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Various Mn-oxides can oxidize Cr(III) to Cr(VI). Behaviors of chromium species in the oxidation system, especially on the oxide surface, are expected to control the reaction. During Cr(III) oxidation by birnessite and pyrolusite, Cr species in the reaction system were determined to elucidate their effects on the oxidation. Capacities of Cr oxidation of the two Mn-oxides were quite different. Solution pH and initial Cr(III) concentration also had significant effects on the Cr(III) oxidation by Mn-oxides. Chromium oxidation by pyrolusite was less than 5% of the oxidation by birnessite. The high crystallinity of pyrolusite could be one of the reasons and the difficulty of Cr (III) diffusion to the positive pyrolusite surface and Cr(VI) and Cr(III) adsorption seems to be other controlling factors. At pH 3, adsorption or precipitation of Cr species on the surface of birnessite were not found. Small amount of Cr(VI) adsorption was found on the surface of pyrolusite, but arty Cr precipitation on the oxide surface was not found. Therefore Cr(III) oxidation at pH 3 seems to be controlled mainly by the characteristics of Mn-oxides. Chromiun oxidation by Mn-oxides is thermodynamically more favorable at higher solution pH. However as solution pH increased Cr oxidation by birnessite was significantly inhibited. For Cr oxidation by pyrolusite, as pH increased the oxidation increased, but as Cr(III) addition increased the reaction was inhibited. Under these conditions some unidentified fraction of Cr species was found and this fraction is considered to be Cr(III) precipitation an the oxide surface. Chromium(III) precipitation on the oxide surface seems to play an important role in limiting Cr(III) oxidation by armoring the reaction surface on Mn-oxides as well as lowering Cr(III) concentration available for the oxidation reaction.
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