entropy Article The Gibbs Paradox: Early History and Solutions Olivier Darrigol UMR SPHere, CNRS, Université Denis Diderot, 75013 Paris, France;
[email protected] Received: 9 April 2018; Accepted: 28 May 2018; Published: 6 June 2018 Abstract: This article is a detailed history of the Gibbs paradox, with philosophical morals. It purports to explain the origins of the paradox, to describe and criticize solutions of the paradox from the early times to the present, to use the history of statistical mechanics as a reservoir of ideas for clarifying foundations and removing prejudices, and to relate the paradox to broad misunderstandings of the nature of physical theory. Keywords: Gibbs paradox; mixing; entropy; irreversibility; thermochemistry 1. Introduction The history of thermodynamics has three famous “paradoxes”: Josiah Willard Gibbs’s mixing paradox of 1876, Josef Loschmidt reversibility paradox of the same year, and Ernst Zermelo’s recurrence paradox of 1896. The second and third revealed contradictions between the law of entropy increase and the properties of the underlying molecular dynamics. They prompted Ludwig Boltzmann to deepen the statistical understanding of thermodynamic irreversibility. The Gibbs paradox—first called a paradox by Pierre Duhem in 1892—denounced a violation of the continuity principle: the mixing entropy of two gases (to be defined in a moment) has the same finite value no matter how small the difference between the two gases, even though common sense requires the mixing entropy to vanish for identical gases (you do not really mix two identical substances). Although this paradox originally belonged to purely macroscopic thermodynamics, Gibbs perceived kinetic-molecular implications and James Clerk Maxwell promptly followed him in this direction.