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

For liquid-vapor equilibrium, use molar quantities. At low vapor pressure the gas is dilute, approximately ideal, and has a much larger molar volume than the liquid. HenceSubstitution into the Clapeyron equation givesIf the molar latent heat varies sufficiently slowly to be treated as constant over the temperature interval, integration givesThe positive constant $p_0$ has pressure units and is an integration constant. It is not necessarily a real infinite-temperature pressure, since the approximations fail before that limit.

For mercury between $300$ and $500\mathrm{K}$, the original plot places this range above the triple point and below the normal boiling and critical temperatures. Its vapor pressure is low relative to the critical pressure, making a dilute-gas description reasonable; the vapor's molar volume greatly exceeds that of the dense liquid. The interval is also far from the critical region where $L$ tends to zero, so a roughly constant latent heat is a useful first approximation. The approximations are not exact: Kirchhoff's law of thermochemistry gives, at fixed pressure, the temperature derivative of a transformation enthalpy as the difference between the two molar heat capacities, so a precise fit over a wide interval would allow $L$ to vary.