Complexation of High-Valency Mid-Actinides by a Lipophilic Schiff Base Ligand: Synthesis, Structural Characterization, and Progress toward Selective Extraction.

Separation of U, Np, and Pu from used nuclear fuel (UNF) would result in lower long-term radiotoxicity, alleviating constraints on the storage and handling of the material. The complexity of UNF requires several industrial-scale processes with multiple waste streams. A one-step solution to the group removal of the elements, U-Pu, is desirable. Here we present a possible solution to group actinide separation utilizing the unique dioxy conformation of An(V/VI) cations and demonstrate the ability of a tetradentate lipophilic Schiff base ligand (L) to yield isostructural complexes of the general formula [(AnVIO2)(L)(CH3CN)] (where An = U, Np, or Pu). Extraction of An(VI) with the ligand follows the order U > Pu > Np, likely reflecting the decreased stability of the hexavalent actinide across the series. While the results indicate a promising path toward a one-step process, further improvement in the ligand stability and control of the redox chemistry is required.

Water-soluble Schiff base-actinyl complexes and their effect on the solvent extraction of f-elements.

Conventional solvent extraction of selected f-element cations by bis(2-ethylhexyl)phosphoric acid (HDEHP) yields increased extraction from aqueous to organic solution along the series Np(v) < Cm(iii) < Eu(iii) < U(vi), with distribution ratios all within two orders of magnitude. However, in the presence of the water-soluble tetradentate Schiff base (N,N'-bis(5-sulfonatosalicylidene)-ethylenediamine or H2salenSO3), selective complexation of the two actinyl cations (Np(v) and U(vi)) resulted in an extraction order of Np(v) < U(vi) ≪ Eu(iii) < Cm(iii). The extraction of neither Cm(iii) or Eu(iii) by HDEHP are significantly impacted by the presence of the aqueous phase Schiff base. Despite observed hydrolytic decomposition of H2salenSO3 in aqueous solutions, the calculated high conditional stability constant (ß11 = 26) for the complex [UO2(salenSO3)]2- demonstrates its capacity for aqueous hold-back of U(vi). UV-visible-NIR spectroscopy of solutions prepared with a Np(vi) stock and H2salenSO3 suggest that reduction of Np(vi) to Np(v) by the ligand was rapid, resulting in a pentavalent Np complex that was substantially retained in the aqueous phase. Results from 1H NMR of aqueous solutions of H2salenSO3 with U(vi) and La(iii), Eu(iii), and Lu(iii) provides additional evidence that the ligand readily chelates U(vi), but has only weak interactions with trivalent lanthanide ions.

Rapid quantification of imidazolium-based ionic liquids by hydrophilic interaction liquid chromatography: Methodology and an investigation of the retention mechanisms.

The separation of nine N,N'-dialkylimidazolium-based ionic liquids (ILs) by an isocratic hydrophilic interaction high-performance liquid chromatographic method using an unmodified silica column was investigated. The chosen analytical conditions using a 90:10 acetonitrile-ammonium formate buffer mobile phase on a high-purity, unmodified silica column were found to be efficient, robust, and sensitive for the determination of ILs in a variety of solutions. The retention window (k' = 2-11) was narrower than that of previous methods, resulting in a 7-min runtime for the nine IL homologues. The lower limit of quantification of the method, 2-3 µmol L(-1), was significantly lower than those reported previously for HPLC-UV methods. The effects of systematically modifying the IL cation alkyl chain length, column temperature, and mobile-phase water and buffer content on solute retention were examined. Cation exchange was identified as the dominant retention mechanism for most of the solutes, with a distinct (single methylene group) transition to a dominant partitioning mode at the highest solute polarity.

Computational study of molecular structure and self-association of tri-n-butyl phosphates in n-dodecane.

Tri-n-butyl phosphate (TBP) is an important extractant used in the solvent extraction process for recovering uranium and plutonium from used nuclear fuel. An atomistic molecular dynamics study was used to understand the fundamental molecular-level behavior of extracting agents in solution. Atomistic parametrization was carried out using the AMBER force field to model the TBP molecule and n-dodecane molecule, a commonly used organic solvent. Validation of the optimized force field was accomplished through various thermophysical properties of pure TBP and pure n-dodecane in the bulk liquid phase. The mass density, dipole moment, self-diffusion coefficient, and heat of vaporization were calculated from our simulations and compared favorably with experimental values. The molecular structure of TBPs in n-dodecane at a dilute TBP concentration was examined based on radial distribution functions. 1D and 2D potential mean force studies were carried out to establish the criteria for identifying TBP aggregates. The dimerization constant of TBP in the TBP/n-dodecane mixture was also obtained and matched the experimental value.

Evaluation of solid-supported room-temperature ionic liquids containing crown ethers as media for metal ion separation and preconcentration.

Extraction chromatographic (EXC) resins incorporating an appropriate crown ether in an oxygenated organic solvent such as 1-octanol are well established as sorbents for the analytical-scale separation and preconcentration of radiostrontium from a variety of sample types. Recent solvent extraction studies employing crown ethers in various 1-alkyl-3-methylimidazolium-based (CnC1im(+)) room-temperature ionic liquids (RTILs) indicate that under certain conditions, distribution ratios (DSr) for strontium far in excess of those observed with conventional organic solvents are observed. To determine if this increase in liquid-liquid extraction efficiency will lead to improved strontium sorbents, several EXC resins and sol-gel glasses incorporating di-tert-butylcyclohexano-18-crown-6 (DtBuCH18C6) in either 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (C10C1imTf2N) or the related hydroxyalkyl-functionalized IL 1-(12-hydroxydodecyl)-3-butylimidazolium bis[(trifluoromethyl)sulfonyl]imide (C12OHC4im Tf2N) were prepared and characterized. Unexpectedly the performance of these materials was not uniformly better than that of a conventional EXC resin, an apparent result of the greater viscosity of the ionic liquids and the lower solubility of the crown ether in ILs versus conventional organic solvents.

Effect of aqueous phase anion on the mode of facilitated ion transfer into room-temperature ionic liquids.

Measurements of the partitioning of various alkali and alkaline earth cations between solutions of hydrochloric acid and a series of 1,3-dialkylimidazolium-based ionic liquids (ILs) to which a crown ether has been added have revealed substantial differences in extraction behavior versus both conventional molecular solvents (e.g., 1-octanol) under the same conditions and the same ILs when nitric acid solutions are employed as the aqueous phase. These results can be rationalized by application of a three-path model for metal ion partitioning into ILs in the presence of a neutral extractant. Additionally, the results point to a significant role for anion hydration energy in determining the balance amongst the possible modes of partitioning and strongly suggest that ion exchange involving the cationic metal complex and the cationic constituent of the ionic liquid constitutes the "default" route for metal ion extraction in IL systems incorporating a neutral extractant.

Novel tandem column method for the rapid isolation of radiostrontium from human urine.

A method has been developed for the isolation of strontium from human urine for subsequent determination in sample volumes as low as 5-20 mL. This method involves the acidification of the sample using methanesulfonic acid and its decolorization using charcoal, treatment of the filtrate with Diphonix(®) resin, and subsequent concentration of strontium on Sr resin. Data from retention model simulations provided the initial conditions which were then optimized by actual column separations. Diphonix(®) resin was shown to be effective at removing alkali metal ions from the urine matrix under conditions that retain higher valence ions. The suggested processing method provides 99% recovery of Sr(2+), a concentration factor of 50, and an expected per sample processing time of less than 1 h.