The study of the electrochemical oxidation mechanism of diphenylamine derivatives in dipolar aprotic solvents: III. Effect of acids and bases of different strengths

The effect of addition of different acids and bases in a wide range of concentration on the voltammetric oxidation of both Variamine blue (VB) and 4-aminodiphenylamine (4-ADPA) was examined in acetonitrile (AcN). The oxidation potential values of either wave of both depolarizers were found to depend on the acid or base strength of the additive—relative to the depolarizer and solvent—and on their concentration in solution. Addition of strong acid as CH₃SO₃H resulted in a single oxidation wave at potentials either equal to or more positive than that of the original second wave. Relatively weak acids as picric and pyridinium ion only shifted the oxidation potential of the first wave to more positive values without affecting the general oxidation pattern.On the other hand, strong bases like ethanolamine, resulted in the formation of a preoxidation wave at more negative potential when present in low concentration and a single wave at identical negative potential at high enough concentrations. Bases of comparable strengths, as that of the depolarizer, like pyridine do not form prewaves but only shifted the final single oxidation wave to more negative potential values. Weaker bases like water and ethanol mainly shifted the oxidation potential of the second wave to less positive values.