Abstract
The pairwise nearest-neighbour interaction free energies in an adsorbed lattice gas consisting of solvent dipoles and chemisorbed adatoms bearing small charges are calculated assuming a primitive model of the double layer. These free energies are combined according to the Bragg-Williams and quasi-chemical approximations of lattice-gas theory to give expressions for the chemical potentials of adsorbed species, and hence for the total free energy of mixing, that do not involve assumptions that the adsorbed solvent dipoles behave as a dielectric continuum. The results of this analysis are used to derive equilibrium isotherms for the formation of chemisorbed monolayers.
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