The coordination of the trivalent 4f ions, Ln = La3+, Dy3+, and Lu3+, with neutral and acidic organophosphorus reagents, both individually and combined, was studied by use of X-ray absorption spectroscopy. These studies provide metrical information about the interatomic interactions between these cations and the ligands tri-n-butyl phosphate (TBP) and di-n-butyl phosphoric acid (HDBP), whose behavior are of practical importance to chemical separation processes that are currently used on an industrial scale. Previous studies have suggested the existence of complexes involving a mixture of ligands, accounting for extraction synergy. Through systematic variation of the aqueous phase acidity and extractant concentration and combination, we have found that complexes with Ln and TBP : HDBP at any mixture and HDBP alone involve direct Ln–O interactions involving 6 oxygen atoms and distant Ln–P interactions involving on average 3–5 phosphorus atoms per Ln ion. It was also found that Ln complexes formed by TBP alone seem to favor eight oxygen coordination, though we were unable to obtain metrical results regarding the distant Ln–P interactions due to the low signal attributed to a lower concentration of Ln ions in the organic phases. Our study does not support the existence of mixed Ln–TBP–HDBP complexes but, rather, indicates that the lanthanides are extracted as either Ln–HDBP complexes or Ln–TBP complexes and that these complexes exist in different ratios depending on the conditions of the extraction system. This fundamental structural information offers insight into the solvent extraction processes that are taking place and are of particular importance to issues arising from the separation and disposal of radioactive materials from used nuclear fuel.

Tri-n-butyl phosphate (TBP), a representative of neutral organophosphorous ligands, is an important extractant used in the solvent extraction process for the recovery of uranium and plutonium from spent nuclear fuel. Microscopic pictures of TBP isomerism and its behavior in n-dodecane diluent were investigated utilizing MD simulations with previously optimized force field parameters for TBP and n-dodecane. Potential mean force (PMF) calculations on a single TBP molecule show seven probable TBP isomers. Radial distribution functions (RDFs) of TBP suggest the existence of TBP trimers at high TBP concentrations in addition to dimers. 2D PMF calculations were performed to determine the angle and distance criteria for TBP trimers. The dimerization and trimerization constants of TBP in n-dodecane were obtained and match our own experimental values using the FTIR technique. The new insights into the conformational behaviors of the TBP molecule as a monomer and as part of an aggregate could greatly aid in the understanding of the complexation between TBP and metal ions in a solvent extraction system.

Tri-n-butyl phosphate (TBP), a representative of neutral organophosphorous metal-ion-extracting reagents, is an important ligand used in solvent extraction processes for the recovery of uranium and plutonium from spent nuclear fuel, as well as other non-nuclear applications. Ligand–ligand and organic solvent–ligand interactions play an important role in these processes. The self-association behavior of TBP in various alkane diluents of different chain lengths (8, 12, and 16 carbons) and a branched alkane (iso-octane) was investigated by Fourier transform infrared spectroscopic measurements. By careful deconvolution of the spectra into multiple peaks, our results indicate that TBP self-associates to form not only dimers, as previous studies showed, but also trimers in the practical concentration range. Using a mathematical fitting procedure, the dimerization and trimerization constants were determined. As expected, these equilibrium constants are dependent on the solvent used. As the alkane chain for linear hydrocarbon solvents becomes longer, dimerization decreases whereas trimerization increases. For the more branched hydrocarbon, we observe a significantly higher dimerization constant. These effects are most likely due to the intermolecular van der Waals interactions between the butyl tails of each TBP molecule and the diluent hydrocarbon chain as all solvents in this study are relatively nonpolar.

The extraction of lanthanides using a combination of tri-n-butyl phosphate (TBP) and dibutyl phosphoric acid (HDBP) was found to display characteristics of microemulsion aggregates, which may be related to synergistic effects. We studied the extraction of lanthanides and actinides, in our case dysprosium, europium, and uranium, with TBP and HDBP in conjunction with 2D fluorescence spectrometry. The results presented indicate that the coordination environment around the metal ion in the organic phase changes as the ratio between TBP and HDBP changes. This suggests the presence of mixed complexes of M:TBP:HDBP but does not rule out the presence of reverse micelles.

Radioactive lanthanides have become an important imaging, diagnostic and therapeutic tool in the medical field. The objective of our research was to investigate the feasibility of producing radioactive lanthanides with high specific activity in a small-scale research reactor using the Szilard–Chalmers method. The results indicate that the activated nuclides recoil out of the target after neutron capture and we obtain enrichment of the radionuclide compared to the bulk irradiation. These first attempts, result in enrichment factors and yields that are low but indicates a possibility of using this technique if the method is further optimized.

The water soluble tetradentate Schiff base, N,N′-bis(5-sulfonatosalicylidene)-diaminoethane (H2salen-SO3), will readily coordinate to the uranyl(VI) cation, but not to the same extent to trivalent lanthanide cations. This allows for the reversal of conventional solvent extraction properties and opens the possibility for novel separation processes.

