Uranium(VI) chemistry in strong alkaline solution: speciation and oxygen exchange mechanism.

The mechanism by which oxygen bound in UO2(2+) exchanges with that from water under strong alkaline conditions remains a subject of controversy. Two recent NMR studies independently revealed that the key intermediate species is a binuclear uranyl(VI) hydroxide, presumably of the stoichiometry [(UO2(OH)4(2-))(UO2(OH)5(3-))]. The presence of UO2(OH)5(3-) in highly alkaline solution was postulated in earlier experimental studies, yet the species has been little characterized. Quantum-chemical calculations (DFT and MP2) show that hydrolysis of UO2(OH)4(2-) yields UO3(OH)3(3-) preferentially over UO2(OH)5(3-). X-ray absorption spectroscopy was used to study the uranium(VI) speciation in a highly alkaline solution supporting the existence of a species with three U-O bonds, as expected for UO3(OH)3(3-). Therefore, we explored the oxygen exchange pathway through the binuclear adduct [(UO2(OH)4(2-))(UO3(OH)3(3-))] by quantum-chemical calculations. Assuming that the rate-dominating step is proton transfer between the oxygen atoms, the activation Gibbs energy for the intramolecular proton transfer within [(UO2(OH)4(2-))(UO3(OH)3(3-))] at the B3LYP level was estimated to be 64.7 kJ mol(-1). This value is in good agreement with the activation energy for "yl"-oxygen exchange in [(UO2(OH)4(2-))(UO2(OH)5(3-))] obtained from experiment by Szabó and Grenthe (Inorg. Chem. 2010, 49, 4928-4933), which is 60.8 ± 2.4 kJ mol(-1). Both the presence of UO3(OH)3(3-) and the scenario of an "yl"-oxygen exchange through a binuclear species in strong alkaline solution are supported by the present study.