Abstract
The results of dielectric relaxation experiments on solutions of LiClO 4, NaClO 4 and Bu 4NClO 4 in N, N-dimethylformamide (DMF), and N, N-dimethylacetamide (DMA), performed at 25°C in the frequency range 0.2≤ ν/GHz≤89 are presented. For all electrolytes, a solute relaxation process due to ion pairs is observed in addition to the solvent relaxation. The alkali salts form predominantly solvent-shared ion pairs in DMF and DMA, whereas contact ion pairs are observed for Bu 4NClO 4. In all cases, the rate of ion-pair formation is nearly diffusion-controlled. Effective solvation numbers were deduced from the solvent dispersion amplitude. Data suggest that the anion–solvent interactions are weak, whereas the alkali ions form a well-defined primary solvation shell. Interestingly, irrotational bonding of solvent molecules by Bu 4N + is observed, possibly due to steric interactions.
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