Prediction of surface charge on oxides in salt solutions: Revisions for 1:1 (M +L −) electrolytes

Abstract

Quantitative characterization of the development of proton surface charge on the surfaces of minerals is necessary for a fundamental understanding of reactions between minerals and aqueous electrolyte solutions. Despite many experimental studies of charge development, few attempts have been made to integrate the results of such studies with a theoretical framework that permits prediction. The present study builds on a theoretical framework to analyze a total of 55 sets of proton surface charge data referring to wide ranges of ionic strengths, and types of electrolyte and oxide. The resulting parameters were interpreted with the aid of crystal chemical, electrostatic, and thermodynamic theory, which enable a number of generalizations. Prediction of values of the pH ZPC and Δ pK n θ reduces the number of triple-layer parameters to be estimated. New standard states for the equilibrium constants for electrolyte adsorption ( K M + θ and K L − θ) permit direct comparison of samples with a range of surface areas or site densities. Predicted cation binding on high dielectric constant solids (e.g., rutile) shows K M + θ, increasing in the sequence Cs +, Rb +, K +, Na +, Li +. In contrast, on low dielectric constant solids (e.g., amorphous silica), the predicted sequence is Li +, Na +, K +, Rb +, Cs +. The opposite sequences are attributable to the large solvation energy contribution opposing adsorption on low-dielectric constant solids. Cation and anion binding constants are in general different, which enables direct prediction of the point-of-zero-salt effect ( pH PZSE ) relative to the pristine point-of-zero charge. The inner and outer capacitances in the triple-layer model ( C 1 and C 2) are predictable parameters consistent with physically reasonable distances and interfacial dielectric constants for water. In summary, all the parameters in the triple-layer model can be estimated with the revised equations of this study, which enables prediction of proton surface charge for any oxide in 1:1 electrolyte solutions independent of experiments. Such predictions can serve as a complement to the experimental study of new oxide/electrolyte systems, or more complex systems, where additional mechanisms of charge development are likely.