History of scientific ideas

by William Whewell

6. Affinity is Elective.—When the idea of chemical affinity, or disposition to unite, was brought into view by the experiments and reasonings of chemists, they found it necessary to consider this disposition as elective;—each element chose one rather than another of the elements which were presented to it, and quitted its union with one to unite with another which it preferred. This has already appeared in the passage just quoted from Mayow. He adds in the same strain, ‘I have no doubt that fixed salts choose one acid rather than another, in order that they may coalesce with it [22] in a more intimate union.’—‘Nullus dubito salia fixa acidum unum præ aliis eligere, ut cum eodem arctiore unione coalescant.’ The same thought is expressed and exemplified by other chemists: they notice innumerable cases in which, when an ingredient is combined with a liquid, if a new substance be immersed which has a greater affinity for the liquid, the liquid combines with the new substance by election, and the former ingredient is precipitated. Thus Stahl says[22], ‘In spirit of nitre dissolve silver; put in copper and the silver is thrown down; put in iron and the copper goes down; put in zinc, the iron precipitates; put in volatile alkali, the zinc is separated; put in fixed alkali, the volatile quits its hold.’—As may be seen in this example, we have in such cases, not only a preference, but a long gradation of preferences. The spirit of nitre will combine with silver, but it prefers copper; prefers iron more; zinc still more; volatile alkali yet more; fixed alkali the most.

[22] Zymotechnia, 1697, p. 117.

The same thing was proved to obtain with regard to each element; and when this was ascertained, it became the object of chemists to express these degrees of preference, by lists in which substances were arranged according to their disposition to unite with another substance. In this manner was formed Geoffroy’s Table of Affinities (1718), which we have already mentioned. This Table was further improved by other writers, as Gellert (1751) and Limbourg (1761). Finally Bergman improved these Tables still further, taking into account not only the order of affinities of each element for others, but the sum of the tendencies to unite of each two elements, which sum, he held, determined the resulting combination when several elements were in contact with each other.

7. As we have stated in the History[23], when the doctrine of elective affinities had assumed this very definite and systematic form, it was assailed by Berthollet, who maintained, in his Essai de Statique [23] Chimique, (1803,) that chemical affinities are not elective:—that, when various elements are brought together, their combinations do not depend upon the kind of elements alone, but upon the quantity of each which is present, that which is most abundant always entering most largely into the resulting compounds. It may seem strange that it should be possible, at so late a period of the science, to throw doubt upon a doctrine which had presided over and directed its progress so long. Proust answered Berthollet, and again maintained that chemical affinity is elective. I have, in the History, given the judgment of Berzelius upon this controversy. ‘Berthollet,’ he says, ‘defended himself with an acuteness which makes the reader hesitate in his judgment; but the great mass of facts finally decided the point in favour of Proust.’ I may here add the opinion pronounced upon this subject by Dr. Turner[24]: ‘Bergman erred in supposing the result of the chemical action to be in every case owing to elective affinity [for this power is modified in its effects by various circumstances]: but Berthollet ran into the opposite extreme in declaring that the effects formerly ascribed to that power are never produced by it. That chemical attraction is exerted between different bodies with different degrees of energy, is, I apprehend, indisputable.’ And he then proceeds to give many instances of differences in affinity which cannot be accounted for by the operation of any modifying causes. Still more recently, M. Dumas has taken a review of this controversy; and, speaking with enthusiasm of the work of Berthollet, as one which had been of inestimable service to himself in his early study of chemistry, he appears at first disposed to award to him the victory in this dispute. But his final verdict leaves undamaged the general principle now under our consideration, that chemical affinity is elective. ‘For my own part,’ he says[25], ‘I willingly admit the notions of Berthollet when we have to do with acids or [24] with bases, of which the energy is nearly equal: but when bodies endued with very energetic affinities are in presence of other bodies of which the affinities are very feeble, I propose to adopt the following rule: In a solution, everything remaining dissolved, the strong affinities satisfy themselves, leaving the weak affinities to arrange matters with one another. The strong acids take the strong bases, and the weak acids can only unite with the weak bases. The known facts are perfectly in accordance with this practical rule.’ It is obvious that this recognition of a distinction between strong and weak affinities, which operates to such an extent as to determine entirely the result, is a complete acknowledgement of the Elective nature of Affinity, as far as any person acquainted with chemical operations could contend for it. For it must be allowed by all, that solubility, and other collateral circumstances, influence the course of chemical combinations, since they determine whether or not there shall take place that contact of elements without which affinity cannot possibly operate.

[23] Hist. Ind. Sc. b. xiv. c. iii.

[24] Chemistry, p. 199. 6th edition.

[25] Leçons de Philosophie Chimique, p. 386.

8. Affinity is Definite as to quantity.—In proportion as chemists obtained a clearer view of the products of the laboratory as results of the composition of elements, they saw more and more clearly that these results were definite; that one element not only preferred to combine with another of a certain kind, but also would combine with it to a certain extent and no further, thus giving to the result not an accidental and variable, but a fixed and constant character. Thus salts being considered as the result of the combination of two opposite principles, acid and alkali, and being termed neutral when these principles exactly balanced each other, Rouelle (who was Royal Professor at Paris in 1742) admits of neutral salts with excess of acid, neutral salts with excess of base, and perfect neutral salts. Beaume maintained[26] against him that there were no salts except those perfectly neutral, the other classes being the results of mixture and imperfect [25] combination. But this question was not adequately treated till chemists made every experiment with the balance in their hands. When this was done, they soon discovered that, in each neutral salt, the proportional weights of the ingredients which composed it were always the same. This was ascertained by Wenzel, whose Doctrine of the Affinities of Bodies appeared in 1777. He not only ascertained that the proportions of elements in neutral chemical compounds are definite, but also that they are reciprocal; that is, (to express his results in a manner now employed by chemists), that if a, a certain weight of a certain acid, neutralize m, a certain weight of a certain base, and b, a certain weight of a certain other acid, neutralize n, a certain weight of a certain other base; the compound of a and n will also be neutral; as also that of b and m. The same views were again presented by Richter in 1792, in his Principles of the Measure of Chemical Elements. And along with these facts, that of the combination of elements in multiple proportions being also taken into account, the foundations of the Atomic Theory were laid; and that Theory was propounded in 1803 by Mr. Dalton. That theory, however, rests upon the Idea of Substance, as well as upon that Idea of Chemical Affinity which we are here considering; and the discussion of its evidence and truth must be for the present deferred.

[26] Dumas, Phil. Chim. p. 198.

9. The two principles just explained,—that Affinity is Definite as to the Kind, and as to the Quantity of the elements which it unites,—have here been stated as results of experimental investigation. That they could never have been clearly understood, and therefore never firmly established, without laborious and exact experiments, is certain; but yet we may venture to say that being once fully known, they may seem to thoughtful men to possess an evidence beyond that of mere experiment. For how, in fact, can we conceive combinations, otherwise than as definite in kind and quantity? If we were to suppose each element ready to combine with any other indifferently, and indifferently in any quantity, we should have a world in [26] which all would be confusion and indefiniteness. There would be no fixed kinds of bodies. Salts, and stones, and ores, would approach to and graduate into each other by insensible degrees. Instead of this, we know that the world consists of bodies distinguishable from each other by definite differences, capable of being classified and named, and of having general propositions asserted concerning them. And as we cannot conceive a world in which this should not be the case, it would appear that we cannot conceive a state of things in which the laws of the combination of elements should not be of that definite and measured kind which we have above asserted.