Past exam of the mathematics course of the year 1 of the natural sciences course of the University of Cambridge / 2005 / Paper 2 / 7 / a / Solution

The required Legendre transform is the Helmholtz free energy, $\boxed{F=U-TS}$ up to an additive constant. Its differential is $dF=dU-TdS-SdT=-SdT-pdV$, so $F_T{|}_V=-S$ and $F_V{|}_T=-p$. Equality of mixed partial derivatives for a smooth thermodynamic state gives the Maxwell relationNext use the total differential $dS=S_T{|}_{V}dT+S_V{|}_{T}dV$. Along a fixed-pressure path, divide by $dT$ to get $S_T{|}_p=S_T{|}_V+S_V{|}_T{V}_T{|}_p$. Substitute the Maxwell relation to obtainMultiplying by $T$ gives the usual difference between the heat capacity at constant pressure and the heat capacity at constant volume.