The macroscopic phase behaviors of a solvent system containing two extractants, tri-n-butyl phosphate (TBP) and di-n-butyl phosphoric acid (HDBP) in n-dodecane, were investigated through use of liquid–liquid extraction and small-angle X-ray scattering (SAXS) experiments. Five organic solutions, each containing a total extractant concentration (TBP + HDBP) of 1 M in varying molar ratios (0, 0.25, 0.5, 0.75, and 1.0 [TBP]:[TBP + HDBP]), were contacted with 0.2 M HNO3 aqueous solutions without and with dysprosium(III) at a concentration of 10–4 M. An enhancement of the extraction of Dy3+—due to effects of synergism arising from the binary combination of extractants—was observed. SAXS data were collected for all solution compositions from 0 to 1 mol-fraction end ratios of TBP after contact with the acidic aqueous solutions both in the absence and presence of Dy as well as for the organic phases before aqueous contact. In the precontacted solutions, no notable changes in the SAXS data were observed upon combining the extractants so that the scattering intensity (I) measured at zero angle (Q = 0 Å–1)—parameter I(0)—the experimental radius of gyration (Rg), and the maximum linear extent (MLE) of the extractant aggregates were arithmetic averages of the two end members, 1 M HDBP, on the one hand, and 1 M TBP, on the other. In contrast, after contact with the aqueous phases with and without Dy3+, a significant reorganization occurs with larger aggregates apparent in the extractant mixtures and smaller in the two end member solutions. In particular, the maximum values of the metrical parameters (I(0), Rg, and MLE) correlate with the apparent optimal synergistic extraction mole ratio of 0.25. The SAXS data were further analyzed using the recently developed generalized indirect Fourier transformation (GIFT) method to provide pair-distance distribution functions with real-space information on aggregate morphology. Before aqueous contact, the organic phases show a systematically varying response from globular-like reverse micelles in the case of 1 M TBP to rod-shaped architectures in the case of 1 M HDBP. After aqueous contact, the aggregate morphologies of the mixed extractant systems are not simple linear combinations of those for the two end members. Rather, they have larger and more elongated structures, showing sharp discontinuities in the metrics of the aggregate entities that are coincident with the synergistic extraction mixture for Dy3+. The results in this initial study suggest a supramolecular, micellization aspect to synergism that remains underexplored and warrants further investigation, especially as it concerns the contemporary relevance to decades-old process chemistry and practices for high throughput separations systems.

This work characterizes the non-ideal behavior of the solvent extraction agent di-(2-ethylhexyl) phosphoric acid (HDEHP), constituting one piece of an effort to develop increasingly accurate models of advanced fuel separation processes such as TALSPEAK. Robust models are particularly important for processing high-level radioactive material in order to minimize the generation of secondary waste and to ensure reliable process control. Here, vapor pressure osmometry (VPO) data on binary solutions of HDEHP in toluene, dodecane, or cyclooctane yields the activity coefficients for each component after analysis. Initially, diluent activity data is obtained using the VPO results and then modeled using Scatchard-Hildebrand theory to provide the activity coefficients for HDEHP.

Reagents used in chemical separation processes for used nuclear fuel are susceptible to radiolysis. Here we investigate the 10B(n,α)7Li reaction for inducing high linear energy transfer (LET) radiolysis. A solution of tributyl phosphate (TBP) in n-dodecane, representing the PUREX solvent, was irradiated by gamma rays from a137Cs source and by high LET particles from the 10B(n,α)7Li reaction in the UC Irvine TRIGA reactor. TBP degradation and Dibutyl phosphate (DBP) formation were quantified by gas chromatography. Our data show a significantly larger formation of DBP in the presence of gamma radiation compared to high LET radiation.

The water soluble tetradentate Schiff base, N,N′-bis(5-sulfonatosalicylidene)-diaminoethane (H2salen-SO3), will readily coordinate to the uranyl(VI) cation, but not to the same extent to trivalent lanthanide cations. This allows for the reversal of conventional solvent extraction properties and opens the possibility for novel separation processes.

The coordination of the trivalent 4f ions, Ln = La3+, Dy3+, and Lu3+, with neutral and acidic organophosphorus reagents, both individually and combined, was studied by use of X-ray absorption spectroscopy. These studies provide metrical information about the interatomic interactions between these cations and the ligands tri-n-butyl phosphate (TBP) and di-n-butyl phosphoric acid (HDBP), whose behavior are of practical importance to chemical separation processes that are currently used on an industrial scale. Previous studies have suggested the existence of complexes involving a mixture of ligands, accounting for extraction synergy. Through systematic variation of the aqueous phase acidity and extractant concentration and combination, we have found that complexes with Ln and TBP:HDBP at any mixture and HDBP alone involve direct Ln–O interactions involving 6 oxygen atoms and distant Ln–P interactions involving on average 3–5 phosphorus atoms per Ln ion. It was also found that Ln complexes formed by TBP alone seem to favor eight oxygen coordination, though we were unable to obtain metrical results regarding the distant Ln–P interactions due to the low signal attributed to a lower concentration of Ln ions in the organic phases. Our study does not support the existence of mixed Ln–TBP–HDBP complexes but, rather, indicates that the lanthanides are extracted as either Ln–HDBP complexes or Ln–TBP complexes and that these complexes exist in different ratios depending on the conditions of the extraction system. This fundamental structural information offers insight into the solvent extraction processes that are taking place and are of particular importance to issues arising from the separation and disposal of radioactive materials from used nuclear fuel.