To the historian of chemistry the last volume of the series is hardly less interesting than any one of its predecessors, not so much as affording knowledge of new “airs” as by reason of Priestley’s relation to the waning doctrine of phlogiston, and on account of the part that his own work was playing, in spite of himself, in completing its overthrow. The volume indeed significantly opens with “Experiments relating to Phlogiston,” a reprint with notes of his paper in the 73rd volume of the Philosophical Transactions. Priestley truly says:—
“There are few subjects, perhaps none, that have occasioned more perplexity to chemists than that of phlogiston, or, as it is sometimes called, the principle of inflammability. It was the great discovery of Stahl that this principle, whatever it be, is transferable from one substance to another, how different soever in their other properties, such as sulphur, wood, and all the metals, and therefore is the same thing in them all. But what has given an air of mystery to this subject has been that it was imagined that this principle, or substance, could not be exhibited except in combination with other substances, and could not be made to assume separately either a fluid or solid form. It was also asserted by some that phlogiston was so far from adding to the weight of bodies that the addition of it made them really lighter than they were before; on which account they chose to call it the principle of levity. This opinion had great patrons.
“Of late it has been the opinion of many celebrated chemists, Mr Lavoisier among others, that the whole doctrine of phlogiston has been founded on mistake, and that in all cases in which it was thought that bodies parted with the principle of phlogiston, they in fact lost nothing, but on the contrary acquired something; and in most cases an addition of some kind of air; that a metal, for instance, was not a combination of two things, viz., an earth and phlogiston, but was probably a simple substance in its metallic state; and that the calx is produced not by the loss of phlogiston, or of anything else, but by the acquisition of air.”
He then goes on to say that the arguments in favour of this opinion, especially those which were drawn from the experiments of Lavoisier on mercury, were “so specious” that he owns he was much inclined to adopt it. But he was evidently loth to part company with a conception which had hitherto been the central idea of his chemical creed, the very key-stone of the structure which he was pleased to regard as his philosophy. As an abstract conception, as the principle of levity, as something which was the negation of mass and which gravity repelled, phlogiston was eminently unsatisfactory. But what if phlogiston were an entity? A ponderable substance, no matter how light? In that case Stahl’s generalisation might still afford salvation. “My friend, Mr Kirwan”—a clever, ingenious Irishman, with a nimble wit and a facile pen—supplied the hint—“Phlogiston was inflammable air”—and Priestley by a series of experiments, faultless as to execution but utterly fallacious as to interpretation, persuades himself that Kirwan is right and that Mr Lavoisier’s opinion and his “specious arguments” are therefore to be discountenanced. The paper, in certain respects, is one of the most noteworthy of Priestley’s productions. The experiments are original, ingenious and striking, but as an example of his inductive capacity, or as an indication of its author’s logical power, or of his ability to try judicially the very issue he has raised, it is significant only of the profound truth of his own words that
“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.”
The next paper in the volume, on “The Seeming Conversion of Water into Air,” is a record of experiments which cost Priestley much labour and the Lunar Society, for a time, much mystification. Priestley eventually detected the fallacy in the observation which originally induced him to believe that it was possible to transmute water into a permanently elastic fluid, but he got no further in his explanation than that air has a faculty of passing through the pores of an earthern vessel “by means of a power very different from that of pressure.”
This and the third paper in the series are classical, and this partly by reason of, and partly in spite of, their blunders, for they are the record of the work upon which James Watt largely based his conjectures concerning the real chemical nature of water, whereby his name has been associated with that of Cavendish and Lavoisier as the true discoverer of its composition. In the course of his inquiry Priestley studied the action of steam upon red-hot iron by an arrangement generally similar to that employed by Lavoisier, but his explanation of the phenomena is essentially different from that of the French chemist, as may be seen from the following quotation:—
“Since iron gains the same addition of weight by melting it in dephlogisticated air, and also by the addition of water when red-hot, and becomes, as I have already observed, in all respects the same substance, it is evident that this air or water, as existing in the iron, is the very same thing; and this can hardly be explained but upon the supposition that water consists of two kinds of air, viz., inflammable and dephlogisticated.”
This, however, is how Priestley actually does explain it:—
“When iron is melted in dephlogisticated air we may suppose that, though part of its phlogiston escapes to enter into the composition of the small quantity of fixed air which is then procured, yet enough remains to form water with the addition of the dephlogisticated air which it has imbibed, so that this calx of iron consists of the intimate union of the pure earth of iron and of water; and therefore when the same calx, thus saturated with water, is exposed to heat in inflammable air, this air enters into it, destroys the attraction between the water and the earth, and revives the iron while the water is expelled in its proper form.
“Consequently, in the process with steam, nothing is necessary to be supposed but the entrance of the water and the expulsion of the phlogiston belonging to the iron, no more phlogiston remaining in it than what the water brought along with it, and which is retained as a constituent part of the water or of the new compound.”
No more striking illustration of how a man’s ingenuity may help him to deceive himself could be given than is afforded by this passage. Priestley to the end of his days never got a just conception of the real chemical constitution of water.