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The oxidation of U(IV) to U(VI) with molecular oxygen in acidic aqueous NaClO 4  (I=0.5 M) solutions at different temperatures was studied. It was found that the reaction kinetics is a combination of a first-order reaction and an autocatalytic reaction. The speciation of tetravalent uranium is important since it was found that the two first hydrolysed uranium(IV) species are the reactive species under the conditions studied. One problem in interpreting the results comes from the lack of thermodynamic data. However, oxidation kinetic experiments may be a method for determining stability constants for redox sensitive tetravalent actinides. The stability constants for the formation of the first two hydrolysed complexes of U(IV) are reported in this work, e.g. log  * β 1  (I = 0.5;M, T = 303.15;K)= 1.39±0.42, as compared to the literature value of -1.39±0.20.

A kinetic model for the oxidation of U(IV) to U(VI) with O 2 : Determination of stability constants via oxidation kinetic experiments