The Combination of Hydrogen and Oxygen Into Water
Henry Cavendish
In Dr. Priestley’s last volume of experiments is related an experiment of Mr. Warltire’s, in which it is said that, on firing a mixture of common and inflammable air by electricity in a close copper vessel holding about three pints, a loss of weight was always perceived, on an average about two grains, though the vessel was stopped in such a manner that no air could escape by the explosion. It is also related, that on repeating the experiment in glass vessels, the inside of the glass, though clean and dry before, immediately became dewy; which confirmed an opinion he had long entertained, that common air deposits its moisture by phlogistication. As the latter experiment seemed likely to throw great light on the subject I had in view, I thought it well worth examining more closely. The first experiment also, if there was no mistake in it, would be very extraordinary and curious; but it did not succeed with me; for though the vessel I used held more than Mr. Warltire’s, namely, 24,000 grains of water, and though the experiment was repeated several times with different proportions of common and inflammable air, I could never perceive a loss of weight of more than one-fifth of a grain, and commonly none at all. It must be observed, however, that though there were some of the experiments in which it seemed to diminish a little in weight, there were none in which it increased.
In all the experiments, the inside of the glass globe became dewy, as observed by Mr. Warltire; but not the least sooty matter could be perceived. Care was taken in all of them to find how much the air was diminished by the explosion, and to observe its test. The result is as follows, the bulk of the inflammable air being expressed in decimals of the common air:
qqq
xyzCommon flammable Diminution. Air Remaining Test of this Standard,
Air. Air. after the Air in the
Explosion. First
1 1.241 .686 1.555 .055 .0
1.955 .642 1.423 .063 .0
.706 .647 1.059 .066 .0
.423 .612 .811 .097 .03
.331 .476 .855 .339 .27
.206 .294 .912 .648 .58
In these experiments the inflammable air was procured from zinc, as it was in all my experiments, except where otherwise expressed: but I made two more experiments, to try whether there was any difference between the air from zinc and that from iron, the quantity of inflammable air being the same in both, namely, 0.331 of the common; but I could not find any difference to be depended on between the two kinds of air, either in the diminution which they suffered by the explosion, or the test of the burnt air.
From the fourth experiment it appears, that 423 measures of inflammable air are nearly sufficient to completely phlogisticate 1000 of common air; and that the bulk of the remaining air after the explosion is then very little more than four-fifths of the common air employed; so that as common air cannot be reduced to a much less bulk than that by any method of phlogistication, we may safely conclude, that when they are mixed in this proportion, and exploded, almost all the inflammable air, and about one-fifth part of the common air, lose their elasticity, and are condensed into the dew which lines the glass.
The better to examine the nature of this dew, 500,000 grain measures of inflammable air were burnt with about two and one-half times that quantity of common air, and the burnt air made to pass through a glass cylinder eight feet long and three-quarters of an inch in diameter, in order to deposit the dew. The two airs were conveyed slowly into this cylinder by separate copper pipes, passing through a brass plate which stopped up the end of the cylinder; and as neither inflammable nor common air can burn by themselves, there was no danger of the flame spreading into the magazines from which they were conveyed. Each of these magazines consisted of a large tin vessel, inverted into another vessel just big enough to receive it. The inner vessel communicated with the copper pipe, and the air was forced out of it by pouring water into the outer vessel; and in order that the quantity of common air expelled should be two and one-half times that of the inflammable, the water was let into the outer vessels by two holes in the bottom of the same tin pan, the hole which conveyed the water into that vessel in which the common air was confined being two and one-half times as big as the other.
In trying the experiment, the magazines being first filled with their respective airs, the glass cylinder was taken off, and water let, by the two holes, into the outer vessels, till the airs began to issue from the ends of the copper pipes; they were then set on fire by a candle, and the cylinder put on again in its place. By this means upwards of 135 grains of water were condensed in the cylinder, which had no taste nor smell, and which left no sensible sediment when evaporated to dryness; neither did it yield any pungent smell during evaporation; in short, it seemed pure water.
