38. The New Gases
Of Dephlogisticated Air and of the Constitution of the Atmosphere
SOURCE: Joseph Priestley, Experiments and Observations on Different Kinds of Air (London, 1775), II, 29-61.
The contents of this section will furnish a very striking illustration of the truth of a remark, which I have more than once made in my philosophical writings, and which can hardly be too often repeated as it tends greatly to encourage philosophical investigations; viz. that more is owing to what we call chance, that is, philosophically speaking, to the observation of events arising from unknown causes, than to any proper design, or pre-conceived theory in this business. This does not appear in the works of those who write synthetically upon these subjects, but would, I doubt not, appear very strikingly in those who are the most celebrated for their philosophical acumen, did they write analytically and ingenuously.
For my own part, I will frankly acknowledge that, at the commencement of the experiments recited in this section, I was so far from having formed any hypothesis that led to the discoveries I made in pursuing them that they would have appeared very improbable to me had I been told of them; and when the decisive facts did at length obtrude themselves upon my notice, it was very slowly, and with great hesitation that I yielded to the evidence of my senses. And yet, when I re-consider the matter, and compare my last discoveries relating to the constitution of the atmosphere with the first, I see the closest and the easiest connection in the world between them, so as to wonder that I should not have been led immediately from the one to the other. That this was not the case, I attribute to the force of prejudice, which, unknown to ourselves, biases not only our judgments, properly so called, but even the perceptions of our senses: for we may take a maxim so strongly for granted, that the plainest evidence of sense will not entirely change, and often hardly modify our persuasions; and the more ingenious a man is, the more effectually he is entangled in his errors; his ingenuity only helping him to deceive himself, by evading the force of truth.
There are, I believe, very few maxims in philosophy that have laid firmer hold upon the mind, than that air, meaning atmospherical air (free from various foreign matters, which were always supposed to be dissolved, and intermixed with it) is a simple elementary substance, indestructable and unalterable, at least as much so as water is supposed to be. In the course of my enquiries, I was, however, soon satisfied that atmospherical air is not an unalterable thing; for that the phlogiston with which it becomes loaded from bodies burning in it, and animals breathing it, and various other chemical processes, so far alters and depraves it, as to render it altogether unfit for inflammation, respiration and other purposes to which it is subservient;1 and I had discovered that agitation in water, the process of vegetation, and probably other natural processes, by taking out the superfluous phlogiston, restore it to its original purity. But I own I had no idea of the possibility of going any farther in this way, and thereby procuring air purer than the best common air. I might, indeed, have naturally imagined that such would be air that should contain less phlogiston than the air of the atmosphere; but I had no idea that such a composition was possible.
It will be seen in my last publication, that, from the experiments which I made on the marine acid air ,2 I was led to conclude, that common air consisted of some acid (and I naturally inclined to the acid that I was then operating upon) and phlogiston; because the union of this acid vapour and phlogiston made inflammable air;3 and inflammable air, by agitation in water, ceases to be inflammable, and becomes respirable.4 And though I could never make it quite so good as common air, I thought it very probable that vegetation, in more favourable circumstances than any in which I could apply it, or some other natural process, might render it more pure.
1. This is a clear and simple statement of the function of phlogiston as conceived at this time (and indeed never relinquished by Priestley): that it was given off in combustion and respiration and that substances which supported either of these processes were necessarily rich in phlogiston.
2. Hydrochloric acid gas (HCl).
4. Priestley here is somewhat confused; hydrogen does not react with water, but it is probable that his original "inflammable air" was mixed with ordinary air to a certain extent.
Upon this, which no person can say was an improbable supposition, was founded my conjecture, of volcanos having given birth to the atmosphere of this planet, supplying it with a permanent air, first inflammable, then deprived of its inflammability by agitation in water, and farther purified by vegetation.
