The Discovery of Oxygen
Joseph Priestly
Presently, after my return from abroad, I went to work upon the mercurius calcinatus, which I had procured from Mr. Cadet; and, with a very moderate degree of heat, I got from about one-fourth of an ounce of it, an ounce-measure of air, which I observed to be not readily imbibed, either by the substance itself from which it had been expelled (for I suffered them to continue a long time together before I transferred the air to any other place) or by water, in which I suffered this air to stand a considerable time before I made any experiment upon it.
In this air, as I had expected, a candle burned with a vivid flame; but what I observed new at this time (November 19), and which surprised me no less than the fact I had discovered before, was, that, whereas a few moments agitation in water will deprive the modified nitrous air of its property of admitting a candle to burn in it; yet, after more than ten times as much agitation as would be sufficient to produce this alteration in the nitrous air, no sensible change was produced in this. A candle still burned in it with a strong flame; and it did not, in the least, diminish common air, which I have observed that nitrous air, in this state, in some measure does.
But I was much more surprised, when, after two days, in which this air had continued in contact with water (by which it was diminished about one-twentieth of its bulk) I agitated it violently in water about five minutes, and found that a candle still burned in it as well as in common air. The same degree of agitation would have made phlogisticated nitrous air fit for respiration indeed, but it would certainly have extinguished a candle.
These facts fully convinced me, that there must be a very material difference between the constitution of the air from mercurius calcinatus, and that of phlogisticated nitrous air, notwithstanding their resemblance in some particulars. But though I did not doubt that the air from mercurius calcinatus was fit for respiration, after being agitated in water, as every kind of air without exception, on which I had tried the experiment, had been, I still did not suspect that it was respirable in the first instance; so far was I from having any idea of this air being, what it really was, much superior, in this respect, to the air of the atmosphere.
In this ignorance of the real nature of this kind of air, I continued from this time (November) to the 1st of March following; having, in the meantime, been intent upon my experiments on the vitriolic acid air above recited, and the various modifications of air produced by spirit of nitre, an account of which will follow. But in the course of this month, I not only ascertained the nature of this kind of air, though very gradually, but was led to it by the complete discovery of the constitution of the air we breathe.
Till this 1st of March, 1775, I had so little suspicion of the air from mercurius calcinatus, etc., being wholesome, that I had not even thought of applying it to the test of nitrous air; but thinking (as my reader must imagine I frequently must have done) on the candle burning in it after long agitation in water, it occurred to me at last to make the experiment; and putting one measure of nitrous air to two measures of this air, I found, not only that it was diminished, but that it was diminished quite as much as common air, and that the redness of the mixture was likewise equal to that of a similar mixture of nitrous and common air.
After this I had no doubt but that the air from mercurius calcinatus was fit for respiration, and that it had all the other properties of genuine common air. But I did not take notice of what I might have observed, if I had not been so fully possessed by the notion of there being no air better than common air, that the redness was really deeper, and the diminution something greater than common air would have admitted.
Moreover, this advance in the way of truth, in reality, threw me back into error, making me give up the hypothesis I had first formed, viz. that the mercurius calcinatus had extracted spirit of nitre from the air; for I now concluded, that all the constituent parts of the air were equally, and in their proper proportion, imbibed in the preparation of this substance, and also in the process of making red lead. For at the same time that I made the above mentioned experiment on the air from mercurius calcinatus, I likewise observed that the air which I had extracted from red lead, after the fixed air was washed out of it, was of the same nature, being diminished by nitrous air like common air: but, at the same time, I was puzzled to find that air from the red precipitate was diminished in the same manner, though the process for making this substance is quite different from that of making the two others. But to this circumstance I happened not to give much attention.
I wish my reader be not quite tired with the frequent repetition of the word surprise, and others of similar import; but I must go on in that style a little longer. For the next day I was more surprised than ever I had been before, with finding that, after the above-mentioned mixture of nitrous air and the air from mercurius calcinatus, had stood all night, (in which time the whole diminution must have taken place; and, consequently, had it been common air, it must have been made perfectly noxious, and entirely unfit for respiration or inflammation) a candle burned in it, and even better than in common air.
I cannot, at this distance of time, recollect what it was that I had in view in making this experiment; but I know I had no expectation of the real issue of it. Having acquired a considerable degree of readiness in making experiments of this kind, a very slight and evanescent motive would be sufficient to induce me to do it. If, however, I had not happened, for some other purpose, to have had a lighted candle before me, I should probably never have made the trial; and the whole train of my future experiments relating to this kind of air might have been prevented.
Still, however, having no conception of the real cause of this phenomenon, I considered it as something very extraordinary; but as a property that was peculiar to air that was extracted from these substances, and adventitious; and I always spoke of the air to my acquaintance as being substantially the same thing with common air. I particularly remember my telling Dr. Price, that I was myself perfectly satisfied of its being common air, as it appeared to be so by the test of nitrous air; though, for the satisfaction of others, I wanted a mouse to make the proof quite complete.