In my first experiment, the cylinder near that part where the air was fired was a little tinged with sooty matter, but very slightly so; and that little seemed to proceed from the putty with which the apparatus was lured, and which was heated by the flame; for in another experiment, in which it was contrived so that the luting should not be much heated, scarce any sooty tinge could be perceived.
By the experiments with the globe it appeared, that when inflammable and common air are exploded in a proper proportion, almost all the inflammable air, and nearly one-fifth of the common air, lose their elasticity, and are condensed into dew. And by this experiment it appears, that this dew is plain water, and consequently that almost all the inflammable air and about one-fifth of the common air, are turned into pure water.
In order to examine the nature of the matter condensed on firing a mixture of dephlogisticated and inflammable air, I took a glass globe holding 8,800 grain measures, furnished with a brass cock and an apparatus for firing air by electricity. This globe was well exhausted by an air-pump, and then filled with a mixture of inflammable and dephlogisticated air, by shutting the cock, fastening a bent glass tube to its mouth, and letting up the end of it into a glass jar inverted into water, and containing a mixture of 19,500 grain measures of dephlogisticated air, and 37,000 of inflammable; so that, upon opening the cock, some of this mixed air rushed through the bent tube, and filled the globe. The cock was then shut, and the included air fired by electricity, by which means almost all of it lost its elasticity. The cock was then again opened, so as to let in more of the same air, to supply the place of that destroyed by the explosion, which was again fired, and the operation continued till almost the whole of the mixture was let into the globe and exploded. By this means, though the globe held not more than the the sixth part of the mixture, almost the whole of it was exploded therein, without any fresh exhaustion of the globe.
As I was desirous to try the quantity and test of this burnt air, without letting any water into the globe, which would have prevented my examining the nature of the condensed matter, I took a larger globe, furnished also with a stop cock, exhausted it by an air-pump, and screwed it on upon the cock of the former globe; upon which, by opening both cocks, the air rushed out of the smaller globe into the larger, till it became of equal density in both; then, by shutting the cock of the larger globe, unscrewing it again from the former, and opening it under water, I was enabled to find the quantity of the burnt air in it; and consequently, as the proportion which the contents of the two globes bore to each other was known, could tell the quantity of burnt air in the small globe before the communication was made between them. By this means the whole quantity of the burnt air was found to be 2,950 grain measures; its standard was 1.85.
The liquor condensed in the globe, in weight about thirty grains, was sensibly acid to the taste, and by saturation with fixed alkali, and evaporation, yielded near two grains of nitre; so that it consisted of water united to a small quantity of nitrous acid. No sooty matter was deposited in the globe. The dephlogisticated air used in this experiment was procured from red precipitate, that is, from a solution of quicksilver in spirit of nitre distilled till it acquires a red colour.
As it was suspected, that the acid contained in the condensed liquor was no essential part of the dephlogisticated air, but was owing to some acid vapour which came over in making it and had not been absorbed by the water, the experiment was repeated in the same manner, with some more of the same air, which had been previously washed with water, by keeping it a day or two in a bottle with some water, and shaking it frequently; whereas that used in the preceding experiment had never passed through water, except in preparing it. The condensed liquor was still acid.
The experiment was also repeated with dephlogisticated air, procured from red lead by means of oil of vitriol; the liquor condensed was acid, but by an accident I was prevented from determining the nature of the acid. [p.295]
I also procured some dephlogisticated air from the leaves of plants, in the manner of Doctors Ingenhousz and Priestley, and exploded it with inflammable air as before; the condensed liquor still continued acid, and of the nitrous kind.
In all these experiments the proportion of inflammable air was such, that the burnt air was not much phlogisticated; and it was observed, that the less phlogisticated it was, the more acid was the condensed liquor. I therefore made another experiment, with some more of the same air from plants, in which the proportion of inflammable air was greater, so that the burnt air was almost completely phlogisticated, its standard being 1–10. The condensed liquor was then not at all acid, but seemed pure water; so that it appears, that with this kind of dephlogisticated air, the condensed liquor is not at all acid, when the two airs are mixed in such a proportion that the burnt air is almost completely phlogisticated, but is considerably so when it is not much phlogisticated.