Several of the known phenomena of the nitrous acid5 might have led me to think, that this was more proper for the constitution of the atmosphere than the marine acid: but my thoughts had got into a different train, and nothing but a series of observations, which I shall now distinctly relate, compelled me to adopt another hypothesis, and brought me, in a way of which I had then no idea, to the solution of the great problem, which my reader will perceive I have had in view ever since my discovery that the atmospherical air is alterable, and therefore that it is not an elementary substance, but a composition viz. what this composition is, or what is the thing that we breathe, and how is it to be made from its constituent principles
5. Probably the modern nitrogen dioxide (NO2).
At the time of my former publication, I was not possessed of a burning lens of any considerable force; and for want of one, I could not possibly make many of the experiments that I had projected, and which, in theory, appeared very promising. I had, indeed, a mirror of force sufficient for my purpose. But the nature of this instrument is such, that it cannot be applied, with effect, upon substances that are capable of being suspended, or resting on a very slender support. It cannot be directed at all upon any substance in the form of powder, nor hardly upon anything that requires to be put into a vessel of quicksilver; which appears to me to be the most accurate method of extracting air from a great variety of substances, as was explained in the Introduction to this volume. But having afterwards procured a lens of twelve inches diameter, and twenty inches focal distance, I proceeded with great alacrity to examine, by the help of it, what kind of air a great variety of substances, natural and factitious, would yield, putting them into . . . vessels . . . which I filled with quicksilver and kept inverted in a basin of the same. Mr. Warltire, a good chymist, and lecturer in natural philosophy, happening to be at that time in Calne, I explained my views to him, and was furnished by him with many substances, which I could not otherwise have procured.
With this apparatus, after a variety of other experiments, an account of which will be found in its proper place, on the 1st of August, 1774, I endeavoured to extract air from mercurius calcinatus per se6 and I presently found that, by means of this lens, air was expelled from it very readily. Having got about three or four times as much as the bulk of my materials, I admitted water to it, and found that it was not imbibed by it. But what surprised me more than I can well express, was, that a candle burned in this air with a remarkably vigorous flame, very much like that enlarged flame with which a candle burns in nitrous air, exposed to iron or liver of sulphur; but as I had got nothing like this remarkable appearance from any kind of air besides this particular modification of nitrous air, and I knew no nitrous acid was used in the preparation of mercurius calcinatus, I was utterly at a loss how to account for it
6. Mercuric oxide, HgO; here Priestley was decomposing it to get pure
In this case, also, though I did not give sufficient attention to the circumstance at that time, the flame of the candle, besides being larger, burned with more splendor and heat than in that species of nitrous air;. and a piece of red-hot wood sparkled in it, exactly like paper dipped in a solution of nitre, and it consumed very fast; an experiment which I had never thought of trying with nitrous air.
At the same time that I made the above mentioned experiment, I extracted a quantity of air, with the very same property, from the common red precipitate, which being produced by a solution of mercury in spirit of nitre,7 made me conclude that this peculiar property, being similar to that of the modification of nitrous air above mentioned, depended upon something being communicated to it by the nitrous acid; and since the mercurius calcinatus is produced by exposing mercury to a certain degree of heat, where common air has access to it, I likewise concluded that this substance had collected something of nitre, in that state of heat, from the atmosphere.
7. Mercury treated with nitric acid would form mercuric oxide, as Priestley says.
This, however, appearing to me much more extraordinary than it ought to have done, I entertained some suspicion that the mercurius calcinatus, on which I had made my experiments, being bought at a common apothecary's, might in fact, be nothing more than red precipitate; though, had I been anything of a practical chymist, I could not have entertained any such suspicion. However, mentioning this suspicion to Mr. Warltire, he furnished me with some that he had kept for a specimen of the preparation, and which, he told me, he could warrant to be genuine. This being treated in the same manner as the former, only by a longer continuance of heat, I extracted much more air from it than from the other.
