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

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.

Along a change in volume at fixed temperature, the first law of thermodynamics givesUse the Helmholtz Maxwell relation derived in (a) to replace the entropy derivative. This provesFor the stated Van der Waals equation, temperature-independent $a,b$ give $P_T{|}_V=R/(V-b)$. Hence $U_V{|}_T=a/V^2$. Integrating with respect to $V$ yieldsThe dilute-limit condition holds at every fixed $T$ and forces $h(T)=cT$, soThe result is the internal energy of a van der Waals gas in the fixed-amount convention of the question. Its volume derivative is positive even though the attractive energy correction itself is negative.