Past exam of the physics B course of the University of Cambridge / 2017 / Paper 2 / Section C / C11 / Equations of state and transitions

An equation of state relates equilibrium state variables such as pressure, volume, temperature and material amount. At fixed composition, it reduces the number of independent thermodynamic variables. It does not by itself specify all caloric properties: information such as heat capacity or internal energy is also needed.

At a liquid-gas first-order transition, an equilibrium isotherm can contain a constant-pressure interval in which changing total volume changes the phase fractions. A metastable single-phase extrapolation can instead show a region with $(\partial p/\partial V{)}_T>0$; that region has negative isothermal compressibility and is mechanically unstable. Thermodynamic phase coexistence requires equal temperature, pressure and chemical potential, and a consistent free-energy description replaces the unstable region by coexistence. For an appropriate analytic fluid equation of state, a liquid-gas critical point occurs where $(\partial p/\partial V{)}_T=({\partial }^{2}p/\partial V^2{)}_T=0$.

These tests diagnose the phase behaviour represented by that equation of state. They do not guarantee detection of every possible transition involving an additional order parameter which the mechanical equation omits.