This experiment might have satisfied any moderate sceptic; but, however, being at Paris in the October following, and knowing that there were several eminent chymists in that place, I did not omit the opportunity by means of my friend Mr. Magellan, to get an ounce of mercurius calcinatus prepared by Mr. Cadet, of the genuineness of which there could not possibly be any suspicion; and at the same time, I frequently mentioned my surprise at the kind of air which I had got from this preparation to Mr. Lavoisier, Mr. le Roy, and several other philosophers, who honoured me with their notice in that city; and who, I dare say, cannot fail to recollect the circumstance.
At the same time, I had no suspicion that the air which I had got from the mercurius calcinatus was even wholesome, so far was I from knowing what it was that I had really found, taking it for granted, that it was nothing more than such kind of air as I had brought nitrous air to be by the processes above mentioned; and in this air I have observed that a candle would burn sometimes quite naturally, and sometimes with a beautiful enlarged flame, and yet remain perfectly noxious.
At the same time that I had got the air above mentioned from mercurius calcinatus and the red precipitate, I had got the same kind from red lead or minium.8 In this process that part of the minium on which the focus of the lens had fallen, turned yellow. One third of the air, in this experiment, was readily absorbed by water, but, in the remainder, a candle burned very strongly, and with a crackling noise.
8. Lead oxide, Pb3O4.
That fixed air is contained in red lead I had observed before; for I had expelled it by the heat of a candle, and had found it to be very pure. . . I imagine it requires more heat than I then used to expel any of the other kind of air.
This experiment with red lead confirmed me more in my suspicion, that the mercurius calcinatus must get the property of yielding this kind of air from the atmosphere, the process by which that preparation, and this of red lead is made, being similar. As I never make the least secret of anything I observe, I mentioned this experiment also, as well as those with mercurius calcinatus, and the red precipitate, to all my philosophical acquaintance at Paris, and elsewhere, having no idea, at that time, to what these remarkable facts would lead.
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 (Nov. 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 it in; 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 1 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 thus respect, to the air of the atmosphere.
In this ignorance of the real nature of this kind of air, I continued from thus time (November) to the 1st of March following; having, in the mean time, 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 by it to 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 to it 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, riot only that it was diminished, but that it was diminished quite as much as common air, and that the redress of the mixture was likewise equal to that of a similar mixture of nitrous and common air.9
9. "Nitrous air" absorbed oxygen from atmospheric air and hence diminished the volume. The effect was no less marked, obviously, with pure oxygen.
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 dinunished 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 thus substance is quite different from that of making the two others. But to this circumstances 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 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,10 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.
10. Richard Price, a Nonconformist Minister and writer; he was a friend of Priestley's and shared many of his liberal political and theological views. The mouse mentioned later in the sentence would have shown the new air to be as respirable as common air.
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 the 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 better; 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 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 4 1/2 to 3 1/2; 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 11/2 to 2/3 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.
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 in the same quantity of common air, and I did not expect much accuracy from this kind of 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 dinunished 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.
Being now fully satisfied with respect to the nature of this new species of air, viz. that, being capable of taking more phlogiston from nitrous air, it therefore originally contains less of this principle; my next enquiry was, by what means it comes to be so pure, or philosophically speaking, to be so much dephlogisticated; and since the red lead yields the same kind of air with mercurius calcinatus, though mixed with common air, and is a much cheaper material, I proceeded to examine all the preparations of lead, made by heat in the open air, to see what kind of air they would yield, beginning with the grey calx, and ending with litharge.11
11. Lead dioxide (PbO2) and lead monoxide (PbO), respectively.
The red lead which I used for this purpose yielded a considerable quantity of dephlogisticated air, and very little fixed air; but to what circumstance in the preparation of this lead, or in the keeping of it, this difference is owing, I cannot tell. I have frequently found a very remarkable difference between different specimens of red lead in this respect, as well as in the purity of the air which they contain. This difference, however, may arise in a great measure, from the care that is taken to extract the fixed air from it. In this experiment two measures of nitrous air being put to one measure of this air, reduced it to one third of what it was at first, and nearly three times its bulk of nitrous air made very little addition to its original dimensions; so that this air was exceedingly pure, and better than any that I had procured before.
