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CHAPTER XV - SYSTEMS COMPOSED OF MOLECULES

Published online by Cambridge University Press:  05 August 2011

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Summary

The nature of material bodies is such that especial interest attaches to the dynamics of systems composed of a great number of entirely similar particles, or, it may be, of a great number of particles of several kinds, all of each kind being entirely similar to each other. We shall therefore proceed to consider systems composed of such particles, whether in great numbers or otherwise, and especially to consider the statistical equilibrium of ensembles of such systems. One of the variations to be considered in regard to such systems is a variation in the numbers of the particles of the various kinds which it contains, and the question of statistical equilibrium between two ensembles of such systems relates in part to the tendencies of the various kinds of particles to pass from the one to the other.

First of all, we must define precisely what is meant by statistical equilibrium of such an ensemble of systems. The essence of statistical equilibrium is the permanence of the number of systems which fall within any given limits with respect to phase. We have therefore to define how the term “phase” is to be understood in such cases. If two phases differ only in that certain entirely similar particles have changed places with one another, are they to be regarded as identical or different phases? If the particles are regarded as indistinguishable, it seems in accordance with the spirit of the statistical method to regard the phases as identical.

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Elementary Principles in Statistical Mechanics
Developed with Especial Reference to the Rational Foundation of Thermodynamics
, pp. 187 - 207
Publisher: Cambridge University Press
Print publication year: 2010
First published in: 1902

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