Adsorption of Rb + and Sr 2+ at the orthoclase (0 0 1)–solution interface

Abstract

Adsorption of Rb + and Sr 2+ at the orthoclase (0 0 1)–solution interface is probed with high-resolution X-ray reflectivity and resonant anomalous X-ray reflectivity. Specular X-ray reflectivity data for orthoclase in contact with 0.01 m RbCl solution at pH 5.5 reveal a systematic increase in electron density adjacent to the mineral surface with respect to that observed in contact with de-ionized water (DIW). Quantitative analysis indicates that Rb + adsorbs at a height of 0.83 ± 0.03 Å with respect to the bulk K + site with a nominal coverage of 0.72 ± 0.10 ions per surface unit mesh (55.7 Å 2). These results are consistent with an ion-exchange reaction in which Rb + occupies an inner-sphere adsorption (IS) site. In contrast, X-ray reflectivity data for orthoclase in contact with 0.01 m Sr(NO 3) 2 solution at pH 5.3 reveal few significant changes with respect to DIW. Resonant anomalous X-ray reflectivity was used to probe Sr 2+ adsorption and to image its vertical distribution. This element-specific measurement reveals that Sr 2+ adsorbs with a total coverage of 0.37 ± 0.02 ions per surface unit mesh, at a substantially larger height (3.28 ± 0.05 Å) than found for Rb +, and with a relatively broad density distribution (having a root-mean-square width of 1.88 ± 0.08 Å for a single-peak model), implying that Sr 2+ adsorbs primarily as a fully-hydrated outer-sphere (OS), species. Comparison to a two-height model suggests that 13 ± 5% of the adsorbed Sr 2+ may be present as an IS species. This partitioning implies a ∼5 kJ/mol difference in free energy between the IS and OS Sr 2+ on orthoclase. Differences in the partitioning of Sr 2+ between IS and OS species for orthoclase (0 0 1) and muscovite (0 0 1) suggest control by the geometry of the IS adsorption site. Results for the OS distribution are compared to predictions of the Poisson–Boltzmann equation in the strong coupling regime, which predicts an intrinsically narrow vertical diffuse ion distribution; the OS distribution might thus be thought of as the diffuse ion profile in the limit of high surface charge.