Uranium solution-mineral equilibria at low temperatures with applications to sedimentary ore deposits

I. Introduction. Background. Focus of the review. Review procedure and results. The NEA-TDB data base system. Presentation of the selected data. II. Standards and Conventions. Symbols, terminology and nomenclature. Units and conversion factors. Standard and reference conditions. Fundamental physical constants. III. Selected Uranium Data. IV. Selected Auxiliary Data. V. Discussion of Data Selection. Elemental uranium. Aqua ions. Oxide, hydride and hydroxide species. VI. Discussion of Auxiliary Data Selection. Reference list. Authors list. Formula list. Discussion of selected references. Ionic strength corrections. Assigned uncertainties. The estimation of entropies.

Chemical thermodynamics of uranium

C-13 and O-17 NMR and Raman spectroscopies were used to monitor the fractions of UO2(CO3)(3)(4-) (1) and (UO2)(3)(CO3)(6)(6-) (2) in aqueous carbonate solutions as a function of pH, ionic strength, carbonate concentration, uranium concentration, and temperature. The multinuclear NMR and Raman data are consistent with the formation of (UO2)(3)(CO3)(6)(6-). The pH dependence of the C-13 NMR spectra was used to determine the equilibrium constant for the reaction 3UO(2)(CO3)(3)(4-) + 3H(+) reversible arrow (UO2)(3)(CO3)(6)(6-) + 3HCO(3)(-), log K = 18.1(+/- 0.5) at I-m = 2.5 m and 25 degrees C, and corresponds to log beta(36) = 55.6(+/- 0.5) for the reaction 3UO(2)(2+) + 6CO(3)(2-) reversible arrow (UO2)(3)(CO3)(6)(6-) under the same conditions. Raman spectra showed the uranyl nu(1) stretching band at 831.6 cm(-1) for monomeric 1 and at 812.5 cm(-1) for trimeric (UO2)(3)(CO3)(6)(6-) (2). EXAFS data from solid [C(NH2)(3)](6)[(UO2)(3)(CO3)(6)] and a solution of (UO2)(3)(CO3)(6)(6-) suggest that the same uranium species is present in both the solid and solution states. Fourier transforms of the EXAFS spectra of both solid and solution samples revealed five well-resolved peaks corresponding to nearly identical near-neighbor distances for solid and solution- samples of 2. Fitting of these peaks yields U-O(uranyl) = 1.79, U-O(carbonate) = 2.45, U- -C = 2.90, U- -O(terminal carbonate) = 4.16, and U- -U = 4.91 Angstrom for the solid and similar distances for the solution sample. A peak at 4.75 Angstrom in both Fourier transforms (uncorrected for phase shift) corresponds to a U- -U interaction at 4.91 Angstrom, a conclusion which is supported by the absence of this peak in the Fourier transform of the crystalline monomeric K-4[UO2(CO3)(3)] Multiple scattering along the uranyl vector is believed to play a significant role in the EXAFS of all three systems. The EXAFS data are consistent with the trimeric uranyl carbonate species indicated by NMR spectroscopy. Single crystals of [C(NH2)(3)](6)[(UO2)(3)(CO3)(6)]. 6.5H(2)O were obtained from a solution that contained stoichiometric amounts of uranyl nitrate and guanidinium carbonate and an excess of guanidinium nitrate at pH 6.5 under a CO2 atmosphere. The solid state molecular structure of [C(NH2)(3)](6)[(UO2)(3)(CO3)6]. 6.5H(2)O contains a planar D-3h trimetallic (UO2)(3)(CO3)(6)(6-) anion, the structure that Aberg and co-workers originally proposed for the trimeric solution species. The trimetallic anion contains three uranium atoms and all six carbonate ligands in the molecular plane with three uranyl oxygen atoms above and three below the plane. Uranyl U=O distances average 1.78(1) Angstrom, while U-O distances to the carbonate oxygen atoms average 2.41(1) Angstrom for terminal and 2.48(1) Angstrom for bridging ligands. Particularly significant is the average nonbonding U- -U distance of 4.97 Angstrom which compares favorably to the 4.91 Angstrom distance seen in the EXAFS analysis. The molecule crystallizes in the triclinic space group P ($) over bar 1, with a = 6.941(2) Angstrom, b = 14.488(2) Angstrom, c = 22.374(2) Angstrom, alpha = 95.63(2)degrees, beta = 98.47(2)degrees, gamma = 101.88(2)degrees, R = 0.0555, R(w), = 0.0607, V = 2158.5 Angstrom(3),d(cal), = 2.551 g cm(-3), and Z = 2.

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Multinuclear nmr, raman, exafs, and x-ray-diffraction studies of uranyl carbonate complexes in near-neutral aqueous-solution - x-ray structure of c(nh2)(3) (6) (uo2)(3)(co3)(6) center-dot-6.5h(2)o

Electrochemical, complexation, and electronic properties of uranyl(VI) and -(V) carbonato complexes in an aqueous Na2CO3 solution have been investigated to define the appropriate conditions for preparing pure uranyl(V) samples and to understand the difference in coordination character between UO22+ and UO2+. Cyclic voltammetry using three different working electrodes of platinum, gold, and glassy carbon has suggested that the electrochemical reaction of uranyl(VI) carbonate species proceeds quasi-reversibly. Electrolysis of UO22+ has been performed in Na2CO3 solutions of more than 0.8 M with a limited pH range of 11.7 < pH < 12.0 using a platinum mesh electrode. It produces a high purity of the uranyl(V) carbonate solution, which has been confirmed to be stable for at least 2 weeks in a sealed glass cuvette. Extended X-ray absorption fine structure (EXAFS) measurements revealed the structural arrangement of uranyl(VI) and -(V) tricarbonato complexes, [UO2(CO3)3]n- [n = 4 for uranyl(VI), 5 for uranyl(V)]. ...

J.P Scanlan

Papers

Equilibria in uranyl carbonate systems—I: The overall stability constant of UO2(CO3)34−