Wurm, B. and Münsterer, M. and Richardi, J. and Buchner, Richard and Barthel, Josef (2005) Ion association and solvation of perchlorate salts in N,N-dimethylformamide and N,N-dimethylacetamide. Journal of Molecular Liquids 119 (1-3), pp. 97-106.
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The results of dielec. relaxation expts. on solns. of LiClO4, NaClO4 and Bu4NClO4 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 obsd. in addn. to the solvent relaxation. The alkali salts form predominantly solvent-shared ion pairs in DMF and DMA, whereas contact ion pairs are obsd. for Bu4NClO4. In all cases, the rate of ion-pair formation is nearly diffusion-controlled. Effective solvation nos. 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 mols. by Bu4N+ is obsd., possibly due to steric interactions.
|Institutions:||Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry VI - Physical Chemistry (Solution Chemistry) > PD Dr. Richard Buchner|
|Keywords:||lithium sodium butylammonium perchlorate amide soln solvation ion pairing|
|Subjects:||500 Science > 540 Chemistry & allied sciences|
|Refereed:||Yes, this version has been refereed|
|Created at the University of Regensburg:||Yes|
|Deposited On:||11 Jun 2012 09:09|
|Last Modified:||11 Jun 2012 09:09|