Past exam of the physics B course of the University of Cambridge / 2021 / Paper 2 / Section C / C8 / b / Solution

At coexistence, the two phases of a pure substance have equal chemical potential, or equivalently equal molar Gibbs free energy:For either phase, $d\mu =-s_{m}dT+v_{m}dp$. Move an infinitesimal distance along the coexistence curve, where the equality must remain true. Subtracting the two differentials givesA reversible transformation at this common temperature absorbs latent heat $L=T\Delta s_m$. ThusThe derivation assumes thermodynamic equilibrium between two bulk phases of a single pure substance, with the same temperature and pressure, and only ordinary pressure-volume work. Surface-curvature shifts, additional external-field work and composition changes are omitted. It applies to a first-order phase boundary where the latent heat and volume discontinuity are defined. No ideal-gas assumption and no constant-$L$ assumption are needed for this differential relation. At the critical endpoint both discontinuities vanish, so their ratio requires a limiting treatment rather than direct substitution of two zeros.