Abstract
The effect of dielectric constant on ion association of triethylammonium picrate and methylimidazolium picrate and on ion-ligand complex formation between the cations Et3NH+ and MeImH+ and 1-methylimidazole was investigated from conductance data carried out in nitrobenzene-benzene mixtures (34.8<D<17.9). The ion association constantsK A satisfy in first approximation the relation logK A ∼ 1/D. The center-to-center distance å has been calculated and compared to the value obtained for nonhydrogenbonded ion pairs. The ion-ligand association constantK +1 increases as the dielectric constant of the medium decreases. Plots of logK +1 against 1/D give straight lines, the slopes of which are consistent with the predictions of a theory that interprets the effect of the dielectric constant in terms of changes in the polarization energy of the solvent around the complexed and the uncomplexed ions. For these interactions, the complexed ions can be approximated as charged spheres, the volume of which is equal to that of the bare ion plus the volume of the ligand.
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Van Even, V., Haulait-Pirson, M.C. Influence of the dielectric constant on ion-pair and ion-ligand complex formation. J Solution Chem 6, 757–770 (1977). https://doi.org/10.1007/BF00650452
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DOI: https://doi.org/10.1007/BF00650452