Synergistic chemistry of U(VI), transition metal, and lanthanide(III) complexes in alkaline carbonate-peroxide solutions

INOR 187

George S. Goff, georgeg@lanl.gov1, Lia F. Brodnax, lbrodnax@lanl.gov1, Michael R. Cisneros, mcisneros@lanl.gov2, Felicia L. Taw, ftaw@lanl.gov1, Kevin S. Williamson2, and Wolfgang Runde1. (1) Chemistry Division, Los Alamos National Laboratory, Mailstop J514, Los Alamos, NM 87545, (2) Chemistry Division, Los Alamos National Lab, Mailstop J514, Los Alamos, NM 87545
Differences in the solubility of transition metals (TM), lanthanides (Ln), and uranium(VI) compounds in alkaline carbonate media can be used to develop a new alkaline-based separation process for spent nuclear fuel reprocessing. Hydrogen peroxide, used to dissolve UO2 in carbonate media, readily forms multiple mixed-ligand U(VI)-peroxo-carbonato complexes in solution. These complexes exhibit significantly higher solubility than the limiting binary UO2(CO3)34- species. The solubility of Ln(III) and TM is altered significantly upon the addition of H2O2 due to the formation of insoluble mixed peroxo-carbonato complexes. Mixtures of U(VI)-Ln(III) or U(VI)-TM in carbonate solutions show surprising behavior: Ln(III) and TM solubility increases in the presence of U(VI), with and without H2O2 , and H2O2 preferentially complexes U(VI) over Ln(III). We will present the complex and dynamic chemistry of U(VI), TM, and Ln(III) in H2O2 containing carbonate solutions , including structural characterization, thermodynamic parameters, solution speciation, and synergistic phenomena in multi-metal systems.
 

Chemistry of Lanthanides and Actinides
7:00 PM-10:00 PM, Sunday, August 19, 2007 BCEC -- Exhibit Hall - B2, Poster

Sci-Mix
8:00 PM-10:00 PM, Monday, August 20, 2007 BCEC -- Exhibit Hall - B2, Sci-Mix

Division of Inorganic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007