On the relation between thermodynamical and statistical entropy: The origin of the N!

Abstract

The division by N! in the expression of statistical entropy is usually justified to students by the statement that classical particles should be counted as indistinguishable. Sometimes, quantum indistinguishability is invoked to explain it. In this paper, we try to clarify the issue starting from Clausius thermodynamical entropy and deriving from it Boltzmann statistical entropy for the ideal gas. This approach appears interesting for two reasons: Firstly, it provides a direct heuristic link between thermodynamical and statistical expressions of entropy that is missing in the usual approach. In second place, it explicitly reminds that also statistical entropy is defined with respect to a reference state, chosen to be the quantum-mechanical (T=0) ground state of the N-particles in a box. Both factors $h^{3N}$ and $N!$ at the denominator of the statistical entropy are a consequence of the quantum nature of the reference state: in particular, the $N!$ is not related to the particle identity, but to the identity of the boundary conditions on the quantum-mechanical ground-state momenta, and to a general statistical maximization principle. The introduction of a reference state also allows to reinterpret the standard case of two mixing gases.