Thallium(I) Oxidation by Permanganate and Chlorine: Kinetics and Manganese Dioxide Catalysis

The oxidation of the toxic heavy metal thallium(I) (Tl(I)) is an efficient way to enhance Tl removal from water and wastewater. However, few studies have focused on the kinetics of Tl(I) oxidation in water, especially at environmentally relevant pH values. Therefore, the kinetics and mechanisms of Tl(I) oxidation by the common agents KMnO4 and HOCl under environmentally relevant pH condition were explored in the present study. The results indicated that the pH-dependent oxidation of Tl(I) by KMnO4 exhibited second-order kinetics under alkaline conditions (pH 8-10) with the main active species being TlOH, while the reaction could be characterized by autocatalysis at pH 4-6, and Mn(III) might also play an essential role in the MnO2 catalysis. Furthermore, a two-electron transfer mechanism under alkaline conditions was preliminarily proposed by using linear free energy relationships and X-ray photoelectron spectroscopy (XPS) analysis. Distinctively, the reaction rate of Tl(I) oxidation by HOCl decreased with increasing pH, and protonated chlorine might be the main active species. Moreover, the Tl(I)-HOCl reaction could be regarded as first order with respect to Tl(I), but the order with respect to HOCl was variable. Significant catalysis by MnO2 could also be observed in the oxidation of Tl(I) by HOCl, mainly due to the vacancies on MnO2 as active sites for sorbing Tl. This study elucidates the oxidation characteristics of thallium and establishes a theoretical foundation for the oxidation processes in thallium removal.