Past exam of the physics B course of the University of Cambridge / 2010 / Paper 1 / Section C / C10

For a fixed-composition simple compressible system, $dG=-SdT+Vdp$ gives $S=-(\partial G/\partial T{)}_p$ and $V=(\partial G/\partial p{)}_T$. Equality of mixed derivatives yields $(\partial S/\partial p{)}_T=-(\partial V/\partial T{)}_p$. ThereforeFor one mole of ideal gas, $V_m=RT/p$, so $(\partial V_m/\partial T{)}_p=R/p$. Reversible heat at fixed pressure gives $(\partial S_m/\partial T{)}_p=C_{mp}/T$, and consequentlyWith constant positive molar heat capacity, integrate from a reference state $(p_0,T_0)$:If heat capacity varies, the last term must instead be ${\int }_{T_0}^T{C}_{mp}(T^{\prime })d{T}^{\prime }/T^{\prime }$. The reference ratios make the logarithms dimensionless. The following classical ideal-gas entropy limits test where the constant-heat-capacity expression remains applicable.

At fixed positive pressure, the extrapolated term $C_{mp}\ln (T/T_0)$ tends to $-\infty$ as $T\to 0^{+}$. That prediction is not physically realistic for an equilibrium sample. The classical ideal-gas description with constant heat capacity cannot extend unchanged to absolute zero. A real substance generally undergoes phase changes, and quantum statistics and thermal freeze-out change its heat capacity and entropy. For a nondegenerate equilibrium ground state, the third law gives entropy approaching zero; residual ground-state degeneracy can give a finite residual value rather than this negative divergence. This is a breakdown of the extrapolation, not a violation of the third law by a real gas.

At fixed positive temperature, $-R\ln (p/p_0)$ tends to $+\infty$ as $p\to 0^{+}$. This is a physically meaningful unbounded-volume limit for a fixed mole number: $V_m=RT/p\to \infty$, so the number of accessible translational configurations grows without bound. For an ideal gas the entropy difference is $R\ln (V_{m,2}/V_{m,1})$ at fixed temperature. No finite vessel reaches an infinite entropy, and $p=0$ at finite temperature is not a finite-volume one-mole state. The divergence is approached by dilution; it does not conflict with the third law, which concerns a different temperature limit.