The TALSPEAK process is an established option for lanthanide/minor actinide separations using solvent extraction. In this process, selective extraction of lanthanides is achieved by contacting a water-soluble aminopolycarboxylate complexant in a concentrated carboxylic acid buffer with a liquid cation exchanging extractant in an immiscible organic diluent. Although TALSPEAK process development has been successful on several levels, studies of the detailed fundamental chemistry have revealed undesirable complex interactions between aqueous and organic solute species. These complications threaten to impair process modeling and could impact engineered operations. In the present work, results are reported describing equilibrium partitioning and phase transfer kinetics trends for trivalent lanthanide ions and americium into bis-2-ethyl(hexyl) phosphoric acid (HDEHP) or structural analog 2-ethyl(hexyl) phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) organic phases from aqueous lactate solutions containing diethylenetriamine-N,N,N′,N′′,N′′-pentaacetic acid (DTPA), triethylenetetramine-N,N,N′,N′′,N′′′,N′′′-hexaacetic acid (TTHA), or N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid (HEDTA). The undesirable partitioning of Na+, lactic acid, and water into the organic phase is greatly reduced when HEH[EHP] replaces HDEHP as the extractant. TTHA appears to offer little advantage over DTPA in conventional TALSPEAK, but both DTPA and TTHA are too strong for use in combination with HEH[EHP]. The combination of HEDTA with HEH[EHP] achieves good balance and exhibits a nearly flat pH dependence between 2.5 and 4.5, in contrast with conventional TALSPEAK. The latter combination demonstrates more predictable performance than is seen in conventional TALSPEAK, while providing acceptable americium/lanthanide separation factors. The HEDTA/HEH[EHP] combination offers the additional advantage of more rapid phase transfer kinetics for the heavier lanthanides without the need for high concentrations of a lactate buffer.

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Time-resolved fluorescence spectroscopy and Fourier transform IR spectroscopy have been applied to characterize the coordination environment of lipophilic complexes of Eu(3+) with bis(2-ethylhexyl)phosphoric acid (HDEHP) and (2-ethylhexyl)phosphonic acid mono(2-ethylhexyl) ester (HEH[EHP]) in 1,4-diisopropylbenzene (DIPB). The primary focus is on understanding the role of lactate (HL) in lanthanide partitioning into DIPB solutions of HDEHP or HEH[EHP] as it is employed in the TALSPEAK solvent extraction process for lanthanide separations from trivalent actinides. The broader purpose of this study is to characterize the changes that can occur in the coordination environment of lanthanide ions as metal-ion concentrations increase in nonpolar media. The optical spectroscopy studies reported here complement an earlier investigation of similar solutions using NMR spectroscopy and electrospray ionization mass spectrometry. Emission spectra of Eu(3+) complexes with HDEHP/HEH[EHP] demonstrate that, as long as the Eu(3+) concentration is maintained well below saturation of the organic extractant solution, the Eu(3+) coordination environment remains constant as both [HL](org) and [H(2)O](org) are increased. If the total organic-phase lanthanide concentration is increased (by extraction of moderate amounts of La(3+)), the (5)D(0) → (7)F(1) transition singlet splits into a doublet with a notable increase in the intensity of both (5)D(0) → (7)F(1) and (5)D(0) → (7)F(2) electronic transitions. The increased multiplicity in the emission spectra indicates that Eu(3+) ions are present in multiple coordination environments. The increased emission intensity of the 614 nm band implies an overall reduction in symmetry of the extracted Eu(3+) complex in the presence of macroscopic La(3+). Although [H(2)O](org) increases to above 1 M at high [HL](tot), this water is not associated with the Eu(3+) metal center. IR spectroscopy results confirm a direct Ln(3+)-lactate interaction at high concentrations of lanthanide and lactate in the extractant phase. At low organic-phase lanthanide concentrations, the predominant complex is almost certainly the well-known Ln(DEHP·HDEHP)(3). As lanthanide concentrations in the organic phase increase, mixed-ligand complexes with the general stoichiometry Ln(L)(n)(DEHP)(3-n) or Ln(L)(n)(DEHP·HDEHP)(3-n) become the dominant species.

The novel metal chelator N-2-(pyridylmethyl)diethylenetriamine-N,N',N″,N″-tetraacetic acid (DTTA-PyM) was designed to replace a single oxygen-donor acetate group of the well-known aminopolycarboxylate complexant diethylenetriamine-N,N,N',N″,N″-pentaacetic acid (DTPA) with a nitrogen-donor 2-pyridylmethyl. Potentiometric, spectroscopic, computational, and radioisotope distribution methods show distinct differences for the 4f and 5f coordination environments and enhanced actinide binding due to the nitrogen-bearing heterocyclic moiety. The Am, Cm, and Ln complexation studies for DTTA-PyM reveal an enhanced preference, relative to DTPA, for trivalent actinide binding. Fluorescence studies indicate no changes to the octadentate coordination of trivalent curium, while evidence of heptadentate complexation of trivalent europium is found in mixtures containing EuHL complexes at the same aqueous acidity. The denticity change observed for Eu suggests that complex protonation occurs on the pyridyl nitrogen. Formation of the CmHL complex is likely due to the protonation of an available carboxylate group because the carbonyl oxygen can maintain octadentate coordination through a rotation. The observed suppressed protonation of the pyridyl nitrogen in the curium complexes may be attributed to stronger trivalent actinide binding by DTTA-PyM. Density functional theory calculations indicate that added stabilization of the actinide complexes with DTTA-PyM may originate from π-back-bonding interactions between singly occupied 5f orbitals of Am and the pyridyl nitrogen. The differences between the stabilities of trivalent actinide chelates (Am, Cm) and trivalent lanthanide chelates (La-Lu) are observed in liquid-liquid extraction systems, yielding unprecedented 4f/5f differentiation when using DTTA-PyM as an aqueous holdback reagent. In addition, the enhanced nitrogen-donor softness of the new DTTA-PyM chelator was perturbed by adding a fluorine onto the pyridine group. The comparative characterization of N-(3-fluoro-2-pyridylmethyl)diethylenetriamine-N,N',N″,N″-tetraacetic acid (DTTA-3-F-PyM) showed subdued 4f/5f differentiation due to the presence of this electron-withdrawing group.