NMR Shift and Diffusion Study of Electrolytes in 50% Dioxane—Water Mixtures

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Abstract
High‐resolution chemical shift measurements were carried out on electrolytic solutions in 50% dioxane—water mixtures. Whereas the water proton resonance position was displaced significantly by the addition of electrolyte, the dioxane signal in all mixtures remained unperturbed. Further, the results, particularly those obtained with chloride solutions of the small or highly charged Be, La, and Th ions indicated that strong selective solvation of cations by the water was occurring. This conclusion was substantiated by differences in the dioxane and the water linewidths observed in several solutions, including those of paramagnetic salts. Self‐diffusion coefficients of dioxane in these electrolytic mixtures were also measured by the nuclear magnetic resonance spin‐echo technique. The observed diffusion data could be interpreted solely on a hydrodynamical basis, again indicating that no significant interaction was occurring between dioxane and the added electrolyte.