The preparation called massicot12 (which is said to be a state between the grey calx and the red lead) also yielded a considerable quantity of air, of which about one half was fixed air, and the remainder was such, that when an equal quantity of nitrous air was put to it, it was something less than at first; so that this air was about twice as pure as common air
12. A yellow form of litharge, less stable than the ordinary red form.
I thought it something remarkable, that in the preparations of lead by heat, those before and after these two, viz. the red lead and massicot, yielded only fixed air. I would also observe by the way, that a very small quantity of air was extracted from lead ore by the burning lens. The bulk of it was easily absorbed by water. The remainder was not affected by nitrous air, and it extinguished a candle.
I got a very little air by the same process from the grey calx of lead, of precisely the same quality with the former. That part of it which was not affected by nitrous air extinguished a candle, so that both of them may be said to have yielded fixed air, only with a larger portion than usual of that part of it which does not unite with water.
Litharge (which is a state that succeeds the red lead) yielded air pretty readily; but this also was fixed air. That which was not absorbed by water, was not affected by nitrous air.
Much more than I had any opportunity of doing remains to be done in order to ascertain upon what circumstances, in these preparations of lead, the quality of the air which they contain, depends. It can only be done by some person who shall carefully attend to the processes, so as to see himself in what manner they are made, and examine them in all their different states. I very much wished to have attempted something of this kind myself, but I found it impossible in my situation. However, I got Dr. Higgins13 (who furnished me with several preparations that I could not easily have procured elsewhere) to make me a quantity of red lead, that I might, at least, try it when fresh made, and after keeping it some time in different circumstances; and though by the help of this preparation, I did not do the thing that I expected, I did something else, much more considerable.
13. Bryan Higgins (c. 1737-1820), uncle of the better known William Higgins. Priestley attended some of Bryan Higgins' lectures and bought chemicals from him.
This fresh made red lead had a yellowish cast, and had in it several pieces entirely yellow. I tried it immediately, in the same manner in which I had made the preceding experiments, viz. with the burning lens in quicksilver, and found that it yielded very little air, and with great difficulty; requiring the application of a very intense heat. With an equal quantity of nitrous air, a part of this air was reduced to one half of its original bulk, and 3%z measures saturated it. The air, therefore, was very pure, and the quantity that it yielded being very small, it proved to be in a very favourable state for ascertaining on what circumstances its acquiring this air depended.
My object now was to bring this fresh made red lead, which yielded very little air, to that state in which other red lead had yielded a considerable quantity; and taking it, in a manner, for granted, in consequence of the reasoning intimated above, that red lead must imbibe from the atmosphere some kind of acid, in order to acquire that property, I took three separate half-ounces of this fresh made red lead, and moistened them till they made a kind of paste, with each of the three mineral acids, viz. the vitriolic, the marine and the nitrous, and as I intended to make the experiments in a gun-barrel, lest the iron should be too much affected by them, I dried all these mixtures, till they were perfectly hard; then pulverizing them, I put them separately into my gun-barrel, filled up to the mouth with pounded flint, which I had found by trial to yield little, or no air when treated in this manner. I had also found that no quantity of air sufficient to make an experiment could be procured from an equal quantity of this red lead by this process.
Those portions of the red lead which had been moistened with the vitriolic and marine acids became white; but that which had been moistened with the nitrous acid, had acquired a deep brown colour. The mixtures with the nitrous and marine acids dried pretty readily but that with the vitriolic acid was never perfectly dry; but a great part of it remained in the form of softish paste.
