Thermodynamics, interfacial structure, and pH hysteresis of Rb+ and Sr2+ adsorption at the muscovite (001)-solution...

The coverage and average height of adsorbed Rb+ and Sr2+ at the muscovite (001)-solution interface were measured with resonant anomalous X-ray reflectivity (RAXR) as a function of cation concentration (10-8 < [Sr2+] < 10(-1) m, 10-6 < [Rb+] < 10(-1) m at pH 5.5 and 3.5) and pH (1.5 to 5.5 at [Me(n+)] = 10(-3) m) without background electrolyte. At pH 5.5, Rb+ uptake approximately follows a Langmuir isotherm with deltaG(Rb)(o) = -23.5 +/- 4.0 kJ x mol(-1) and a saturation coverage of Tmax = 0.94 +/- 0.06 Rb+ per unit cell area, Auc = 46.72 A2, compensating the nominal surface charge density (1 e-/Auc). The Sr2+ isotherm has a saturation coverage of 0.47 +/- 0.05 Sr2+/Auc that also compensates the muscovite's charge, but the adsorption edge is both more abrupt and shifted significantly to lower concentration than that for Rb+. The uptake of Sr2+ is consistent with a Frumkin isotherm with an intrinsic adsorption constant, deltaG(Sr)(o) = -28.8 +/- 6.0 kJ x mol(-1) and a correlation energy, gamma(Sr) = -7.2 +/- 3.7 kJ x mol(-1). The average height of each adsorbed cation, corresponding to inner-sphere dominant Rb+ and coexisting inner- and outer-sphere Sr2+ distributions, was independent of ion coverage at pH 5.5. At pH 3.5, the adsorption edges of both ions shift to higher cation concentration, indicating competition with hydronium, and the shifts are accompanied by an irreversible reduction in the saturation coverage. The inner-sphere dominant mode of Rb+ adsorption did not change at pH 3.5, while that of Sr2+ changed to an outer-sphere dominant distribution. Hysteresis in both the amount and height of the adsorbed ion was observed as a function of the direction in which pH was changed, indicating that the intrinsic surface charge density decreased after reaction with acidic solutions. These results suggest new and unexpected interrelationships among the distribution of adsorbed ions, competitive adsorption of hydronium, and surface charge density at the mineral-solution interface.