Speciation of Technetium Dibutylphosphate in the Third Phase Formed in the TBP/HNO3 Solvent Extraction System.

The speciation of technetium in the nitric acid/dibutylphosphoric acid (HDBP)-n-dodecane system was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy and theoretical methods. Tetravalent technetium, produced by the hydrazine reduction of TcO4- in 3 M HNO3, was extracted by HDBP in n-dodecane (30% by volume). During extraction, the splitting of the organic phase into a heavy phase and a light phase was observed. EXAFS analysis is consistent with the presence of Tc(NO3)3(DBP)(HDBP)2 in the light phase and Tc(NO3)2(DBP)2(HDBP)2 in the heavy phase. Density functional theory calculations at the B3LYP/6-31G* level confirm the stability of the proposed species and indicate that stereoisomers -mer- and fac-Tc(NO3)3(DBP)(HDBP)2 for the light phase and cis- and trans-Tc(NO3)2(DBP)2(HDBP)2 for the heavy phase] could coexist in the system (in the n-dodecane solution). Mechanisms of formation of Tc(NO3)3(DBP)(HDBP)2 and Tc(NO3)2(DBP)2(HDBP)2 are proposed.

Structural Investigation of Technetium Dibutylphosphate Species Using X-ray Absorption Fine Structure Spectroscopy.

The speciation of Tc after the extraction of Tc(IV) from H2O and 1 M HNO3 by dibutylphosphoric acid (HDBP) in dodecane has been studied by X-ray absorption fine structure (XAFS) spectroscopy. Results show the formation of dimeric species with Tc2O2 and Tc2O units, and the formulas [Tc2O2(DBP·HDBP)4] (1) and [Tc2O(NO3)2(DBP)2(DBP·HDBP)2] (2) were, respectively, proposed for the species extracted from H2O and 1 M HNO3. The interatomic Tc-Tc distances found in the Tc2O2 and Tc2O units [2.55(3) and 3.57(4) Å, respectively] are similar to the ones found in Tc(IV) dinuclear species. It is likely that the speciation of Tc(IV) in dodecane is due to the extraction of a species with a Tc2O unit for (2) and to the redissolution of a Tc(IV)-DBP solid for (1). The XAFS results for (1) and (2) were compared to that obtained for the extraction of Tc(IV) with TBP/HDBP/dodecane from 0.5 M HNO3, (3) which highlight the formation of Tc mononuclear nitrate species {i.e., [Tc(NO3)3(DBP)] or [Tc(NO3)2(DBP·HDBP)]}. These results confirm the importance of the preparation and speciation of the Tc(IV) aqueous solutions prior to extraction and how much this influences and drives the final Tc speciation in organic extraction. These studies outline the complexity of Tc separation chemistry and provide insights into the behavior of Tc during the reprocessing of used nuclear fuel.

Structure Activity Relationship Approach toward the Improved Separation of Rare-Earth Elements Using Diglycolamides.

The separation of adjacent lanthanides continues to be a challenge worldwide because of the similar physical and chemical properties of these elements and a necessity to advance the use of clean-energy applications. Herein, a systematic structure-performance relationship approach toward understanding the effect of N-alkyl group characteristics in diglycolamides (DGAs) on the separation of lanthanides(III) from a hydrochloric acid medium is presented. In addition to the three most extensively studied DGA complexants [N,N,N',N'-tetra(n-octyl)diglycolamide, TODGA; N,N,N',N'-tetra(2-ethylhexyl)diglycolamide, TEHDGA; N,N'-dimethyl-N,N'-di(n-octyl)diglycolamide, DMDODGA], 12 new extracting agents with varying substitution patterns were designed to study the interplay of steric and electronic effects that control rare-earth element extraction. Subtle changes in the structure around diglycolamide carbonyl oxygen atoms result in dramatic shifts in the lanthanide extraction strength and selectivity. The effects of the chain length and branching position of N-alkyl substituents in DGAs are elaborated on with the use of experimental, computational, and solution-structure characterization techniques.

