Quasi-static decomposition and the Gibbs factorial in small thermodynamic system
Abstract
For small thermodynamic systems in contact with a heat bath, we determine the free energy by imposing the following two conditions. First, the quasi-static work in any configuration change is equal to the free energy difference. Second, the temperature dependence of the free energy satisfies the Gibbs-Helmholtz relation. We find that these prerequisites uniquely lead to the free energy of a classical system consisting of -interacting identical particles, up to an additive constant proportional to . The free energy thus determined contains the Gibbs factorial in addition to the phase space integration of the Gibbs-Boltzmann factor. The key step in the derivation is to construct a quasi-static decomposition of small thermodynamic systems.
Keywords
Cite
@article{arxiv.2205.05863,
title = {Quasi-static decomposition and the Gibbs factorial in small thermodynamic system},
author = {Shin-ichi Sasa and Ken Hiura and Naoko Nakagawa and Akira Yoshida},
journal= {arXiv preprint arXiv:2205.05863},
year = {2022}
}
Comments
11 pages, 2 figures