Part 2

+8. Air must be composed of elastic fluids of two kinds.+

+First Experiment.+--I dissolved one ounce of alkaline liver of sulphur in eight ounces of water; I poured 4 ounces of this solution into an empty bottle capable of holding 24 ounces of water, and closed it most securely with a cork; I then inverted the bottle and placed the neck in a small vessel with water; in this position I allowed it to stand for 14 days. During this time the solution had lost a part of its red colour and had also deposited some sulphur: afterwards I took the bottle and held it in the same position in a larger vessel with water, so that the mouth was under and the bottom above the water-level, and withdrew the cork under the water; immediately water rose with violence into the bottle. I closed the bottle again, removed it from the water, and weighed the fluid which it contained. There were 10 ounces. After subtracting from this the 4 ounces of solution of sulphur there remain 6 ounces, consequently it is apparent from this experiment that of 20 parts of air 6 parts have been lost in 14 days.

+9. Second Experiment.+--(a.) I repeated the preceding experiment with the same quantity of liver of sulphur, but with this difference that I only allowed the bottle to stand a week, tightly closed. I then found that of 20 parts of air only 4 had been lost. (b.) On another occasion I allowed the very same bottle to stand 4 months; the solution still possessed a somewhat dark yellow colour. But no more air had been lost than in the first experiment, that is to say 6 parts.

+10. Third Experiment.+--I mixed 2 ounces of caustic ley, which was prepared from alkali of tartar and unslaked lime and did not precipitate lime water, with half an ounce of the preceding solution of sulphur which likewise did not precipitate lime water. This mixture had a yellow colour. I poured it into the same bottle, and after this had stood 14 days, well closed, I found the mixture entirely without colour and also without precipitate. I was enabled to conclude that the air in this bottle had likewise diminished, from the fact that air rushed into the bottle with a hissing sound after I had made a small hole in the cork.

+11. Fourth Experiment.+--(a.) I took 4 ounces of a solution of sulphur in lime water; I poured this solution into a bottle and closed it tightly. After 14 days the yellow colour had disappeared, and of 20 parts of air 4 parts had been lost. The solution contained no sulphur, but had allowed a precipitate to fall which was chiefly gypsum. (b.) Volatile liver of sulphur likewise diminishes the bulk of air. (c.) Sulphur, however, and volatile spirit of sulphur, undergo no alteration in it.

+12. Fifth Experiment.+--I hung up over burning sulphur, linen rags which were dipped in a solution of alkali of tartar. After the alkali was saturated with the volatile acid, I placed the rags in a flask, and closed the mouth most carefully with a wet bladder. After 3 weeks had elapsed I found the bladder strongly pressed down; I inverted the flask, held its mouth in water, and made a hole in the bladder; thereupon water rose with violence into the flask and filled the fourth part.

+13. Sixth Experiment.+--I collected in a bladder the nitrous air which arises on the dissolution of the metals in nitrous acid, and after I had tied the bladder tightly I laid it in a flask and secured the mouth very carefully with a wet bladder. The nitrous air gradually lost its elasticity, the bladder collapsed, and became yellow as if corroded by aqua fortis. After 14 days I made a hole in the bladder tied over the flask, having previously held it, inverted, under water; the water rose rapidly into the flask, and it remained only 2/3 empty.

+14. Seventh Experiment.+--(a.) I immersed the mouth of a flask in a vessel with oil of turpentine. The oil rose in the flask a few lines every day. After the lapse of 14 days the fourth part of the flask was filled with it; I allowed it to stand for 3 weeks longer, but the oil did not rise higher. All those oils which dry in the air, and become converted into resinous substances, possess this property. Oil of turpentine, however, and linseed oil rise up sooner if the flask is previously rinsed out with a concentrated sharp ley. (b.) I poured 2 ounces of colourless and transparent animal oil of Dippel into a bottle and closed it very lightly; after the expiry of two months the oil was thick and black. I then held the bottle, inverted, under water and drew out the cork; the bottle immediately became 1/4 filed with water.

