Theory of monolayer physical adsorption. I. Flat surface

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Abstract
The general statistical mechanical expression for the adsorption isotherm of a classical gas interacting with an inert solid is simplified by imposing the two‐dimensional approximation and by Fourier expanding the factors in the configurational integral that arise from the periodic gas–solid interaction. The leading term in the resulting expression describes a two‐dimensional fluid; approximate pair correlation functions and thermodynamic properties of such a system of Lennard‐Jones atoms are evaluated and compared with published computer simulations. The method of calculation consists in an adaptation of statistical mechanical perturbation theory which allows one to treat two‐dimensional systems at the temperatures and densitites that are of interest experimentally. Reasonably good agreement with the simulations is obtained. The usefulness and significance of these results are discussed.