Priestley imagined that as the liquid marine acid—that is hydrochloric acid—readily yielded an “air” on heating it might be that vitriolic acid, or oil of vitriol, would also afford a characteristic “air” when treated in a similar manner. Acting upon a suggestion of Mr Lane he heated oil of vitriol with olive oil, when he readily obtained a new species of air, which he collected over mercury as he “had been used to do it with the marine acid air; and the whole process was as pleasing and as elegant.” Priestley at once surmised that the olive oil worked by transferring its phlogiston to the vitriolic acid, and he naturally concluded that any substance rich in phlogiston would bring about the same result. He next tried charcoal.
“I put some bits of charcoal into my phial instead of the oil or other inflammable matter which I had used before, and applying the flame of a candle I presently found that the vitriolic acid air was produced as well as in the former process, and in several respects more conveniently, the production of air being equable, whereby the disagreeable effect of a sudden explosion is avoided.... Finding that a great variety of substances containing phlogiston enabled the oil of vitriol to throw out a permanent acid air, I had some suspicion that mere heat might do the same, but I did not find that there was any foundation for that suspicion.... But though I got no air from the oil of vitriol by this process, air was produced at the same time in a manner that I little expected, and I paid pretty dearly for the discovery it occasioned. Despairing to get any air from the longer application of my candles, I withdrew them, but before I could disengage the phial from the vessel of quicksilver a little of it passed through the tube into the hot acid, when instantly it was all filled with dense white fumes, a prodigious quantity of air was generated, the tube through which it was transmitted was broken into many pieces, and part of the hot acid being spilled upon my hand burned it terribly, so that the effect of it is visible to this day. The inside of the phial was coated with a white saline substance, and the smell that issued from it was extremely suffocating.
“This accident taught me what I am surprised I should not have suspected before, viz., that some metals will part with their phlogiston to hot oil of vitriol, and thereby convert it into a permanent elastic air, producing the very same effect with oil, charcoal, or any other inflammable substance.
“Not discouraged by the disagreeable accident above mentioned, the next day I put a little quicksilver into the phial with the ground stopple and tube, along with the oil of vitriol, when, long before it was boiling hot, air issued plentifully from it, and being received in a vessel of quicksilver appeared to be genuine vitriolic acid air, exactly like that which I had procured before, being readily imbibed by water and extinguishing a candle in the same manner as the other had done....
“After this I repeated the experiment with several other metals.... Copper treated in the same manner yielded air very freely, with about the same degree of heat that quicksilver had required, and the air continued to be generated with very little application of more heat.”
The theory apart, this paper is as important as these on ammonia and the marine acid air, and exhibits Priestley at his best. The observations he makes concerning the main properties of the new gas and its solubility in water, its inability to burn and to support flame, its heaviness, its power to unite with ammonia, to be absorbed by charcoal and to liquefy camphor, are all accurate.
“Having hit upon a method of exhibiting some of the acids in the form of air, nothing could be easier than to extend this process to the rest.”
Accordingly he attempted to procure what he called the vegetable acid air by heating “exceedingly strong concentrated acid of vinegar,” and states that he succeeded in obtaining an air which extinguished the flame of a candle and was soluble in water. The paper is very short and is full of contradictions. In reality, as he subsequently found, he was dealing with vinegar largely adulterated with oil of vitriol. The “vegetable acid air” had no real existence.
The next paper in the series is the most important of the whole, and the one of all others that has contributed most largely to Priestley’s reputation. It is entitled “Of Dephlogisticated Air, and of the Constitution of the Atmosphere,” and deals with the discovery of oxygen. It begins in the following characteristic fashion:—
“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 preconceived 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 reconsider 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.”
He then points out that there are few maxims in philosophy that have laid firmer hold upon the mind than that air, meaning atmospherical air ... is a simple elementary substance, indestructible and unalterable, at least as much so as water was supposed to be. Priestley, in the course of his inquiries, was soon satisfied that atmospherical air was not an unalterable thing; that bodies burning in it, and animals breathing it and various other chemical processes, so far alter and deprive it as to render it altogether unfit for the purposes to which it is subservient; and he had discovered methods, particularly the process of vegetation, which tended to restore it to its original purity.
“But,” he says, “I own I had no idea of the possibility of going any further in this way and thereby procuring air purer than the best common air.”
As this paper is one of the classics of chemistry, as well as the chief corner-stone in the monument which Priestley erected to himself, it is necessary to examine it, as well as certain other papers which grew immediately out of it, in some degree of detail.