+15. Eighth Experiment.+--(a.) I dissolved 2 ounces of vitriol of iron in 32 ounces of water, and precipitated this solution with a caustic ley. After the precipitate had settled, I poured away the clear fluid and put the dark green precipitate of iron so obtained, together with the remaining water, into the before-mentioned bottle (§ 8), and closed it tightly. After 14 days (during which time I shook the bottle frequently), this green calx of iron had acquired the colour of crocus of iron, and of 40 parts of air 12 had been lost. (b.) When iron filings are moistened with some water and preserved for a few weeks in a well closed bottle, a portion of the air is likewise lost. (c.) The solution of iron in vinegar has the same effect upon air. In this case the vinegar permits the dissolved iron to fall out in the form of a yellow crocus, and becomes completely deprived of this metal. (d.) The solution of copper prepared in closed vessels with spirit of salt likewise diminishes air. In none of the foregoing kinds of air can either a candle burn or the smallest spark glow.

+16.+ It is seen from these experiments that phlogiston, the simple inflammable principle, is present in each of them. It is known that the air strongly attracts to itself the inflammable part of substances and deprives them of it: not only this may be seen from the experiments cited, but it is at the same time evident that on the transference of the inflammable substance to the air a considerable part of the air is lost. But that the inflammable substance alone is the cause of this action, is plain from this, that, according to the 10th paragraph, not the least trace of sulphur remains over, since, according to my experiments this colourless ley contains only some vitriolated tartar. The 11th paragraph likewise shews this. But since sulphur alone, and also the volatile spirit of sulphur, have no effect upon the air (§ 11. c.), it is clear that the decomposition of liver of sulphur takes place according to the laws of double affinity,--that is to say, that the alkalies and lime attract the vitriolic acid, and the air attracts the phlogiston.

It may also be seen from the above experiments, that a given quantity of air can only unite with, and at the same time saturate, a certain quantity of the inflammable substance: this is evident from the 9th paragraph, letter b. But whether the phlogiston which was lost by the substances was still present in the air left behind in the bottle, or whether the air which was lost had united and fixed itself with the materials such as liver of sulphur, oils, &c., are questions of importance.

From the first view, it would necessarily follow that the inflammable substance possessed the property of depriving the air of part of its elasticity, and that in consequence of this it becomes more closely compressed by the external air. In order now to help myself out of these uncertainties, I formed the opinion that any such air must be specifically heavier than ordinary air, both on account of its containing phlogiston and also of its greater condensation. But how perplexed was I when I saw that a very thin flask which was filled with this air, and most accurately weighed, not only did not counterpoise an equal quantity of ordinary air, but was even somewhat lighter. I then thought that the latter view might be admissible; but in that case it would necessarily follow also that the lost air could be separated again from the materials employed. None of the experiments cited seemed to me capable of shewing this more clearly than that according to the 10th paragraph, because this residuum, as already mentioned, consists of vitriolated tartar and alkali. In order therefore to see whether the lost air had been converted into fixed air, I tried whether the latter shewed itself when some of the caustic ley was poured into lime water; but in vain--no precipitation took place. Indeed, I tried in several ways to obtain the lost air from this alkaline mixture, but as the results were similar to the foregoing, in order to avoid prolixity I shall not cite these experiments. Thus much I see from the experiments mentioned, that the air consists of two fluids, differing from each other, the one of which does not manifest in the least the property of attracting phlogiston, while the other, which composes between the third and the fourth part of the whole mass of the air, is peculiarly disposed to such attraction. But where this latter kind of air has gone to after it has united with the inflammable substance, is a question which must be decided by further experiments, and not by conjectures.

We shall now see how the air behaves towards inflammable substances when they get into fiery motion. We shall first consider that kind of fire which does not give out during the combustion any fluid resembling air.

+17. First Experiment.+--I placed 9 grains of phosphorus from urine in a thin flask, which was capable of holding 30 ounces of water, and closed its mouth very tightly. I then heated, with a burning candle, the part of the flask where the phosphorus lay; the phosphorus began to melt, and immediately afterwards took fire; the flask became filled with a white cloud, which attached itself to the sides like white flowers; this was the dry acid of phosphorus. After the flask had become cold again, I held it, inverted, under water and opened it; scarcely had this been done when the external air pressed water into the flask; this water amounted to 9 ounces.

+18. Second Experiment.+--When I placed pieces of phosphorus in the same flask and allowed it to stand, closed, for 6 weeks, or until it no longer glowed, I found that 1/3 of the air had been lost.

