THE HYDROLYSIS OF DIOXOURANIUM(VI) INVESTIGATED USING EXAFS AND 17O-NMR

The hydrolysis of uranium(VI) has been the subject of extensive studies since 50 years and is relatively well-known under acidic and near-neutral conditions. A comprehensive discussion and review of the thermodynamic data is published in [1]. At total uranium(VI) concentrations above 10-4 M and in a slightly acidic (pH: 2 to 5) aqueous media, polymeric cations [e.g., (UO2)2(OH)22+, (UO2)3(OH)5+] are the major species. Structure investigations of such hydrolysis products of uranyl in solutions at environmental relevant uranium concentrations are rare [2].
We investigated the structure of dioxouranium(VI) as a function of pH at different (CH3)4N-OH concentrations with the aid of U LIII EXAFS. Polynuclear hydroxo species were identified by an U-U interaction at 3.808 Å at pH = 4.1.
The speciation of uranium(VI) in the neutral and slightly alkaline pH region is dominated by the precipitation of schoepite. The EXAFS measurements performed at the precipitate formed at pH = 7 showed a schoepite like structure.
The investigation of uranyl hydroxide complexes in alkaline solutions is challenging due to the formation of highly insoluble alkali metal mono- and polyuranate salts. Mononuclear species, UO2(OH)3- and UO2(OH)42-, have been identified mainly by solubility experiments [3] to be the major uranium(VI) complexes at pH > 12. Several attempts have been made to characterize the structure of uranyl complexes under highly alkaline conditions using potentiometric titrations, EXAFS, NMR techniques and quantum chemical methods [4-6]. In solution at high pH [0.5M (CH3)4N-OH], our EXAFS data are consistent with the formation of a monomeric four coordinated uranium(VI) hydroxide complex UO2(OH)42- of octahedral geometry. The first shell contains two O atoms with a U=O distance of 1.830 Å, and four O atoms were identified at a U-Oeq distance of 2.266 Å.
We have extended a previous study [6] by determining the structure of uranium(VI) at (CH3)4N-OH concentration below 1 M over a broad pH-range. The objective was to decide if binary polynuclear hydroxo species also occur in (CH3)4N-OH media. Additional information is provided by comparing the EXAFS results with new 17O-NMR measurements. In strong alkaline solutions [> 1 M (CH3)4N)-OH], 17O-NMR spectra indicate the presence of two species, presumably UO2(OH)42- and UO2(OH)53-, which are in rapid equilibrium with one another at 268 K in aqueous solution. New EXAFS and 17O-NMR data will be presented.

References
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