Neither the vitriolic nor the marine acid mixtures gave the least air when treated in the manner above mentioned; but the moment that the composition into which the nitrous acid had entered became warm, air began to be produced; and I received the produce in quicksilver. About one ounce-measure was quite transparent, but presently after it became exceedingly red; and being satisfied that this redness was owing to the nitrous acid vapour having dissolved the quicksilver, I took no more than two ounce-measures in this way, but received all the remainder, which was almost two pints, in water. Far the greatest part of this was fixed air, being readily absorbed by water, and extinguishing a candle. There was, however, a considerable residuum, in which the flame of a candle burned with a crackling noise, from which I concluded that it was true dephlogisticated air.
In this experiment I had moistened the red lead with spirit of nitre several times, and had dried it again. When I repeated this experiment, I moistened it only once with the same acid, when I got from it not quite a pint of air; but it was almost all of the dephlogisticated kind, about five times as pure as common air. N.B. All the acids made a violent effervescence with the red lead.
Though there was a difference in the result of these experiments, which I shall consider hereafter, I was now convinced that it was the nitrous acid which the red lead had acquired from the air, and which had enabled it to yield the dephlogisticated air, agreeable to my original conjecture. Finding also, as will be seen in the following section, that the same kind of air is produced by moistening with the spirit of nitre any kind of earth14 that is free from phlogiston, and treating it as I had done the red lead in the last mentioned experiment, there remained no doubt in my mind, but that atmospherical air, or the thing that we breathe, consists of the nitrous acid and earth, with so much phlogiston as is necessary to its elasticity; and likewise so much more as is required to bring it from its state of perfect purity to the mean condition in which we find it.
14. Priestley was still, like his contemporaries, inclined to use the ancient "elements" to denote the generalized characteristics of bodies. As the next section shows, he is thinking here of inert minerals.
For this purpose I tried, with success, flowers of zinc, chalk, quick-lime, slaked-lime, tobacco-pipe clay, flint and Muscovy talc, with other similar substances, which will be found to comprise all the kinds of earth that are essentially distinct from each other, according to their chymical properties. A particular account of the processes with these substances, I reserve for another section; thinking it sufficient in this to give a history of the discovery, and a general account of the nature of this dephlogisticated air, with this general inference from the experiment, respecting the constitution of the atmosphere.
I was the more confirmed in my idea of spirit of nitre and earth constituting respirable air, by finding, that when any of these matters, on which I had tried the experiment, had been treated in the manner above mentioned, and they had thereby yielded all the air that could be extracted from them by this process; yet when they had been moistened with fresh spirit of nitre, and were treated in the same manner as before, they would yield as much dephlogisticated air as at the first. This may be repeated till all the earthy matter be exhausted. It will be sufficient to recite one or two facts of this kind from my register.
April 18, I took the remains of the fresh made red lead, out of which a great quantity of dephlogisticated air had been extracted, and moistening about three quarters of an ounce of it a second time with spirit of nitre, I got from it about two pints of air, all of which was nearly six times as pure as common air. This air was generated very fast and the glass tube through which it was transmitted was filled with red fumes; the nitrous acid, I suppose, prevailing in the composition of the air, but being absorbed by the water in which it was afterwards received.
In this, and many other processes, my reader will find a great variety in the purity of the air procured from the same substances. But this will not be wondered at, if it be considered that a small quantity of phlogistic matter, accidentally mixing with the ingredients for the composition of this air, depraves it. It will also be unavoidably depraved, in some measure, if the experiment be made in a gun-barrel, which I commonly made use of, as was generally the case, it was sufficiently exact for my purpose, on account of its being the easiest, and in many respects, the most commodious process.
The reason of this is, that if the produce of air be not very rapid, there will be time for the phlogiston to be disengaged from the iron itself, and to mix with the air. Accordingly I have seldom failed to find, that when I endeavoured to get all the air I possibly could from any quantity of materials, and received the produce at different times (as for my satisfaction I generally did) the last was inferior in purity to that which came first. Not unfrequently it was phlogisticated air; that is, air so charged with phlogiston, as to be perfectly noxious; and sometimes, as the reader will find in the next section, it was even nitrous air.