Speciation of Molybdenum(VI) in Chloride Media at Elevated Mo Concentrations.

Speciation of Mo(VI) in chloride media (0.5-11 M HCl) at elevated Mo concentrations (0.1-300 mM Mo) was investigated using UV spectroscopy. In addition to five major monomeric species, H2MoO4, H3MoO4 +, H3MoO4Cl, MoO2Cl2, and MoO2Cl3 -, chemometric analysis of UV spectra suggests the presence of three cationic dinuclear species that predominate in solutions of 1-4.5 M HCl at >20 mM Mo concentrations. Thermodynamic values and molar absorptivity spectra were calculated from UV spectrophotometric data using refined numerical methods. The stability constants determined for three Mo dimers are log ß = 3.53 ± 0.05 (H2Mo2O5 2+), log ß = 3.60 ± 0.04 (H3Mo2O5 3+), and log ß = 2.91 ± 0.03 (H3Mo2O6Cl2+).

Sequestration of trivalent americium and lanthanide nitrates with bis-lactam-1,10-phenanthroline ligand in a hydrocarbon solvent.

Efficient separation of minor actinides and lanthanides from used nuclear fuel could potentially lead to the development of sustainable nuclear fuel cycles. Herein, we report an in-depth study on selectivity and speciation in the extraction of the trivalent minor actinide Am and rare earth metal ions with a pre-organized phenanthroline-based ligand in a hydrocarbon solvent system relevant to nuclear fuel reprocessing. The 1 : 1 and 2 : 1 ligand-to-metal complexes dominate the speciation in the organic solvent over a range of ligand-to-metal concentrations, as evidenced by experimental data and supported by modeling.

Extraction of Water and Speciation of Trivalent Lanthanides and Americium in Organophosphorus Extractants.

Complexes of the trivalent lanthanides and Am with di-2-ethylhexylphosphoric acid (HDEHP) dissolved in an aliphatic diluent were probed with UV-vis, X-ray absorption fine structure, and time-resolved fluorescence spectroscopy while the water concentration was determined by Karl Fischer titrations. In particular, our work focuses on the Nd-hypersensitive UV-vis absorbance region to identify the cause of changing absorbance values at 570 and 583 nm in relation to the pseudooctahedral Nd environment when coordinated with three HDEHP dimers. In contrast to recently reported interpretations, we establish that while impurities have an effect on this electronic transition band, a high water content can cause distortion of the pseudooctahedral symmetry of the six-coordinate Nd, resembling the reported spectra of the seven-coordinate Nd compounds. Extended X-ray absorption fine structure analysis of the Nd in high-concentration HDEHP solutions also points to an increase in the coordination number from 6 to 7. The spectral behavior of other lanthanides (Pr, Ho, Sm, and Er) and AmIII as a function of the HDEHP concentration suggests that water coordination with the metal likely depends on the metal's effective charge. Fluorescence data using lifetime studies and excitation and emission spectra support the inclusion of water in the Eu coordination sphere. Further, the role of the effective charge was confirmed by a comparison of the Gibbs free energies of six- and seven-coordinate La-HDEHP-H2O and Lu-HDEHP-H2O complexes using density functional theory. In contrast, HEH[EHP], the phosphonic acid analogue of HDEHP, exhibits a smaller capacity for water, and the electronic absorption spectra of Nd or Am appear to be unchanged, although the Pr spectra show a noticeable change in intensity as a function of the water content. Electronic absorption extinction coefficients of AmIII, NdIII, PrIII, SmIII, ErIII, and HoIII as a function of the HDEHP concentration are reported for the first time.

Aqueous complexation of citrate with neodymium(III) and americium(III): a study by potentiometry, absorption spectrophotometry, microcalorimetry, and XAFS.

