The great first step was the substitution of the one principle, phlogiston, for the three principles, salt, sulphur, and mercury. We have seen how the experiment of burning or calcining such a metal as lead "destroyed" the lead as such, leaving an entirely different substance in its place, and how the original metal could be restored by the addition of wheat to the calcined product. To the alchemist this was "mortification" and "revivification" of the metal. For, as pointed out by Paracelsus, "anything that could be killed by man could also be revivified by him, although this was not possible to the things killed by God." The burning of such substances as wood, wax, oil, etc., was also looked upon as the same "killing" process, and the fact that the alchemist was unable to revivify them was regarded as simply the lack of skill on his part, and in no wise affecting the theory itself.

But the iconoclastic spirit, if not the acceptance of all the teachings, of the great Paracelsus had been gradually taking root among the better class of alchemists, and about the middle of the seventeenth century Robert Boyle (1626-1691) called attention to the possibility of making a wrong deduction from the phenomenon of the calcination of the metals, because of a very important factor, the action of the air, which was generally overlooked. And he urged his colleagues of the laboratories to give greater heed to certain other phenomena that might pass unnoticed in the ordinary calcinating process. In his work, The Sceptical Chemist, he showed the reasons for doubting the threefold constitution of matter; and in his General History of the Air advanced some novel and carefully studied theories as to the composition of the atmosphere. This was an important step, and although Boyle is not directly responsible for the phlogiston theory, it is probable that his experiments on the atmosphere influenced considerably the real founders, Becker and Stahl.

Boyle gave very definitely his idea of how he thought air might be composed. "I conjecture that the atmospherical air consists of three different kinds of corpuscles," he says; "the first, those numberless particles which, in the form of vapors or dry exhalations, ascend from the earth, water, minerals, vegetables, animals, etc.; in a word, whatever substances are elevated by the celestial or subterraneal heat, and thence diffused into the atmosphere. The second may be yet more subtle, and consist of those exceedingly minute atoms, the magnetical effluvia of the earth, with other innumerable particles sent out from the bodies of the celestial luminaries, and causing, by their influence, the idea of light in us. The third sort is its characteristic and essential property, I mean permanently elastic parts. Various hypotheses may be framed relating to the structure of these later particles of the air. They might be resembled to the springs of watches, coiled up and endeavoring to restore themselves; to wool, which, being compressed, has an elastic force; to slender wires of different substances, consistencies, lengths, and thickness; in greater curls or less, near to, or remote from each other, etc., yet all continuing springy, expansible, and compressible. Lastly, they may also be compared to the thin shavings of different kinds of wood, various in their lengths, breadth, and thickness. And this, perhaps, will seem the most eligible hypothesis, because it, in some measure, illustrates the production of the elastic particles we are considering. For no art or curious instruments are required to make these shavings whose curls are in no wise uniform, but seemingly casual; and what is more remarkable, bodies that before seemed unelastic, as beams and blocks, will afford them."[1]

Although this explanation of the composition of the air is most crude, it had the effect of directing attention to the fact that the atmosphere is not "mere nothingness," but a "something" with a definite composition, and this served as a good foundation for future investigations. To be sure, Boyle was neither the first nor the only chemist who had suspected that the air was a mixture of gases, and not a simple one, and that only certain of these gases take part in the process of calcination. Jean Rey, a French physician, and John Mayow, an Englishman, had preformed experiments which showed conclusively that the air was not a simple substance; but Boyle's work was better known, and in its effect probably more important. But with all Boyle's explanations of the composition of air, he still believed that there was an inexplicable something, a "vital substance," which he was unable to fathom, and which later became the basis of Stahl's phlogiston theory. Commenting on this mysterious substance, Boyle says: "The, difficulty we find in keeping flame and fire alive, though but for a little time, without air, renders it suspicious that there be dispersed through the rest of the atmosphere some odd substance, either of a solar, astral, or other foreign nature; on account of which the air is so necessary to the substance of flame!" It was this idea that attracted the attention of George Ernst Stahl (1660-1734), a professor of medicine in the University of Halle, who later founded his new theory upon it. Stahl's theory was a development of an earlier chemist, Johann Joachim Becker (1635-1682), in whose footsteps he followed and whose experiments he carried further.

