The Apparent Overall Oxidation Kinetics of Uranium (IV) By Oxygen Gas in Aqueous Perchloric Acid Solutions

The kinetics of the oxidation of uranium(IV) by oxygen gas in aqueous systems is dependent on acid concentration, oxygen partial pressure, and temperature. In order to better understand the relationship between these variables and the speed of oxidation, a series of experiments have been conducted where each parameter has been varied in turn. Data were collected continuously using UVVis spectroscopy, allowing for a detailed examination of the reaction rate over the course of each experiment. The data fit an overall apparent rate law that is 1.5order in uranium(IV), -2order in H+, first order in oxygen, and unaffected by uranium(VI). This relationship does not appear to hold for solutions with <0.2 mol/L initial acid, where a different kinetic mechanism appears to be dominant.