The aqueous complexation of Nd(III) and Am(III) with anions of citrate was studied by potentiometry, absorption spectrophotometry, microcalorimetry, and X-ray absorption fine structure (XAFS). Using potentiometric titration data fitting the metal-ligand (L) complexes that were identified for Nd(III) were NdHL, NdL, NdHL2, and NdL2; a review of trivalent metal-citrate complexes is also included. Stability constants for these complexes were calculated from potentiometric and spectrophotometric titrations. Microcalorimetric results concluded that the entropy term of complex formation is much more dominant than the enthalpy. XAFS results showed a dependence in the Debye-Waller factor that indicated Nd(iii)-citrate complexation over the pH range of 1.56-6.12.

Aqueous complexation of thorium(IV), uranium(IV), neptunium(IV), plutonium(III/IV), and cerium(III/IV) with DTPA.

Aqueous complexation of Th(IV), U(IV), Np(IV), Pu(III/IV), and Ce(III/IV) with DTPA was studied by potentiometry, absorption spectrophotometry, and cyclic voltammetry at 1 M ionic strength and 25 °C. The stability constants for the 1:1 complex of each trivalent and tetravalent metal were calculated. From the potentiometric data, we report stability constant values for Ce(III)DTPA, Ce(III)HDTPA, and Th(IV)DTPA of log ß(101) = 20.01 ± 0.02, log ß(111) = 22.0 ± 0.2, and log ß(101) = 29.6 ± 1, respectively. From the absorption spectrophotometry data, we report stability constant values for U(IV)DTPA, Np(IV)DTPA, and Pu(IV)DTPA of log ß(101) = 31.8 ± 0.1, 32.3 ± 0.1, and 33.67 ± 0.02, respectively. From the cyclic voltammetry data, we report stability constant values for Ce(IV) and Pu(III) of log ß(101) = 34.04 ± 0.04 and 20.58 ± 0.04, respectively. The values obtained in this work are compared and discussed with respect to the ionic radius of each cationic metal.

Redox reactions of Pu(IV) and Pu(III) in the presence of acetohydroxamic acid in HNO(3) solutions.

The reduction of Pu(IV) in the presence of acetohydroxamic acid (HAHA) was monitored by vis-NIR spectroscopy. All experiments were performed under low HAHA/Pu(IV) ratios, where only the Pu(IV)-monoacetohydroxamate complex and Pu uncomplexed with HAHA were present in relevant concentrations. Time dependent concentrations of all absorbing species were resolved using molar extinction coefficients for Pu(IV), Pu(III), and the Pu(AHA)(3+) complex by deconvolution of spectra. From fitting of the experimental data by rate equations integrated by a numeric method three reactions were proposed to describe a mechanism responsible for the reduction and oxidation of plutonium in the presence of HAHA and HNO(3). Decomposition of Pu(AHA)(3+) follows a second order reaction mechanism with respect to its own concentration and leads to the formation of Pu(III). At low HAHA concentrations, a two-electron reduction of uncomplexed Pu(IV) with HAHA also occurs. Formed Pu(III) is unstable and slowly reoxidizes back to Pu(IV), which, at the point when all HAHA is decomposed, can be catalyzed by the presence of nitrous acid.

Spectroscopic study of the uranyl-acetohydroxamate adduct with tributyl phosphate.

The ultraviolet-visible (UV-Vis) and Fourier transform infrared (FT-IR) spectroscopic studies carried out for the system UO2(NO3)/AHA/TBP (uranyl-acetohydroxamate-tributyl phosphate) confirmed the presence of the adduct of UO2(NO3)(AHA) 2TBP with 1:1 stoichiometry for UO2:AHA (acetohydroxamic acid). The spectrum of this complex is identical to the infrared spectrum of the organic phase formed in the uranium distribution experiments with 30% TBP/n-dodecane and AHA present in aqueous phase. Disappearance of the hydroxyl stretching band and a shift in the position of the carbonyl band in the infrared spectra revealed that both the hydroxyl and the carbonyl group of acetohydroxamic acid are involved in the chelate ring with uranium. Also, acetic acid, accrued after acidic hydrolysis of acetohydroxamic acid, was identified in the extraction organic phase.