The Gibbs "volume" entropy is incorrect

Robert H. Swendsen, Jian-Sheng Wang

Published 2015-06-23Version 1

In recent papers, several authors have claimed that a definition of the thermodynamic entropy in terms of the logarithm of a volume in phase space, originally suggested by Gibbs, is the only valid definition. Arguing from the Gibbs entropy, these authors claim that thermodynamics cannot be extended to include negative temperatures. However, the Gibbs entropy fails to satisfy the postulates of thermodynamics, leading to serious errors. In particular, predictions of the Gibbs entropy for systems with non-monotonic energy densities are incorrect. We show that the correct expression for the equilibrium entropy contains an integral over a surface in phase space, and negative temperature is a valid thermodynamic concept.