Abstract
Retention data on an immobilised artificial membrane have been taken from the work of Li et al. and from Liu et al., and have been correlated with a set of descriptors that includes descriptors for ionized species, that is anions from deprotonated acids and cations from protonated bases. Logk(IAM) values can be predicted for acids or bases that are partially ionized at the experimental pH and logk(IAM) values for acids and bases can be predicted as a function of the fraction present as the ionized species, equivalent to prediction as a function of pH. It is shown that anions reduce the value of logk(IAM) by about 1.1log units but that cations have almost no effect by comparison to the neutral species. By comparison to non-polar solvents, carboxylate anions and protonated base cations are considerably stabilized by both water and the IAM phase to about 6–8log units and so the rather small influence of anions (−1.1log unit) and cations (−0.1log unit) on logk(IAM) is due to substantial cancellation of these stabilization effects. Indeed, the effect of change of phase from water to IAM on the neutral species is at least as large as the effect of change of phase on the ionic species.
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