STUDIES OF THE KINETICS AND MECHANISM OF THE OXIDATION OF URANIUM BY DRY AND MOIST AIR - A MODEL FOR DETERMINING THE OXIDATION RATE OVER A WIDE-RANGE OF TEMPERATURES AND WATER-VAPOR PRESSURES

The rate of oxidation of uranium metal by moist air has been measured at temperatures from 115 to 350-degrees-C and water vapour pressures from 0 to 47 kPa (350 Torr). From this and from previously reported data, a model has been developed which allows the rate of uranium oxidation to be calculated at any particular combination of temperature and water vapour pressure of interest, in the range 0-350-degrees-C and 0-101.3 kPa (760 Torr). The model is based on the assumption that the surface concentration of water determines the rate of reaction and that the adsorption of water onto the oxide follows a Langmuir type isotherm. Theoretical plots of rate as a function of water vapour pressure and Arrhenius plots derived from the model have been shown to be in good agreement with experimental data. The model assumes separate contributions to the overall observed rate from oxygen and water vapour. Surface studies have been carried out using SIMS (secondary ion mass spectrometry). Depth profiling of the oxide produced by isotopically labelled reagents (O-18(2) and (H2O)-O-18, has shown that oxygen from both reactants is incorporated into the oxide layer in the ratio predicted by the kinetic model. This supports a mechanism in which oxygen and water vapour produce separate diffusing species (possibly O2- and OH- ).