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Some Early Kinetic Theories of Gases: Herapath and his Predecessors
Published online by Cambridge University Press: 05 January 2009
Synopsis
This paper summarizes ideas about the nature of gases proposed during the period following the discovery of Boyle's law. Particular stress is laid on the hypotheses of the Bernoullis, and later, on the equally speculative work of Herapath. Reasons for the success of Herapath's theory, and the neglect of Daniel Bernoulli's are discussed, but it has not been thought necessary to take the story beyond the initial acceptance of Herapath's theory by J. P. Joule, because the paper is concerned only with the antecedents of the modern kinetic theory.
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References
1 More properly, theories of the nature of air, because air was the only gaseous substance recognized in the seventeenth century.
2 e.g. Galileo, , Il Saggiatore, 1623Google Scholar, quoted by Drake, Stillman, Discoveries and Opinions of Galileo, New York, 1957, pp. 276–278.Google Scholar
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11 The role of attractive forces in chemical combination was discussed in Opticks, Query 31 (Dover reprint, see especially p. 395).
12 Principia, proposition xxiii, theorem xviii (ed. Cajori, , 1934, pp. 300–302)Google Scholar. Newton's working is given in the scholium, and deals also with the general case where the repulsive force is as the nth power of the distance between particles.
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The circular motions of each particle were supposed to trace out a sphere. If air in a cylinder is compressed by a piston until it occupies an eighth part of its previous volume, the radius of each of these spheres is “reduced by half… and assuming that the degree of heat does not change, the circular motions … continue with the same velocity after the compression … Then each of the circular motions will give rise to twice the centrifugal force than before the compression, and each sphere will tend to expand with twice the force. The piston will have four times as many particles contiguous to it, each of which will exert twice as much force. The result will be a total pressure on the piston eight times as great” (ibid., p. 105). Thus, after the compression, the pressure has increased and the volume decreased by the same factor, which means that Boyle's law is obeyed.
32 Ibid., p. 92.
33 Ibid., p. 100.
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39 Ibid., pp. 202–203; the symbols have been altered.
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43 Ibid., § 18.
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60 Davy also suggested rectilinear motion for the “imponderable” particles which he thought the probable cause of the phenomena of radiant heat and light. Thus his scheme encompassed all three types of motion possible in a kinetic theory.
61 As one example, Ure strongly supported Davy's claims on behalf of William Higgins as originator of the atomic theory.
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72 His latent heat theory required all sorts of curious assumptions to be made about shapes of particles in order to avoid the conclusion that phase changes could only take place at absolute zero. This was because Herapath's collision theory did not envisage any means by which particles could coalesce unless they had no relative velocity. (Ibid., n.s., ii ( 1821 ), 267.)
73 For example, he pleaded quite justly that Newton had not specifically affirmed that air consisted of particles repelling one another inversely as their distances. (Ibid., n.s., ii (1821) 306 n.)
74 Except for one critic who thought the question important but held the view that a purely mathematical demonstration as given by Herapath was not proof but only a strong argument. (Ibid., n.s., ii (1821), 418.)
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