Kinetic and thermodynamic studies of the dissolution of thoria-urania solid solutions

摘要

The dissolution of Th1-xUxO2 was investigated through leaching experiments combined with X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) analyses. These experiments were performed in acidic and in oxidizing conditions (nitric solutions), for several compositions of solid solutions ranging from x = 0.24 to 0.81. Static sequential experiments in acidic media performed at room temperature confirmed that higher concentration of uranium in the solid solution leads to higher release of uranium in the leachate whatever the pH. The normalized dissolution rate in oxidizing media is increasing all the more the content of uranium is increases in the mixed oxide. While for Th enriched solids, kinetic parameters remain similar to that of ThO2, in the case of uranium enriched solids, a drastic change is observed, and kinetic parameters are similar to that Of UO2 ones. For x > 0.50, the saturation is reached in the leachate after 100 days. XPS and EXAFS analysis on leached samples pointed out an oxidation of U(IV) at the surface for x < 0.5, and in the bulk for x > 0.5. Enrichment in Th is also observed at the surface of the solid, indicating the formation of a protective layer of hydrated thorium oxide, or hydroxide. Finally, the solubility product of secondary phase was determined. The values obtained are in good agreement with that of ThO2, Th(OH)(4) and ThO2, xH2O reported in the literature. (C) 2004 Elsevier B.V. All rights reserved.