On the same account it frequently happened, that when I used a considerable degree of heat, the red lead which I used in these experiments would be changed into real lead, from which it was often very difficult to get the gun-barrel perfectly clear.
A good deal will also depend upon the ingredients which have been used in the gun-barrel in preceding experiments: for it is not easy to get such an instrument perfectly clean from all the matters that have been put into it: and though it may be presumed, in general, that every kind of air will be expelled from such ingredients by making the tube red hot; yet matters containing much phlogiston, as charcoal, etc., will not part with it in consequence of the application of heat, unless there be at hand some other substance with which it may combine. Though, therefore, a gunbarrel, containing such small pieces of charcoal as cannot be easily wiped out of it, be kept a long time in a red heat, and even with its mouth open; yet if it be of a considerable length, some part of the charcoal may remain unconsumed, and the effect of it will be found in the subsequent experiment. Of this I had the following very satisfactory proof.
Being desirous to show some of my friends the actual production of dephlogisticated air, and having no other apparatus at hand, I had recourse to my gun-barrel; but apprized them, that having used it the day before to get air from charcoal, with which it had been filled for that purpose, though I had taken all the pains I could to get it all out, yet so much would probably remain, that I could not depend on the air I should get from it being dephlogisticated; but that it would probably be of an inferior quality, and perhaps even nitrous air. Accordingly, having put into it a mixture of spirit of nitre and red lead (being part of a quantity which I had often used before for the same purpose) dried, and pounded, I put it into the fire, and received the air in water.
The first produce, which was about a pint, was so far nitrous, that two measures of common air, and one of this, occupied the space of little more than two measures; that is, it was almost as strongly nitrous as that which is produced by the solution of metals in spirit of nitre. The second pint was very little different from common air, and the last produce was better still, being more than twice as good as common air. If, therefore, any person shall propose to make dephlogisticated air, in large quantities, he should have an apparatus appropriated to that purpose; and the greatest care should be taken to keep the instruments as clear as possible from all phlogistic matter, which is the very bane of purity with respect to air, they being exactly plus and minus to each other.
The hypothesis maintained in this section viz. that atmospherical air consists of the nitrous acid and earth, suits exceedingly well with the facts relating to the production of nitre; for it is never generated but in the open air, and by exposing to it such kinds of earth as are known to have an affinity with the nitrous acid; so that by their union common nitre may be formed.
Hitherto it has been supposed by chymists, that this nitrous acid, by which common nitre is formed, exists in the atmosphere as an extraneous substance, like water, and a variety of other substances, which float in it, in the form of effluvia; but since there is no place in which nitre may not be made, it may, I think, with more probability be supposed, according to my hypothesis, that nitre is formed by a real decomposition of the air itself, the bases that are presented to it having, in such circumstances, a nearer affinity with the spirit of nitre than that kind of earth with which it is united in the atmosphere.
My theory also supplies an easy solution of what has always been a great difficulty with chymists, with respect to the detonation of nitre. The question is, what becomes of the nitrous acid in this case? The general, I believe the universal, opinion now is, that it is destroyed, that is, that the acid is properly decomposed, and resolved into its original elements, which Stahl15 supposed to be earth and water. On the other hand, I suppose that, through the common properties of the acid, as combined with water, disappear, it is only in consequence of its combination with some earthy or inflammable matter, with which it forms some of the many species of air, into the composition of which this wonderful acid enters. It may be common air, it may be dephlogisticated air, or it may be nitrous air, or some of the other kinds, of which an account will be given in a subsequent section. That it should really be the nitrous acid, though so much disguised by its union with earthy, or other matters, will not appear extraordinary to any person who shall consider how little the acid of vitriol is apparent in common sulphur.
15. G. E. Stahl, the early eighteenth-century proponent of the phlogiston theory.
With respect to mercurius calcinatus, and red lead, their red colour favours the supposition of their having extracted spirit of nitre from the air.