Ultrasonic degradation of trichloroethylene and chlorobenzene at micromolar concentrations: kinetics and modelling

Although most papers in the field of sonochemical degradation of volatile organics in aqueous media describe experiments at the millimolar concentration range, this study focuses on the degradation kinetics of chlorobenzene (CB) and trichloroethylene (TCE) in the micromolar range. It was found that the reaction kinetics increase with decreasing initial substrate concentrations. For example, the pseudo-first-order reaction rate constant of CB increases by a factor of 14.3, if the initial concentration drops from 3440 to 1 μM. Previous work in the millimolar range has shown that the degradation of these volatiles is mainly due to pyrolytic reactions. The enhancement of the reaction kinetics at lower concentrations, in this work, could no longer be explained by this mechanism, even by taking into account the effect of the concentration of the solutes on the reaction temperature. Therefore, a new model was developed, incorporating gas phase OH radical induced degradation, next to pyrolysis. The model, fitting the experimental results, illustrated that at micromolar concentrations the OH radical induced degradation becomes significant. Simulations showed that at initial concentrations of CB>1000 μM degradation is due to pyrolysis for over 99.97%, but it was also demonstrated that at concentrations between 1 and 5 μM, the OH radical mechanism contributed 48.5% of the total degradation.