Separation of limiting equivalent conductances into ionic contributions in non-aqueous solutions by indirect methods

Abstract

All existing indirect methods for the separation of Λ₀ values into ionic components in organic solvents are analysed. A general method, based on the phenomenon of the non-solvation of large tetraalkyl(aril)onium ions, is proposed. The method is shown to be independent of the chemical nature of organic solvents and temperature. This permits us to examine the relationship between ionic limiting equivalent conductances and values calculated on their basis, and the intrinsic structure of organic solvents. By using this method, the ionic limiting equivalent conductances are calculated for 50 organic solvents at 25 °C and for 9 solvents over a wide temperature interval. The use of the method for obtaining ionic limiting equivalent conductances in organic mixtures is demonstrated. The values calculated by the suggested method under various conditions are in good agreement with the experimental literature values.