Descriptive chemistry was now assuming considerable proportions; the experimental inquiries suggested by Boyle were being assiduously developed; and a wealth of observations Lavoisier. was being accumulated, for the explanation of which the resources of the dominant theory were sorely taxed. To quote Antoine Laurent Lavoisier, “. . . chemists have turned phlogiston into a vague principle, . . . which consequently adapts itself to all the explanations for which it may be required. Sometimes this principle has weight, and sometimes it has not; sometimes it is free fire and sometimes it is fire combined with the earthy element; sometimes it passes through the pores of vessels, sometimes these are impervious to it; it explains both causticity and non-causticity, transparency and opacity, colours and their absence; it is a veritable Proteus changing in form at each instant.” Lavoisier may be justly regarded as the founder of modern or quantitative chemistry. First and foremost, he demanded that the balance must be used in all investigations into chemical changes. He established as fundamental that combustion and calcination were attended by an increase of weight, and concluded, as did Jean Rey and John Mayow in the 17th century, that the increase was due to the combination of the metal with the air. The problem could obviously be completely solved only when the composition of the air, and the parts played by its components, had been determined. At all times the air had received attention, especially since van Helmont made his far-reaching investigations on gases. Mayow had suggested the existence of two components, a spiritus nitroaerus which supported combustion, and a spiritus nitri acidi which extinguished fire; J. Priestley and K. W. Scheele, although they isolated oxygen, were fogged by the phlogistic tenets; and H. Cavendish, who had isolated the nitrogen of the atmosphere, had failed to decide conclusively what had really happened to the air which disappeared during combustion.
Lavoisier adequately recognized and acknowledged how much he owed to the researches of others; to himself is due the co-ordination of these researches, and the welding of his results into a doctrine to which the phlogistic theory ultimately succumbed. He burned phosphorus in air standing over mercury, and showed that (1) there was a limit to the amount of phosphorus which could be burned in the confined air, (2) that when no more phosphorus could be burned, one-fifth of the air had disappeared, (3) that the weight of the air lost was nearly equal to the difference in the weights of the white solid produced and the phosphorus burned, (4) that the density of the residual air was less than that of ordinary air. The same results were obtained with lead and tin; and a more elaborate repetition indubitably established their correctness. He also showed that on heating mercury calx alone an “air” was liberated which differed from other “airs,” and was slightly heavier than ordinary air; moreover, the weight of the “air” set free from a given weight of the calx was equal to the weight taken up in forming the calx from mercury, and if the calx be heated with charcoal, the metal was recovered and a gas named “fixed air,” the modern carbon dioxide, was formed. The former experiment had been performed by Scheele and Priestley, who had named the gas “phlogisticated air”; Lavoisier subsequently named it oxygen, regarding it as the “acid producer” (ὀξύς, sour). The theory advocated by Lavoisier came to displace the phlogistic conception; but at first its acceptance was slow. Chemical literature was full of the phlogistic modes of expression—oxygen was “dephlogisticated air,” nitrogen “phlogisticated air,” &c.—and this tended to retard its promotion. Yet really the transition from the one theory to the other was simple, it being only necessary to change the “addition or loss of phlogiston” into the “loss or addition of oxygen.” By his insistence upon the use of the balance as a quantitative check upon the masses involved in all chemical reactions, Lavoisier was enabled to establish by his own investigations and the results achieved by others the principle now known as the “conservation of mass.” Matter can neither be created nor destroyed; however a chemical system be changed, the weights before and after are equal. To him is also due a rigorous examination of the nature of elements and compounds; he held the same views that were laid down by Boyle, and with the same prophetic foresight predicted that some of the elements which he himself accepted might be eventually found to be compounds.
It is unnecessary in this place to recapitulate the many results which had accumulated by the end of the 18th century, or to discuss the labours and theories of individual workers since these receive attention under biographical headings; in this article only the salient features in the history of our science can be treated. The beginning of the 19th century was attended by far-reaching discoveries in the nature of the composition of compounds. Investigations proceeded in two directions:—(1) the nature of chemical affinity, (2) the laws Chemical Affinity. of chemical combination. The first question has not yet been solved, although it has been speculated upon from the earliest times. The alchemists explained chemical action by means of such phrases as “like attracts like,” substances being said to combine when one “loved” the other, and the reverse when it “hated” it. Boyle rejected this terminology, which was only strictly applicable to intelligent beings; and he used the word “affinity” as had been previously done by Stahl and others. The modern sense of the word, viz. the force which holds chemically dissimilar substances together (and also similar substances as is seen in di-, tri-, and poly-atomic molecules), was introduced by Hermann Boerhaave, and made more precise by Sir Isaac Newton. The laws of chemical combination were solved, in a measure, by John Dalton, and the solution expressed as Dalton’s “atomic theory.” Lavoisier appears to have assumed that the composition of every chemical compound was constant, and the same opinion was the basis of much experimental inquiry at the hands of Joseph Louis Proust during 1801 to 1809, who vigorously combated the doctrine of Claude Louis Berthollet (Essai de statique chimique, 1803), viz. that fixed proportions of elements and compounds combine only under exceptional conditions, the general rule being that the composition of a compound may vary continuously between certain limits.
This controversy was unfinished when Dalton published the first part of his New System of Chemical Philosophy in 1808, although the per saltum theory was the most popular. Led thereto byDalton. speculations on gases, Dalton assumed that matter was composed of atoms, that in the elements the atoms were simple, and in compounds complex, being composed of elementary atoms. Dalton furthermore perceived that the same two elements or substances may combine in different proportions, and showed that these proportions had always a simple ratio to one another. This is the “law of multiple proportions.” He laid down the following arbitrary rules for determining the number of atoms in a compound:—if only one compound of two elements exists, it is a binary compound and its atom is composed of one atom of each element; if two compounds exist one is binary (say A + B) and the other ternary (say A + 2B); if three, then one is binary and the others may be ternary (A + 2B, and 2A + B), and so on. More important is his deduction of equivalent weights, i.e. the relative weights of atoms. He took hydrogen, the lightest substance known, to be the standard. From analyses of water, which he regarded as composed of one atom of hydrogen and one of oxygen, he
- This dictum was questioned by the researches of H. Landolt, A. Heydweiller and others. In a series of 75 reactions it was found that in 61 there was apparently a diminution in weight, but in 1908, after a most careful repetition and making allowance for all experimental errors, Landolt concluded that no change occurred (see Element).
- The theory of Berthollet was essentially mechanical, and he attempted to prove that the course of a reaction depended not on affinities alone but also on the masses of the reacting components. In this respect his hypothesis has much in common with the “law of mass-action” developed at a much later date by the Swedish chemists Guldberg and Waage, and the American, Willard Gibbs (see Chemical Action). In his classical thesis Berthollet vigorously attacked the results deduced by Bergman, who had followed in his table of elective attractions the path traversed by Stahl and S. F. Geoffroy.