Oxidation of carbamazepine by Mn(VII) and Fe(VI): Reaction kinetics and mechanism

Experimental studies were conducted to examine the oxidation of carbamazepine, an anticonvulsant drug widely detected in surface waters and sewage treatment effluent, by potassium salts of permanganate (Mn(VII); KMnO ₄) and ferrate (Fe(VI); K ₂FeO ₄). Results show that both Mn(VII) and Fe(VI) rapidly oxidize carbamazepine by electrophilic attack at an olefinic group in the central heterocyclic ring, leading to ring-opening and a series of organic oxidation products. Reaction kinetics follow a generalized second-order rate law, with apparent rate constants at pH 7.0 and 25°C of 3.0(±0.3) × 10 ² M ^-1 s ^-1 for Mn(VII) and 70(±3) M ^-1 s ^-1 for Fe(VI). Mn(VII) reaction rates exhibit no pH dependence, whereas Fe(VI) reaction rates increase dramatically with decreasing pH, due to changing acid-base speciation of Fe(VI). Further studies with Mn(VII) show that most common nontarget water constituents, including natural organic matter, have no significant effect on rates of carbamazepine oxidation; reduced metals and (bi)sulfide exert a stoichiometric Mn(VII) demand that can be incorporated into the kinetic model. The removal of carbamazepine in two utility source waters treated with KMnO ₄ agrees closely with predictions from the kinetic model that was parametrized using experiments conducted in deionized water at much higher reagent concentrations.