Abstract
Separation of the trivalent actinides from the trivalent lanthanides relevant to used nuclear fuel reprocessing remains still a challenging task. One of the options currently being investigated is the combination of two extraction processes, TRUEX and TALSPEAK. However, the two extractants used in the individual processes, when combined, result in a system with complex extraction behavior. To better understand the interactions in this combined extraction system, FT-IR spectroscopy was used in combination with small-scale solvent extraction tests. The data indicate that in the presence of CMPO, HDEHP dimer cleaves and interacts with CMPO through hydrogen bonding between POH and phosphoryl group of CMPO. The formation of a new HDEHP-CMPO adduct (log β = 3.4) at [HDEHP] > [CMPO] significantly lowers the concentration of free CMPO available for complexation with metal. The distribution ratios of Eu(III) decrease significantly with increasing nitric acid concentration and point to the acidic properties of this mixed extractant. The data presented suggest that several species containing HDEHP-CMPO adduct, HDEHP, and nitrate are formed upon extraction of Eu(III) by the mixture of HDEHP and CMPO.
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