Dissociation constants of a host of substituted benzole acids, phenols, and some substituted acetic acids and their tetraethylammonium salts have been determined in ferf-butyl alcohol, isopropyl alcohol, and some In n-hexyl alcohol. Plots of pKd(HA) in ferf-butyl alcohol vs. those in water yielded slopes of 3.1 for benzole acids, 2.1 for phenols, and only 1.2 for substituted acetic acids and
... [Show full abstract] diethylbarbituric acid. Corresponding values for isopropyl alcohol are 2.0, 1.4, and 1.1, as compared to 1.4, 1.1, and 1.0, respectively, for methanol. The large resolution in t-BuOH is attributed to an increase in dispersion interaction of A- with solvent upon introduction of electronegative substituants. This conclusion is substantiated by the effects of substituants on Kd of the tetraethylammonium salts and on values of transfer activity coefficients of A- between t-BuOH and methanol.
