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Diffusion in compacted clays is often studied in sandwich-like arrangements where the clay is confined by porous filter plates in order to control its swelling. In some clays (for example, Na-montmorillonite) equilibrated with dilute electrolyte solutions, the fluxes of cationic radiotracers can be quite high due to cation-exchange reactions. Accordingly, the diffusion resistance of clay layers can become comparable with or even smaller than the diffusion resistance of porous filters (such layers are called "thin" in this study). In view of the typical uncertainties (ca. 20%) of diffusion permeability of porous filters reported in the literature, the diffusion resistance of clay layers cannot be reliably determined from the steady-state diffusion permeability of the filter-clay-filter "sandwich" in this case. In this study, it is shown that, rather unexpectedly, information on the diffusion permeability of "thin" clay layers can be obtained from the time dependence of diffusant flux into the outlet compartment because at very short times, there is a characteristic flux delay that does not occur in the limiting case of infinitely large diffusion permeability of clay. The flux behavior at longer times is controlled by the diffusion permeability of the filters, which makes possible its determination directly from through-diffusion data and makes superfluous independent diffusion experiments with filters. This approach has been validated via theoretical interpretation of literature data on the diffusion of (22)Na radiotracers through confined compacted montmorillonite equilibrated with 0.01 M NaClO(4) solution. The filter and clay properties estimated in this way are in good agreement with the literature data.

It is shown theoretically that the experimentally observed shifts of isoelectric points of various oxide surfaces toward more basic pH's in concentrated and mixed-solvent electrolyte solutions can be explained by a model previously used to predict the phenomenon of "coagulation zones" in the stability of colloids with adsorption layers of nonionic polymers. The model assumes the standard solvation energies of ions near a solid-liquid interface to be different from those in the bulk due to changes in the solvent structure. To reproduce the trends of experimental data in aqueous solutions, the solubilities of both cations and anions must be decreased, but for cations that must occur to a smaller extent. In mixed solvents a qualitative agreement with the experimental data is achieved by assuming that there is a water-enriched layer near the oxide surface. Copyright 2001 Academic Press.