Kinetic studies on dissolution of UO2 powders in acid solutions by using cerium (IV) or chlorine dioxide as oxidants

The UO2 powders of 100-150, 150-212, 212-250, and 250-300 μm were dissolved in HNO3 or HCl solutions containing strong oxidants to examine their effect on the dissolution rates. Cerium(IV) species and ClO2 were used as oxidants in HNO3 and HCl solutions, respectively. The Ce(IV) species were prepared by bubbling O3 gas into HNO3 solutions containing Ce(NO3)3. All dissolution experiments were carried out under rapid stirring conditions which make it possible to neglect the diffusion effect. Dissolution reactions were analyzed on the assumptions that the UO2 powders are spherical particles and homogeneously dissolved from their external surface. Dissolution rate constants (Φ) in mol·cm-2·min-1 were measured at various concentrations of oxidants and temperatures. Furthermore, the effect of acid concentrations on the dissolution rate was also examined. As a result, the dissolution rate constants Φ were found to be expressed as Φ=kN[Ce(IV)][H+]0.6 for HNO3 solution([HNO3]=1-5M, Temp.≤30degC) and Φ=kH[ClO2][H+]-0.3 for HCl solution([HCl]=1-5M, Temp.≤30degC), respectively. Activation energies(kJ·mol-1) for the apparent dissolution rate constants are 44.1±1.9 for the HNO3 solution system and 33.5±2.8 for the HCl solution system, respectively. (author)