On the 8th of this month I procured a mouse, and put it into a glass vessel, containing two ounce-measures of the air from mercurius calcinatus. Had it been common air, a full-grown mouse, as this was, would have lived in it about a quarter of an hour. In this air, however, my mouse lived a full half hour; and though it was taken out seemingly dead, it appeared to have been only exceedingly chilled; for, upon being held to fire, it presently revived, and appeared not to have received any harm from the experiment.
By this I was confirmed in my conclusion, that the air extracted from mercurius calcinatus, etc., was, at least, as good as common air; but I did not certainly conclude that it was any belief; because, though one mouse would live only a quarter of an hour in a given quantity of air, I knew it was not impossible but that another mouse might have lived in it half an hour; so little accuracy is there in this method of ascertaining the goodness of air; and indeed I have never had recourse to it [p.282] for my own satisfaction, since the discovery of that most ready, accurate, and elegant test that nitrous air furnishes. But in this case I had a view to publishing the most generally satisfactory account of my experiments that the nature of the thing would admit of.
This experiment with the mouse, when I had reflected upon it some time, gave me so much suspicion that the air into which I had put it was better than common air, that I was induced, the day after, to apply the test of nitrous air to a small part of that very quantity of air which the mouse had breathed so long; so that, had it been common air, I was satisfied it must have been very nearly, if not altogether, as noxious as possible, so as not to be affected by nitrous air; when, to my surprise again, I found that though it had been breathed so long, it was still better than common air. For after mixing it with nitrous air, in the usual proportion of two to one, it was diminished in the proportion of four and one-half to three and one-half; that is, the nitrous air had made it two-ninths less than before, and this in a very short space of time; whereas I had never found that, in the longest time, any common air was reduced more than one-fifth of its bulk by any proportion of nitrous air, nor more than one-fourth by any phlogistic process whatever. Thinking of this extraordinary fact upon my pillow, the next morning I put another measure of nitrous air to the same mixture, and, to my utter astonishment, found that it was farther diminished to almost one-half of its original quantity. I then put a third measure to it; but this did not diminish it any farther; but, however, left it one measure less than it was even after the mouse had been taken out of it.
Being now fully satisfied that this air, even after the mouse had breathed it half an hour, was much better than common air; and having a quantity of it still left, sufficient for the experiment, viz. an ounce-measure and a half, I put the mouse into it; when I observed that it seemed to feel no shock upon being put into it, evident signs of which would have been visible, if the air had not been very wholesome; but that it remained perfectly at its ease another full half hour, when I took it out quite lively and vigorous. Measuring the air the next day, I found it to be reduced from one and one-half to two-thirds of an ounce-measure. And after this, if I remember well (for in my register of the day I only find it noted, that it was considerably diminished by nitrous air), it was nearly as good as common air. It was evident, indeed, from the mouse having been taken out quite vigorous, that the air could not have, been rendered very noxious. [p.283]
For my farther satisfaction I procured another mouse, and putting it into less than two ounce-measures of air extracted from mercurius calcinatus and air from red precipitate (which, having found them to be of the same quality, I had mixed together) it lived three-quarters of an hour. But not having had the precaution to set the vessel in a warm place, I suspect that the mouse died of cold. However, as it had lived three times as long as it could probably have lived in the same quantity of common air, and I did not expect much accuracy from this kind of a test, I did not think it necessary to make any more experiments with mice.
Being now fully satisfied of the superior goodness of this kind of air, I proceeded to measure that degree of purity, with as much accuracy as I could, by the test of nitrous air; and I began with putting one measure of nitrous air to two measures of this air, as if I had been examining common air; and now I observed that the diminution was evidently greater than common air would have suffered by the same treatment. A second measure of nitrous air reduced it to two-thirds of its original quantity, and a third measure to one-half. Suspecting that the diminution could not proceed much farther, I then added only half a measure of nitrous air, by which it was diminished still more; but not much, and another half measure made it more than half of its original quantity; so that, in this case, two measures of this air took more than two measures of nitrous air, and yet remained less than half of what it was. Five measures brought it pretty exactly to its original dimensions.
At the same time, air from the red precipitate was diminished in the same proportion as that from mercurius calcinatus, five measures of nitrous air being received by two measures of this without any increase of dimensions. Now as common air takes about one-half of its bulk of nitrous air, before it begins to receive any addition to its dimensions from more nitrous air, and this air took more than four half-measures before it ceased to be diminished by more nitrous air, and even five half-measures made no addition to its original dimensions, I conclude that it was between four and five times as good as common air. It will be seen that I have since procured air better than this, even between five and six times as good as the best common air that I have ever met with.