Transport Behavior in Dimethyl Sulfoxide

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Abstract
Conductance of the salts , , , , , and in dimethyl sulfoxide (DMSO) were determined over a concentration range 10−4 mole/liter to near saturation and a temperature range 25°–55°C. , , and are completely dissociated while , , and appear to be slightly associated. Single‐ion conductivities were determined using triisoamylbutylammonium tetraphenylboride as the reference electrolyte. The effective ionic radii for ( , Na+ , , and ions were determined to be 5.12, 4.32, 3.03, 2.82, and 2.37Aå, respectively, at 25° C. Na+ ion is solvated with three DMSO molecules while the ion and the anions are relatively unsolvated. The effective ionic radii in DMSO are insensitive to temperature over the temperature range studied. Activation energies for ionic conductance in dilute solutions of , , , , and are, respectively 3.50, 3.30, 3.23, 3.21, and 3.16 kcal/mole. Limiting ionic mobilities λo, for alkali‐halide ions and other ions in DMSO at 25° are examined in the light of the Fuoss, Boyd, and Zwanzig theories of dielectric relaxation. The limiting ionic mobilities predicted by the Zwanzig theory are in qualitative agreement with the observed values, but the predicted magnitudes are low.

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