First-order phase transformation at constant volume: a continuous transition?

Abstract

We describe a first-order phase transition of a simple system in a process where the volume is kept constant. We show that, unlike what happens when the pressure is constant, (i) the transformation extends over a finite temperature (and pressure) range, (ii) each and every extensive potential (internal energy $U$, enthalpy $H$, Helmholtz energy $F$ and Gibbs energy $G$), and the entropy $S$, is continuous across the transition, and (iii) the constant-volume heat capacity does not diverge during the transition, only exhibits discrete jumps. These non-intuitive results highlight the importance of controlling the correct variables in order to distinguish between continuous and discontinuous transitions. Additionally, they provide a didactic tool to further discuss the phase transitions phenomena. We apply our results to describe the transition between ice VI and liquid water using thermodynamic information available in the literature.