Oxidation of acetaminophen at boron-doped diamond (BDD) and at Ti/SnO 2 anodes in a plug-flow divided electrochemical reactor led to electrochemical combustion, whereas at Ti/IrO 2 benzoquinone was the exclusive product except at very long electrolysis times. The difference is explicable in terms of the different mechanisms of oxidation: direct oxidation at the anode for Ti/IrO 2 vs. indirect oxidation involving electrogenerated hydroxyl radicals at BDD and Ti/SnO 2 . At BDD, at which the efficiency of degradation of acetaminophen was greatest, the rate of electrolysis at constant concentration was linearly dependent on the current, and at constant current linearly dependent on the concentration. Current efficiencies for mineralization up to 26% were achieved without optimization of the cell design.
The goal of the present research was the direct conversion of sulfide, an important contaminant in geothermal brines, to sulfate, whose discharge limits are much less stringent than those for sulfide. By the use of a novel anode material boron-doped diamond (BDD), we achieved near-quantitative electrochemical conversion of sulfide ions to sulfate with current efficiency of 90%. Kinetically, the reaction is first order in current density and zero-order in sulfide concentration. The current efficiency becomes essentially quantitative in the presence of chloride ion; under these conditions the reaction is chloride-mediated, at least in part, through the electrochemical formation of hypochlorite ion. Control experiments showed that hypochlorite oxidizes sulfide to sulfate quantitatively under the same conditions.
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