+19. Third Experiment.+--I placed 3 teaspoonfuls of iron filings in a bottle capable of holding 2 ounces of water; to this I added an ounce of water, and gradually mixed with them half an ounce of oil of vitriol. A violent heating and fermentation took place. When the froth had somewhat subsided, I fixed into the bottle an accurately fitting cork, through which I had previously fixed a glass tube A (Fig. 1). I placed this bottle in a vessel filled with hot water, B B (cold water would greatly retard the solution). I then approached a burning candle to the orifice of the tube, whereupon the inflammable air took fire and burned with a small yellowish-green flame. As soon as this had taken place, I took a small flask C, which was capable of holding 20 ounces of water, and held it so deep in the water that the little flame stood in the middle of the flask. The water at once began to rise gradually into the flask, and when the level had reached the point D the flame went out. Immediately afterwards the water began to sink again, and was entirely driven out of the flask. The space in the flask up to D contained 4 ounces, therefore the fifth part of the air had been lost. I poured a few ounces of lime water into the flask in order to see whether any aerial acid had also been produced during the combustion, but I did not find any. I made the same experiment with zinc filings, and it proceeded in every way similarly to that just mentioned. I shall demonstrate the constituents of this inflammable air further on; for, although it seems to follow from these experiments that it is only phlogiston, still other experiments are contrary to this.

We shall now see the behaviour of air towards that kind of fire which gives off, during the combustion, a fluid resembling air.

+20. Fourth Experiment.+--It is well known that the flame of a candle absorbs air; but as it is very difficult, and, indeed, scarcely possible, to light a candle in a closed flask, the following experiment was made in the first place:--I set a burning candle in a dish full water; I then placed an inverted flask over this candle; at once there arose from the water large air bubbles, which were caused by the expansion, by heat, of the air in the flask. When the flame became somewhat smaller, the water began to rise in the flask; after it had gone out and the flask had become cold, I found the fourth part filled with water. This experiment was very undecisive to me, because I was not assured whether this fourth part of the air had not been driven out by the heat of the flame; since necessarily in that case the external air resting upon the water seeks equilibrium again after the flask has become cold, and presses the same measure of water into the flask as of air had been previously driven out by the heat. Accordingly, I made the following experiment:

+21. Fifth Experiment.+--(a.) I pressed upon the bottom of the dish A (Fig. 2) a tough mass, of the thickness of two fingers, made of wax, resin, and turpentine metal together; in the middle I fastened a thick iron wire which reached to the middle of the flask B; upon the point of this wire C, I stuck a small wax candle, whose wick I had twisted together out of three slender threads. I then lighted the candle, and at the same time placed over it the inverted flask B, which I then pressed very deep into the mass. As soon as this was done, I filled the dish with water. After the flame was extinguished and everything had become quite cold, I opened the flask in the same position under the water, when 2 ounces of water entered; the flask held 160 ounces of water. Accordingly, there is wanting here so much air as occupies the space of 2 ounces of water. Has this air been absorbed by the inflammable substance, or has the heat of the small flame driven it out even before I could press the flask into the tough mass? The latter seems to have taken place in this case, as I conclude from the following:--I took a small flask capable of holding 20 ounces of water; in this I caused a candle to burn as in the preceding; after everything had become cold, I opened this flask likewise under water, whereupon similarly nearly 2 ounces entered. Had the former 2 ounces measure of air been absorbed, then there should have been only 2 drachms measure absorbed in this experiment.

(b.) I repeated the preceding experiment with the large flask in exactly the same way, except that I employed spirit of wine in place of the candle. I fastened three iron wires, which were of equal length and reached up to the middle of the flask, into the tough mass which was firmly pressed on to the bottom of the dish. Upon these wires I laid a four-cornered plate of metal, and upon this I placed a small vessel into which spirit of wine was poured. I set fire to this and placed the flask over it. After cooling, I observed that 3 ounces measure of air had been driven out by the heat of the flame.

(c.) Upon the same stand I placed a few small glowing coals, and allowed then go out in the same way under the flask. I found after cooling that the heat of the coals had driven out three and a half ounces measure of air.

The experiments seem to prove that the transference of phlogiston to the air does not always diminish its bulk, which, however, the experiments mentioned in §§ 8.16 shew distinctly. But the following will shew that that portion of the air which unites with the inflammable substance, and is at the same time absorbed by it, is replaced by the newly formed aerial acid.

