Abstract
N,N′‐dimethyl‐N,N′‐dioctylhexylethoxymalonamide, DMDOHEMA, and di‐n‐hexylphosphoric acid, HDHP, are the extractants of reference for the French DIAMEX–SANEX process for the separation of trivalent actinide ions from the lanthanide ions. In this work, the extraction of Eu3+ and Am3+ by the two extractants, alone or in mixtures, has been investigated under a variety of experimental conditions. The two cations are extracted by HDHP as the M(DHP · HDHP)3 complexes with an Eu/Am separation factor of ∼10. With DMDOHEMA, Eu3+ and Am3+ are extracted as the M(NO3)3(DMDOHEMA)2 disolvate species with an Am/Eu separation factor of ∼2. The metal distribution ratios measured with a mixture of the two reagents indicated that almost all lanthanides are extracted equally well. The extraction of Eu3+ and Am3+ by HDHP‐DMDOHEMA mixtures exhibits a change of extraction mechanism and a reversal of selectivity taking place at ∼1 M HNO3 in the aqueous phase. Below this aqueous acidity, HDHP dominates the metal extraction by the mixture, whereas DMDOHEMA is the predominant extractant at higher aqueous acidities. Some measurements indicated apparent modest antagonism between the two extractants in the extraction of Eu3+ and synergism in the extraction of Am3+. These data were interpreted as resulting from the formation in the organic phase of mixed HDHP‐DMDOHEMA species containing two HDHP and five DMDOHEMA molecules.
Acknowledgments
This work was supported by the U. S. Department of Energy, Office of Basic Energy Science, Division of Chemical Sciences, Biosciences, and Geosciences, under contract No W‐31‐109‐ENG‐38 (for the part performed at the Chemistry Division of Argonne National Laboratory); and by the CEA, DRCP/SCPS, for the part performed at Marcoule. This collaboration was realized in the framework of the CEA‐DOE agreement (C5096).
Notes
The submitted manuscript has been created by the University of Chicago as Operator of Argonne National Laboratory (“Argonne”) under Contract No. W‐31‐109‐ENG‐38 with the U.S. Department of Energy. The U.S. Government retains for itself, and others acting on its behalf, a paid‐up, nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government.