The oxidative dissolution of uranium(IV) dioxide powder at room temperature in aqueous
carbonate media has been investigated. Kinetic studies evaluating the efficacy of various oxidants,
including K2S2O8, NaOCl, and H2O2, for dissolving UO2 in alkaline solution have been performed,
with H2O2 exhibiting the most rapid initial dissolution at 0.1 M oxidant concentrations. This
result is due in part to the ability of peroxide to act as both an oxidant and a ligand under
alkaline conditions. A spectrophotometric titration was used to confirm peroxide coordination
to the U(VI) metal center. The disappearance of characteristic absorbance maxima associated
with UO2(CO3)3
4- (e.g., 448.5 nm) and a subsequent change in solution coloration upon titration
with hydrogen peroxide indicated a change in speciation. Optimization of the hydrogen peroxide
concentration indicated that the initial rate of uranium oxidation increased with increasing
peroxide concentration, with a maximum reaction rate estimated at about 0.9 M peroxide. In
addition, the effects of both the carbonate countercation and the carbonate concentration were
also studied. It was determined that for 40 mg UO2 0.5 M Na2CO3 was the most propitious
choice, exhibiting both a high initial dissolution rate and the highest UO2 dissolution capacity
among the systems studied.