In many experiments Stahl had been struck with the fact that certain substances, while differing widely, from one another in many respects, were alike in combustibility. From this he argued that all combustible substances must contain a common principle, and this principle he named phlogiston. This phlogiston he believed to be intimately associated in combination with other substances in nature, and in that condition not perceivable by the senses; but it was supposed to escape as a substance burned, and become apparent to the senses as fire or flame. In other words, phlogiston was something imprisoned in a combustible structure (itself forming part of the structure), and only liberated when this structure was destroyed. Fire, or flame, was FREE phlogiston, while the imprisoned phlogiston was called COMBINED PHLOGISTON, or combined fire. The peculiar quality of this strange substance was that it disliked freedom and was always striving to conceal itself in some combustible substance. Boyle's tentative suggestion that heat was simply motion was apparently not accepted by Stahl, or perhaps it was unknown to him.

According to the phlogistic theory, the part remaining after a substance was burned was simply the original substance deprived of phlogiston. To restore the original combustible substance, it was necessary to heat the residue of the combustion with something that burned easily, so that the freed phlogiston might again combine with the ashes. This was explained by the supposition that the more combustible a substance was the more phlogiston it contained, and since free phlogiston sought always to combine with some suitable substance, it was only necessary to mix the phlogisticating agents, such as charcoal, phosphorus, oils, fats, etc., with the ashes of the original substance, and heat the mixture, the phlogiston thus freed uniting at once with the ashes. This theory fitted very nicely as applied to the calcined lead revivified by the grains of wheat, although with some other products of calcination it did not seem to apply at all.

It will be seen from this that the phlogistic theory was a step towards chemistry and away from alchemy. It led away from the idea of a "spirit" in metals that could not be seen, felt, or appreciated by any of the senses, and substituted for it a principle which, although a falsely conceived one, was still much more tangible than the "spirit," since it could be seen and felt as free phlogiston and weighed and measured as combined phlogiston. The definiteness of the statement that a metal, for example, was composed of phlogiston and an element was much less enigmatic, even if wrong, than the statement of the alchemist that "metals are produced by the spiritual action of the three principles, salt, mercury, sulphur" - particularly when it is explained that salt, mercury, and sulphur were really not what their names implied, and that there was no universally accepted belief as to what they really were.

The metals, which are now regarded as elementary bodies, were considered compounds by the phlogistians, and they believed that the calcining of a metal was a process of simplification. They noted, however, that the remains of calcination weighed more than the original product, and the natural inference from this would be that the metal must have taken in some substance rather than have given off anything. But the phlogistians had not learned the all-important significance of weights, and their explanation of variation in weight was either that such gain or loss was an unimportant "accident" at best, or that phlogiston, being light, tended to lighten any substance containing it, so that driving it out of the metal by calcination naturally left the residue heavier.

At first the phlogiston theory seemed to explain in an indisputable way all the known chemical phenomena. Gradually, however, as experiments multiplied, it became evident that the plain theory as stated by Stahl and his followers failed to explain satisfactorily certain laboratory reactions. To meet these new conditions, certain modifications were introduced from time to time, giving the theory a flexibility that would allow it to cover all cases. But as the number of inexplicable experiments continued to increase, and new modifications to the theory became necessary, it was found that some of these modifications were directly contradictory to others, and thus the simple theory became too cumbersome from the number of its modifications. Its supporters disagreed among themselves, first as to the explanation of certain phenomena that did not seem to accord with the phlogistic theory, and a little later as to the theory itself. But as yet there was no satisfactory substitute for this theory, which, even if unsatisfactory, seemed better than anything that had gone before or could be suggested.

But the good effects of the era of experimental research, to which the theory of Stahl had given such an impetus, were showing in the attitude of the experimenters. The works of some of the older writers, such as Boyle and Hooke, were again sought out in their dusty corners and consulted, and their surmises as to the possible mixture of various gases in the air were more carefully considered. Still the phlogiston theory was firmly grounded in the minds of the philosophers, who can hardly be censured for adhering to it, at least until some satisfactory substitute was offered. The foundation for such a theory was finally laid, as we shall see presently, by the work of Black, Priestley, Cavendish, and Lavoisier, in the eighteenth century, but the phlogiston theory cannot be said to have finally succumbed until the opening years of the nineteenth century.