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The physics and mathematics of the second law of thermodynamics

1997/08/31 by Elliott H. Lieb, Jakob Yngvason · 6 citations
Engineering · Mathematics · Physics and Astronomy · #Advanced Thermodynamics and Statistical Mechanics #Phase Equilibria and Thermodynamics #Statistical Mechanics and Entropy #cond-mat.soft #math-ph #math.MP

paper · pdf · doi:10.1016/s0370-1573(98)00082-9

published as Phys.Rept. 310 (1999) 1-96 · 93 pages, TeX, 8 eps figures. Updated, published version. A summary appears in Notices of the Amer. Math. Soc. 45 (1998) 571-581, math-ph/9805005

arxiv created 1999/01/28 · openalex publication_date 1999/03/01 · arxiv updated 2009/11/30 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

The essential postulates of classical thermodynamics are formulated, from which the second law is deduced as the principle of increase of entropy in irreversible adiabatic processes that take one equilibrium state to another. The entropy constructed here is defined only for equilibrium states and no attempt is made to define it otherwise. Statistical mechanics does not enter these considerations. One of the main concepts that makes everything work is the comparison principle (which, in essence, states that given any two states of the same chemical composition at least one is adiabatically accessible from the other) and we show that it can be derived from some assumptions about the pressure and thermal equilibrium. Temperature is derived from entropy, but at the start not even the concept of `hotness' is assumed. Our formulation offers a certain clarity and rigor that goes beyond most textbook discussions of the second law.

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