OFR-84-79 Factors Influencing The Solution Rate Of Uranium Dioxide Under Conditions Applicable To In Situ Leaching

The rate of dissolution of U02 was measured in acid solutions similar to those used for in situ leaching, with S04 of 10-1.82 to 10-4 M, Fe(III) of 10-2 to 10-4 M and pH's of 1.1 to 2.3. The dependence of dissolution rate on pH was small and inconsistent, probably reflecting the combined effects of a very weakly polar oxidizing complex, probably FeSO4+, and a nearly neutral U02 surface. Differences in the state of the U02 surface may explain this variability as well as contrasts between these results and results reported in other work. Changing either S04 or Fe(III) concentrations significantly affects dissolution rates. Increasing low sulfate concentrations in solutions containing 10 2 M Fe(III) at pH 2 results in formation of FeSO4+. In such solutions, rates increased with (S04)/(Fe(III)) up to 1:30, thereby indicating that the oxidation of U02 by FeSO4 is more rapid than by Fe3+. However, the dissolution rate decreased at higher (SO4)/ (Fe(III)), due either to sorption of SO42- on the UO2 surface or to formation of other less reactive sulfate complexes such as Fe(S04)2 or FeHSO4+ However, Fe(III) concentration is the dominant factor in determining solution rates. The rate was directly proportional to ferric iron concentration, indicating that the rate-determining step of the dissolution reaction is a single-electron oxidation by a ferric complex. Dissolution rates were lower in solutions of 0.1 and 1.0% H202 (0.029 and 0.29 M) than at similar concentrations of ferric iron because of formation of an insoluble surface coating of uranium peroxide, UO4?4H20. This phase may limit the value of hydrogen peroxide as an oxidant in lixiviants, not only by its very low solubility, but perhaps also by filling pores and reducing permeability in the ore body.