Past exam of the chemistry A course of the University of Cambridge / 2021 / Paper 2 / A8 / b

For a fixed number of non-interacting molecules, $Z_N=q^N/N!$ in the dilute ideal gas limit. The temperature-independent factorial drops out of the internal energy derivative:Differentiate once more at fixed volume to obtainPrimes denote fixed-volume derivatives. If $q$ factorizes into translational, rotational and other independent contributions, their heat capacities add. In particular, the three-dimensional translational factor contributes $3R/2$, while a constant spin degeneracy factor contributes zero. The formula also follows from the positive canonical energy variance, $C_V=\mathrm{Var}(E)/(k_{\mathrm{B}}{T}^2)$.

For a high-temperature linear rigid rotor, $q_{\mathrm{rot}}=T/{\theta }_{\mathrm{rot}}$ up to temperature-independent symmetry/spin factors. Therefore $q^{\prime }/q=1/T$ and $q^{\prime \prime }=0$, givingThis agrees with the equipartition theorem for two quadratic rotational coordinates. It is the rotational contribution; adding free three-dimensional translation gives $C_{V,m}=5R/2$ when vibrations remain unexcited. A constant rotational symmetry number does not affect this derivative.