Past exam of the mathematics course of the year 1 of the natural sciences course of the University of Cambridge / 2013 / Paper 2 / 17 / a / Solution

For fixed amount of substance, take the internal energy $U=U(S,V)$. The first law of thermodynamics identifies $T=U_S{|}_V$ and $-P=U_V{|}_S$. Equality of mixed second derivatives givesFor the Helmholtz free energy, subtract the product differential $d(TS)$ from the first law of thermodynamics to obtain $dF=-SdT-PdV$. Its natural variables are $(T,V)$, so $F_T=-S$ and $F_V=-P$. Exactness therefore givesFor the Gibbs free energy, the product rule gives $dG=-SdT+VdP$. Thus $G_T=-S$, $G_P=V$, andFor the enthalpy, $dH=TdS+VdP$, giving $H_S=T$, $H_P=V$ andThese are the four Maxwell relations, each following from exactness in the appropriate pair of natural variables.