Past exam of the chemistry A course of the University of Cambridge / 2022 / Paper 2 / A6 / d / Solution

For the adsorbed lattice gas, the Helmholtz free energy isUse Stirling's approximation with $M,N,M-N$ large, then differentiate at fixed $M,T,B$. Writing surface coverage as $\theta =N/M$ gives the adsorption chemical potentialThe occupation ratio comes from site-mixing entropy; it is essential near saturation.

Let $N_g$ be the number of free atoms and $n_g=N_g/V$. In the field-free gas, both spin states have zero energy, so the one-atom partition function is $q_g=2V/{\Lambda }^3$, where $\Lambda$ is the thermal de Broglie wavelength. For a dilute ideal gas,ThereforeThe last equality uses $p=n_g{k}_{\mathrm{B}}T$. The bulk spin degeneracy is two even though the bulk magnetic field vanishes: degeneracy is not the absence of spin states.