title: Hydrolysis of uranyl(VI) in acidic and basic aqueous solutions using a noncomplexing organic base: a multivariate spectroscopic and statistical study.
abstract: In the field of actinide aqueous chemistry, this work aims to resolve some controversy about uranyl(VI) hydroxide species present in basic aqueous solutions. We revisit the Raman, IR, and UV-visible spectra with two new approaches. First, Raman, IR and UV data were recorded systematically from aqueous solutions with the noncomplexing electrolyte (C(2)H(5))(4)NNO(3) at 25 °C and 0.1 MPa ([U(total)] = 0.005-0.105 M) in H(2)O and D(2)O over a wide range of -log mH(D)(+) between 2.92 and 14.50. Second, vibrational spectra (IR and Raman) of basic solutions in H(2)O and D(2)O were analyzed using the Bayesian Positive Source Separation method to estimate pure spectra of individual species. In D(2)O solutions, the new spectroscopic data showed the occurrence of the same species as those in H(2)O. As observed for the wavenumber of the symmetric stretching mode, the wavenumber characteristic of the O═U═O antisymmetric stretching mode decreases as the number of OH(D)(-) ligands increases. These kinds of data, completed by (1) analysis of the signal widths, (2) persistence of the apparent exclusion rule between IR and Raman spectra of the uranyl species stretching modes, and (3) interpretation of the absorption UV-visible spectra, allow discussion of the chemistry, structures, and polynuclearity of uranyl(VI) species. In moderate basic solutions, the presence of two trimers is suggested. In highly basic solutions ([OH(-)] ≈ 3 M), the two monomers UO(2)(OH)(4)(2-) and UO(2)(OH)(5)(3-) are confirmed to be in good agreement with earlier EXAFS and NMR results. The occurrence of the UO(2)(OH)(6)(4-) monomer is also suggested from the more basic solutions investigated.
authors.affiliation: Laboratoire de Chimie Physique et Microbiologie pour l'Environnement (LCPME), UMR 7564, CNRS, Nancy-Université, Villers-lès-Nancy, France. fabienne.quiles@lcpme.cnrs-nancy.fr
authors.forename: Fabienne
authors.initials: F
authors.lastname: Quilès
authors.forename: Chinh
authors.initials: C
authors.lastname: Nguyen-Trung
authors.forename: Cédric
authors.initials: C
authors.lastname: Carteret
authors.forename: Bernard
authors.initials: B
authors.lastname: Humbert
mesh_terms: D006868:Hydrolysis; D012996:Solutions; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D013059:Spectrum Analysis, Raman; D017974:Uranium Compounds / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D012996:Solutions; D017974:Uranium Compounds; D014867:Water