Adsorption isotherms based on a microscopic approach using the Percus–Yevick approximation are discussed with respect to those given by both continuum and B.E.T. methods. The microscopic approach predicts a new result, namely, that the onset of multilayer adsorption may not coincide with the bulk saturation vapour pressure. It may, for example, occur even above (but not too far away from) the critical point.
P. Richmond, J. Chem. Soc., Faraday Trans. 2, 1977, 73, 316 DOI: 10.1039/F29777300316
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