But the most important of all Dalton's investigations are those concerned with the Atomic Theory in chemistry, with which his name is inseparably associated. It has been supposed that this theory was suggested to him either by researches on olefiant gas and carburetted hydrogen or by analysis of "protoxide and deutoxide of azote," both views resting on the authority of Dr Thomas Thomson (1773-1852), professor of chemistry in Glasgow university. But from a study of Dalton's own MS. laboratory notebooks, discovered in the rooms of the Manchester society, Roscoe and Harden (_A New View of the Origin of Dalton's Atomic Theory_, 1896) conclude that so far from Dalton being led to the idea that chemical combination consists in the approximation of atoms of definite and characteristic weight by his search for an explanation of the law of combination in multiple proportions, the idea of atomic structure arose in his mind as a purely physical conception, forced upon him by study of the physical properties of the atmosphere and other gases. The first published indications of this idea are to be found at the end of his paper on the "Absorption of gases" already mentioned, which was read on the 21st of October 1803 though not published till 1805. Here he says: "Why does not water admit its bulk of every kind of gas alike? This question I have duly considered, and though I am not able to satisfy myself completely I am nearly persuaded that the circumstance depends on the weight and number of the ultimate particles of the several gases." He proceeds to give what has been quoted as his first table of atomic weights, but on p. 248 of his laboratory notebooks for 1802-1804, under the date 6th of September 1803, there is an earlier one in which he sets forth the relative weights of the ultimate atoms of a number of substances, derived from analysis of water, ammonia, carbon-dioxide, &c. by chemists of the time. It appears, then, that, confronted with the "problem of ascertaining the relative diameter of the particles of which, he was convinced, all gases were made up, he had recourse to the results of chemical analysis. Assisted by the assumption that combination always takes place in the simplest possible way, he thus arrived at the idea that chemical combination takes place between particles of different weights, and this it was which differentiated his theory from the historic speculations of the Greeks. The extension of this idea to substances in general necessarily led him to the law of combination in multiple proportions, and the comparison with experiment brilliantly confirmed the truth of his deduction" (_A New View, &c._, pp. 50, 51). It may be noted that in a paper on the "Proportion of the gases or elastic fluids constituting the atmosphere," read by him in November 1802, the law of multiple proportions appears to be anticipated in the words--"The elements of oxygen may combine with a certain portion of nitrous gas or with twice that portion, but with no intermediate quantity," but there is reason to suspect that this sentence was added some time after the reading of the paper, which was not published till 1805.
Water Report
Encyclopaedia Britannica, 11th Edition, Volume 7, Slice 9 — Part 132
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