Past exam of the quantum condensed matter course of the University of Cambridge / 2004 / Section B / B7 / b

The Clapeyron equation gives the slope of a two-phase phase coexistence curve. Let $s_l,s_v$ and $v_l,v_v$ be entropy and volume per molecule, or consistently per mole. Equality of the two chemical potentials and $d\mu =-sdT+vdP$ implyAt reversible coexistence the latent heat in the same amount convention is $\mathcal{L}=T(s_v-s_l)$. ThereforeThe relation assumes thermodynamic equilibrium between two bulk phases of a pure substance, neglecting curvature and other work terms. For vaporization both latent heat and volume change are positive, giving a positive vapor-pressure slope. If the vapor is approximately ideal and its volume dominates, the ideal-vapor Clausius-Clapeyron approximation gives $d\ln P/dT\simeq \mathcal{L}/(k_B{T}^2)$ with latent heat per molecule.

Experimentally, a sealed two-phase sample in a temperature-controlled bath supplies the coexistence pressure as temperature changes. Independent calorimetry and phase-density measurements supply $\mathcal{L}$ and $\Delta v$, allowing the pressure slope to test the equation. The formula connects those distinct measurements and is a practical route to latent heats.