The anionic forms of 26 drugs and organic model compounds have been extensively explored in the n-octanol/water system using voltammetry at three-phase electrodes. The objective of this study was to validate the ability of this electrochemical system to give reliable values of lipophilicity for organic ions, as well as to gain more information on the lipophilic behaviour of anions in the n-octanol/water system. Results were used to clarify the solvation mechanisms responsible for ion partitioning and to compare the information obtained in the two solvent systems n-octanol/water and 1,2-dichloroethane/water.

A theoretical analysis of reversible and quasireversible electrode reactions of a dissolved redox couple under conditions of the novel technique of differential square-wave voltammetry (DSWV) is presented. The technique is recently introduced as a hybrid form between differential pulse voltammetry (DPV) and square-wave voltammetry (SWV) as the two most advanced and competitive pulse-form voltammetric techniques for a purpose of unifying their advantages and further advancing both techniques in terms of analytical performances, mechanistic analysis, and electrode kinetics. The potential modulation of DSWV consists of potential steps and pulses providing a plethora of voltammetric curves, which enable in-depth characterization of the electrode reaction with a minimal set of measurements. Based on numerical simulations, a set of criteria for characterization and differentiation between reversible and quasireversible electrode reactions are established.