Revisiting the concept of chemical potential in classical and quantum gases: A perspective from Equilibrium Statistical Mechanics

Abstract

In this work we revisit the concept of chemical potential $\mu$ in both classical and quantum gases from a perspective of Equilibrium Statistical Mechanics (ESM). Two new results regarding the equation of state $\mu=\mu(n,T)$, where $n$ is the particle density and $T$ the absolute temperature, are given for the classical interacting gas and for the weakly-interacting quantum Bose gas. In order to make this review self-contained and adequate for a general reader we provide all the basic elements in an advanced-undergraduate or graduate statistical mechanics course required to follow all the calculations. We start by presenting a calculation of $\mu(n,T)$ for the classical ideal gas in the canonical ensemble. After this, we consider the interactions between particles and compute the effects of them on $\mu(n,T)$ for the van der Waals gas. For quantum gases we present an alternative approach to calculate the Bose-Einstein (BE) and Fermi-Dirac (FD) statistics. We show that this scheme can be straightforwardly generalized to determine what we have called Intermediate Quantum Statistics (IQS) which deal with ideal quantum systems where a single-particle energy can be occupied by at most $j$ particles with $0 \leqslant j \leqslant N$ with $N$ the total number of particles. In the final part we address general considerations that underlie the theory of weakly interacting quantum gases. In the case of the weakly interacting Bose gas, we focus our attention to the equation of state $\mu=\mu(n,T)$ in the Hartree-Fock mean-field approximation (HF) and the implications of such results in the elucidation of the order of the phase transitions involved in the BEC phase for non-ideal Bose gases.