Simple equations are presented which allow double-layer potentials of clays to be derived from co-ion exclusion measurements in monovalent and divalent electrolyte solutions. These equations have been used to re-interpret earlier results for illite and montmorillonite. The potentials derived follow the lyotropic series for the various homoionic modification of each clay. We have demonstrated that the Schofield equation, which assumes high double-layer potentials, cannot be applied to co-ion exclusion in clay systems. Re-analysis of earlier measurements has shown that for a given homoionic clay the potentials are almost independent of concentration over the range 0.3 to 0.003 molar. Thus, clay surfaces appear to behave more like constant-potential than constant-charge surfaces.