+22. Sixth Experiment.+--After the fire had gone out and everything had become cold in the experiments mentioned above (§ 21. a. b. c.), I poured into each flask 6 ounces of milk of lime (lime water which has in it more unslaked lime than the water can dissolve); I then placed my hand firmly on the mouth of the flask and swung it several times up and down; then I held the flask inverted under water and drew my hand a little to one side, so that a small orifice might be made. Water immediately rose into the flask. Then I shut the mouth again very tightly with my hand under water, and afterwards shook it several times up and down. I opened it again under water; this operation I repeated twice more until no more water would rise into the flask, or until no more aerial acid was present in it. I then perceived that in each experiment between 7 and 8 ounces of water rose into the flasks, consequently the nineteenth part of the air has been lost. This was indeed something, but since in the combustion of phosphorus (§ 17) nearly the third part of the air was lost, there must be another reason besides, why as much is not absorbed in this case also. It is known that one part of aerial acid mixed with 10 parts of ordinary air extinguishes fire; and there are here in addition, expanded by the heat of the flame and surrounding the latter, the watery vapours produced by the destruction of these oily substances. It is these two elastic fluids, separating themselves from such a flame, which present no small hindrance to the fire which would otherwise certainly burn much longer, especially since there is here no current of air by means of which they can be driven away from the flame. When the aerial acid is separated from this air by milk of lime, then a candle can burn in it again, although only for a very short time.

+23. Seventh Experiment.+--I placed upon the stand (§ 21. b.) a small crucible which was filled with sulphur; I set fire to it and placed the flask over it. After the sulphur was extinguished and everything had become cold, I found that out of 160 parts of air, 2 parts were driven out of the flask by the heat of the flame. I next poured 6 ounces of clear lime water into the flask and dealt with it by shaking, as already explained, and observed that the sixth part of all the air had been lost in consequence of the combustion. The lime water was not in the least precipitated in this case, an indication that sulphur gives out no aerial acid during its combustion, but another substance somewhat resembling air; this is the volatile acid of sulphur, which occupies again the empty space produced by the union of the inflammable substance with air. It is not, as may be seen, a trifling circumstance that phlogiston, whether it separates itself from substances and enters into union with air, with or without a fiery motion, still in every case diminishes the air so considerably in its external bulk.

+24. Experiments which prove that ordinary air, consisting of two kinds of elastic fluids, can be compounded again after these have been separated from each other by means of phlogiston.+

I have already stated in § 16 that I was not able to find again the lost air. One might indeed object, that the lost air still remains in the residual air which can no more unite with phlogiston; for, since I have found that it is lighter than ordinary air, it might be believed that the phlogiston united with this air makes it lighter, as appears to be known already from other experiments. But since phlogiston is a substance, which always presupposes some weight, I much doubt whether such hypothesis has any foundation....

+25.+ How often must not chemists have distilled the fuming acid of nitre from oil of vitriol and nitre, when it is impossible that they should not have observed how this acid went over red in the beginning, white and colourless in the middle of the distillation, but at the end red again; and indeed so dark-red that one could not see through the receiver? It is to be noticed here that if the heat is permitted to increase too much at the end of the distillation, the whole mixture enters into such frothing that everything goes over into the receiver; and, what is of the greatest importance, a kind of air goes over during this frothing which deserves no small attention. If one takes for such distillation a very black oil of vitriol, not only does the acid go over at the beginning of a far darker red than when one takes a white oil of vitriol, but further, when one introduces a burning candle into the receiver after about an ounce has gone over, this goes out immediately. On the other hand, when one places a burning candle in the receiver filled with blood-red vapours, towards the end of the distillation when, as has been said, the mixture froths strongly, not only will it continue to burn, but this will take place with a much brighter light than in ordinary air. The same thing occurs when one attaches, at the close of the distillation, a receiver which is filled with an air in which fire will not burn, for, when this has been attached for half an hour, a candle will likewise continue to burn in the air.

In this case there now arises in the first place the question: Are the vapours of the acid of nitre naturally red? I beg leave to raise this question here because I believe there are people who advance the redness of this acid as a distinguishing characteristic. The colours of the acid of nitre are accidental. When a few ounces of fuming acid of nitre are distilled by a very gentle heat, the yellow separates itself from it and goes into the receiver, and the residuum in the retort becomes white and colourless like water. This acid has all the chief properties of acid of nitre, except that the yellow colour is wanting. This I call the pure acid of nitre; as soon, however, as it comes into contact with an inflammable substance, it becomes more or less red. This red acid is more volatile than the pure, hence heat alone can separate them from one another; and, for exactly the same reason, the volatile spirit must go over first in the distillation of Glauber's spirit of nitre. When this has gone over, the colourless acid follows; but why does the acid make its appearance again so blood-red at the end of the distillation? Why has not this redness already been driven over at the beginning? Where does it now obtain its phlogiston? This is the difficulty.