Physical Chemistry

Divalent Ion-Specific Outcomes on Stern Layer Structure and Total Surface Potential at the Silica:Water Interface

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Abstract

The second-order nonlinear susceptibility, chi(2), in the Stern layer, and the total interfacial potential drop, Phi(0)tot, across the oxide:water interface are estimated from SHG amplitude and phase measurements for divalent cations (Mg2+, Ca2+, Sr2+, Ba2+) at the silica:water interface at pH 5.8 and various ionic strengths. We find that interfacial structure and total potential depend strongly on ion valency. We observe statistically significant differences between the experimentally determined chi(2) value for NaCl and that of the alkali earth series, but smaller differences between ions of the same valency in that series. These differences are particularly pronounced at intermediate salt concentrations, which we attribute to the influence of hydration structure in the Stern layer. Furthermore, we corroborate the differences by examining the effects of anion substitution (SO4 2- for Cl-). Finally, we identify that hysteresis in measuring the reversibility of ion adsorption and desorption at fused silica in forward and reverse titrations manifests itself both in Stern layer structure and in total interfacial potential for some of the salts, most notable CaCl2 and MgSO4, but less so for BaCl2 and NaCl.

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