice of in this part, without anticipating information, which properly belongs to the subsequent chapters. The experiments already adduced may suffice for an elementary treatise; and, in matters of this nature, the choice of our evidences is of far greater consequence than their number.

I shall close this article, by pointing out the property which atmospheric air, and all the known gasses, possess of dissolving water, which is of great consequence to be attended to in all experiments of this nature. Mr Saussure found, by experiment, that a cubical foot of atmospheric air is capable of holding 12 grains of water in solution: Other gasses, as the carbonic acid, appear capable of dissolving a greater quantity; but experiments are still wanting by which to determine their several proportions. This water, held in solution by gasses, gives rise to particular phenomena in many experiments, which require great attention, and which has frequently proved the source of great errors to chemists in determining the results of their experiments.

[9] It will likewise be necessary to take care that the air contained in the glass, both before and after the experiment, be reduced to a common temperature and pressure, otherwise the results of the following calculations will be fallacious.—E.