Electrogenerated HO radical reactions: the role of competing reactions on the degradation kinetics of hydroxy-containing aromatic compounds

The rate of degradation of some aromatic compounds, benzoic acid, 2-hydroxybenzoic acid, 4-hydroxybenzoic acid and 2,3-hydroxybenzoic acid, by electrogenerated HO radicals is investigated. The effect of the addition of secondary species, that can either be a reaction product of the target compound or not is analysed. The presence of the actual reaction products is also considered. The action of these secondary species is integrated in a general model that accounts for the dependency of the anode coverage by HO radicals on the concentration and on the reactivity of HO radical scavengers. From the magnitude of the effect of competing reactions, the reactivity of the hydroxybenzoic acid derivatives was estimated as the product between the stoichiometric coefficients and the rate constants. A possible mechanistic interpretation is provided to explain the unexpected high values of the stoichiometric coefficients estimated that largely exceed the number of radicals required for the complete mineralization of the species.