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The Gibbs “volume” entropy is incorrect

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journal contribution
posted on 23.06.2015, 00:00 by Robert SwendsenRobert Swendsen, Jian-Sheng Wang

We show that the expression for the equilibrium thermodynamic entropy contains an integral over a surface in phase space, and in so doing, we confirm that negative temperature is a valid thermodynamic concept. This demonstration disproves the claims of several recent papers that the Gibbs entropy, which contains an integral over a volume in phase space, is the correct definition and that thermodynamics cannot be extended to include negative temperatures. We further show that the Gibbs entropy fails to satisfy the postulates of thermodynamics and that its predictions for systems with nonmonotonic energy densities of states are incorrect.

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©2015 American Physical Society

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23/06/2015

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