Abstract
A detailed quantitative model for the adsorption of hydrolyzable metal ions at the oxide—water interface is presented in terms of the competition between the free energy changes faavorble to adsorption, i.e., coulombic and chemical energy changes, and the unfavorable change in solvation energy. Because of the quadratic dependence of solvation energy changes on the charge of the ion, this term decreases the adsorption of highly charged species. As hydrolysis occurs and the ionic charge is lowered, the coulombic and chemical energy contributions dominate the adsorption energy change and adsorption is abruptly enhanced. If the oxide has a dielectric constant similar to that of the solvent then solvation energy changes are minimal and do not prevent adsorption of unhydrolyzed species.
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