Abstract

Calcium-sodium exchange on Wyoming bentonite in methanol, ethanol and acetone-water systems were investigated at 0.03 N Cl and at room temperature. Calcium-sodium exchange isotherms were plotted at cosolvent concentrations ranging from 0 to 70% wt./wt. using Ca and Na ionic activities before and after correction for CaCl+ formation. In both cases and in all treatments, a greater selectivity of bentonite surfaces for Ca ions was observed. When compared to water, different trends were observed among and within cosolvents. These trends varied depending on whether or not CaCl+ formation was accounted for. Ignoring the formation of CaCl+, the preference of bentonite for Ca increased in methanol-water systems with increased percent methanol at low equivalent Ca fraction (<0.2). At higher Ca fractions, this preference matched that of water. In ethanol-water, no increased preference of the surface for Ca was observed. In acetone-water, increasing cosolvent concentration decreased the preference of the surface for Ca. The magnitude of this decrease was larger at low equivalent Ca fraction (<0.2). After correction for CaCl+, both in solution and on the surface, the preference of bentonite for Ca2+ was larger in methanol- and ethanol-water systems. In acetone-water, increased surface preference for Ca was only apparent at low acetone fractions (<50%). At higher acetone fractions, there was evidence of increased Na loading but no increase in Ca2+ selectivity. Clearly, ion-pair formation and its effects on Ca-Na exchange reactions cannot be ignored in mixtures of aqueous-organic solvents. After accounting for this effect, Ca-Na exchange in the studied solvents appears to be more of a surface-than a solution-controlled phenomenon that involves both electrostatic and specific solvent-surface types of interactions that have not been elucidated.

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