Oxidation kinetics of p-aminodiphenylamine with peroxydisulphate

The kinetics of oxidation of p-aminodiphenylamine with the peroxydisulphate ion were investigated spectrophotometrically. The oxidation was accompanied by the appearance of a wine-red colour, which changed to become colourless. The reaction rate was measured by the stopped-flow technique with a UV spectrophotometer. The reactions proceeded with second-order kinetics, first-order for each individual reactant. Cationic micelles (cetyltrimethyl ammonium bromide) caused an enhancement in the reaction rate followed by inhibition at higher concentrations. Anionic micelles (sodium dodecyl sulphate), on the other hand, had a slightly retarding effect. The effects of radical scavenger, pH and ionic strength on the fast oxidation rate were examined. A mechanism consistent with the observations is discussed.