A general treatment and classification of the solute adsorption isotherm. I. Theoretical

Abstract A theoretical basis is developed for the classification of adsorption isotherms for solutes in dilute solution, which relates their characteristic shapes to parameters of the solvent and any second solute. Three of the four main classes (S, L, H) are accounted for by differences in relative magnitude of the activation energies of desorption of solutes and solvent. The S-shaped isotherm is also accounted for by an additional concentration-dependence of this parameter, implying cooperative adsorption. The subgroups of each class are also explained. The linear (C) isotherm is explained by penetration of substrate micropores by solute, with or without solvent, whereby new adsorption sites are opened up; the theory predicts the experimentally found sharp inflection to a plateau in the C-curves. Curves of the other classes can also in some cases show a linear branch above the turning point, representing conditions like those for C-curves. The theoretical treatment is valid whether the adsorbing surface is energetically uniform, or, as in most systems, nonuniform.