Effects of substituted ligands on the mobility of complexed anions
From conductance and viscosities measurements on Pr4NCl, Et4NBr, and AgNO3 in acetonitrile and Et3NBr in nitrobenzene, the Walden products of the anion at infinite dilution were determined in presence of various concentrations of substituted benzoic acids. From these data it was possible to compute the values of the Walden products of the once complexed anions and to estimate the order of magnitude of the Walden products of twice complexed anions. Stokes' law is not obeyed, and the Walden products are not proportional to the third root of the molar volume of the complexed ions, as a consequence of their lack of sphericity. The assumption that the drag force which acts on the ions is proportional to the volume of the substituents results in a linear expression between the reciprocals of the Walden products and the molar volume of the ligands. The experimental results fit this expression within the limits of the experimental errors, and the slopes of the lines are nearly the same for all the anions and for the two solvents studied here, namely, 2.5×10−4 ohm-cm−5 mole-cP−1.
Key wordsAcetonitrile conductivity ligands molar volume of ions nitrobenzene solvation Stokes' law viscosity Walden's rule
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