Cation Exchange at the Mineral−Water Interface: H3O+/K+ Competition at the Surface of Nano-Muscovite

Abstract

This article describes a (39)K nuclear magnetic resonance (NMR) spectroscopic study of K+ displacement at the muscovite/water interface as a function of aqueous phase pH. (39)K NMR spectra and T 2 relaxation data for nanocrystalline muscovite wet with a solid/solution weight ratio of 1 at pH 1, 3, and 5.5 show substantial liquid-like K+ only at pH 1. At pH 3 and 5.5, all K+ appears to be associated with muscovite as inner- or outer-sphere complexes, indicating that H(3)O+ does not displace basal surface K+ beyond the (39)K detection limit under these conditions. In our pH 1 mixture, only approximately 1/3 of the initial basal surface K+ population is located more than 3-4 A from the surface. (29)Si and (27)Al MAS NMR spectra and SEM images show no evidence of dissolution during the (39)K experiments, consistent with the liquid-like (39)K fraction originating from displaced basal surface K+. Assuming no muscovite dissolution or interlayer exchange, the K+/H(3)O+ ratio relevant to the solution/surface exchange equilibrium is controlled by the total amount of K+ on the surface and H(3)O+ in solution (K+(surf)/H(3)O+(aq)). These parameters, in turn, depend on the basal surface area, solution pH, and the solid/solution ratio. The results here are consistent with significant displacement of surface K+ only under conditions where the initial K+(surf)/H(3)O+(aq). ratio is less than approximately 1. Computational molecular models of the muscovite/water interface should account for both K+ and H(3)O+ in the near-surface region.