Past exam of the chemistry A course of the University of Cambridge / 2023 / Paper 2 / A7 / b

Use the additive-volume two-level system implicit in the model: each excited particle increases the volume by the same increment. The difference between the two endpoint volumes is $V_0$, so that increment is $v=V_0/N$.

If $N_1$ particles are excited, $V=V_0+(V_0/N)N_1$. Linearity of the expectation gives $⟨N_1⟩=N{P}_1$, henceAs $T\to 0$, $V\to V_0$. As $T\to \infty$, only three quarters of the particles are excited on average, giving $V\to 7V_0/4$, rather than the all-excited endpoint $2V_0$. These limits also check the inclusion of state degeneracy.