Abstract
AbstractThe self‐diffusion coefficients of acetonitrile, methanol and ions in salt free acetonitrile‐methanol mixtures and in solutions of NaI have been measured at 25°C for the whole composition range of the binary solvent, for the salt molarity ranging from 1 · 10−4 to 1 · 10−2. The limiting self‐diffusion coefficients of sodium and iodide ions increase monotonously with increasing concentration of acetonitrile. The composition dependences of the ionic radii allow to postulate a preferential solvation of iodide ions by acetonitrile. That phenomenon has been found for those compositions of the mixed solvent, for which a microheterogeneity of the system has been observed. In methanol rich solvents (xAN < 0.5) the observed microheterogeneity results from the self‐association of methanol. The preferential solvation of iodide ions causes an enlargement of acetonitrile aggregates resulting in enhancement of microheterogeneity of the system. These results confirm a hypothesis that if interactions between ions and components of the mixed solvent are similar the preferential solvation of ions is promoted by the structure of solvent.
Published Version
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