In order to see whether the same thing would obtain with air procured from red precipitate, I made two more experiments with that kind of air, the air in both being taken from the same bottle, and the experiment tried in the same manner, except that the proportions of inflammable air were different. In the first, in which the burnt air was almost completely phlogisticated, the condensed liquor was not at all acid. In the second, in which its standard was 1.86, that is, not much phlogisticated, it was considerably acid; so that with this air, as well as with that from plants, the condensed liquor contains, or is entirely free from, acid, according as the burnt air is less or more phlogisticated; and there can be little doubt but that the same rule obtains with any other kind of dephlogisticated air.
In order to see whether the acid, formed by the explosion of dephlogistlcated air obtained by means of the vitriolic acid, would also be of the nitrous kind, I procured some air from turbith mineral, and exploded it with inflammable air, the proportion being such that the burnt air was not much phlogisticated. The condensed liquor manifested an acidity, which appeared, by saturation with a solution of salt of tartar, to be of the nitrous kind; and it was found, by the addition of some terra ponderosa salita, to contain little or no vitriolic acid.
When inflammable air was exploded with common air, in such a proportion that the standard of the burnt air was about 4–10, the condensed liquor was not in the least acid. There is no difference, however, in this respect between common air, and dephlogisticated air mixed with phlogisticated in such a proportion as to reduce it to the standard of common air; for some dephlogisticated air from red precipitate, being reduced to this standard by the addition of perfectly phlogisticated air, and then exploded with the same proportion of inflammable air as the common air was in the foregoing experiment, the condensed liquor was not in the least acid.
From the foregoing experiments it appears, that when a mixture of inflammable and dephlogisticated air is exploded in such proportion that the burnt air is not much phlogisticated, the condensed liquor contains a little acid, which is always of the nitrous kind, whatever substance the dephlogisticated air is procured from; but if the proportion be such that the burnt air is almost entirely phlogisticated, the condensed liquor is not at all acid, but seems pure water, without any addition whatever; and as, when they are mixed in that proportion, very little air remains after the explosion, almost the whole being condensed, it follows that almost the whole of the inflammable and dephlogisticated air is converted into pure water. It is not easy, indeed, to determine from these experiments what proportion the burnt air, remaining after the explosions, bore to the dephlogisticated air employed, as neither the small nor the large globe could be perfectly exhausted of air, and there was no saying with exactness what quantity was left in them; but in most of them, after allowing for this uncertainty, the true quantity of burnt air seemed not more than 1–17 of the dephlogisticated air employed, or 1–50 of the mixture. It seems, however, unnecessary to determine this point exactly, as the quantity is so small, that there can be little doubt but that it proceeds only from the impurities mixed with the dephlogisticated and inflammable air, and consequently that, if those airs could be obtained perfectly pure, the whole would be condensed.
With respect to common air, and dephlogisticated air reduced by the addition of phlogisticated air to the standard of common air, the case is different; as the liquor condensed in exploding them with inflammable air, I believe I may say in any proportion, is not at all acid; perhaps because if they are mixed in such a proportion as that the burnt air is not much phlogisticated, the explosion is too weak, and not accompanied with sufficient heat.
All the foregoing experiments, on the explosion of inflammable air with common and dephlogisticated airs, except those which relate to the cause of the acid found in the water, were made in the summer of the year 1781, and were mentioned by me to Dr. Priestley, who in consequence of it made some experiments of the same kind, as he relates in a paper printed in the preceding volume of the Transactions. During the last summer also, a friend of mine gave some account of them to M. Lavoisier, as well as of the conclusion drawn from them, that dephlogisticated air is only water deprived of phlogiston; but at that time so far was M. Lavoisier from thinking any such opinion warranted, that, till he was prevailed upon to repeat the experiment himself, he found some difficulty in believing that nearly the whole of the two airs could be converted into water. It is remarkable, that neither of these gentlemen found any acid in the water produced by the combustion; which might proceed from the latter having burnt the two airs in a different manner from what I did; and from the former having used a different kind of inflammable air, namely, that from charcoal, and perhaps having used a greater proportion of it.