Extraction of Uranium in Nitric Media with Novel Asymmetric Tetra-Alkylcarbamide.

ABSTRACT

The use of tetra-alkylcarbamides as novel ligands N,N-butyl-N',N'-hexylurea (L1 ABHU), and N,N-butyl-N',N'-pentylurea (L2 ABPU), for the solvent extraction and complexation behaviors of uranium(VI) was synthesized and investigated in this study. The effects of HNO3 and NO3- concentrations in the aqueous phase on the distribution ratio of U(VI) were examined. Under 5 mol/L HNO3 concentration, DU reached 5.02 and 4.94 respectively without third-phase formation. During the extraction, slope measurements and IR spectral analysis revealed that the U(VI) complexes are a form of UO2(NO3)2·2L for both ligands. In addition, thermodynamic studies showed that the uranium extraction reaction was a spontaneous exothermic reaction. The deep structural analysis of the complexes was realized with DFT calculation. The bond length, bond properties, and topology of the complexes were discussed in detail to analyze the extraction behavior. This study enriches the coordination chemistry of U(VI) by tetra-alkylcarbamides, which may offer new clues for the design and synthesis of novel ligands for the separation, enrichment, and recovery of uranium in the nuclear fuel cycle.