Enhancing f-Element Separations with ADAAM-EH: The Impact of Phase Modifiers and a DGA Aqueous Complexant

Abstract

Recent investigations have used a 2-ethylhexyl diamide amine (ADAAM-EH) for Am/Cm separations in combination with N,N,N′,N′-tetraethyldiglycolamide as an aqueous complexant to achieve an unprecedented separation factor of 41. The aim of this research effort is to understand the speciation of trivalent lanthanide (Ln) and actinide (An) ions in the organic phase of an ADAAM-EH extraction system, both with and without phase modifiers (PM) (1-octanol and tri-n-butyl phosphate (TBP)). Leveraging spectroscopic techniques in combination with distribution ratio measurements provides an understanding of organic phase f-element ligand complexation. In the absence of PM, Ln is extracted in a stoichiometric 1:1 [M(ADAAM-EH) 1 (NO 3 ) x (H 2 O) 1 ](NO 3 ) 3−x complex. The addition of 1-octanol at 20 vol % results in multiple species present. One of the species is the same as the no PM case, and the other species results in an increased −OH coordination to the inner sphere, potentially displacing some NO 3 . In the case of TBP, increasing concentration results in additional red-shifted bands in the UV− visible spectra, suggesting the complexation of additional ligands of either ADAAM-EH or TBP. The new system knowledge obtained by and spectroscopic experiments will provide benchmarking information for computational studies of the inner-and outer-sphere coordination environments of f-element cations and insights into ADAAM-EH adduct formation with PM, like 1octanol and TBP.