Paper 2, Section II, A

Statistical Physics
Part II, 2020

Using the Gibbs free energy G(T,P)=ETS+PVG(T, P)=E-T S+P V, derive the Maxwell relation

SPT=VTP\left.\frac{\partial S}{\partial P}\right|_{T}=-\left.\frac{\partial V}{\partial T}\right|_{P}

Define the notions of heat capacity at constant volume, CVC_{V}, and heat capacity at constant pressure, CPC_{P}. Show that

CPCV=TVTPPTVC_{P}-C_{V}=\left.\left.T \frac{\partial V}{\partial T}\right|_{P} \frac{\partial P}{\partial T}\right|_{V}

Derive the Clausius-Clapeyron relation for dPdT\frac{d P}{d T} along the first-order phase transition curve between a liquid and a gas. Find the simplified form of this relation, assuming the gas has much larger volume than the liquid and that the gas is ideal. Assuming further that the latent heat is a constant, determine the form of PP as a function of TT along the phase transition curve. [You may assume there is no discontinuity in the Gibbs free energy across the phase transition curve.]