Gibbs' paradox and non-uniform convergence

K. G. Denbigh

Michael Redhead

pp. 283-312

in: Synthese 81 (3), 1989.

Abstrakt

It is only when mixing two or more pure substances along a reversible path that the entropy of the mixing can be made physically manifest. It is not, in this case, a mere mathematical artifact. This mixing requires a process of successive stages. In any finite number of stages, the external manifestation of the entropy change, as a definite and measurable quantity of heat, isa fully continuous function of the relevant variables. It is only at an infinite and unattainable limit thata non-uniform convergence occurs. And this occurs when considered in terms of the number of stages together with a ‘distinguishability parameter’ appropriate to the particular device which is used to achieve reversibility. These considerations, which are of technological interest to chemical engineers, resolve a paradox derived in chemical theory called Gibbs' Paradox.