The extraction of trivalent lanthanides from an aqueous phase containing 1 M NaClO4 into the room temperature ionic liquid 1-butyl-3-methylimidazolium nonafluoro-1-butanesulfonate by the beta-diketone extractant 2-thenoyltrifluoroacetone (Htta) was studied. Radiotracer distribution, absorption spectroscopy, time-resolved laser-induced fluorescence spectroscopy, and X-ray absorption fine structure measurements point to the extraction of multiple lanthanide species. At low extractant concentrations, fully hydrated aqua cations of the lanthanides are present in the ionic liquid phase. As the extractant concentration is increased 1:2 and 1:3 lanthanide:tta species are observed. In contrast, 1:4 Ln:tta complexes were observed in the extraction of lanthanides by Htta into 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

The reactions of 237NpO2 with excess iodate under acidic hydrothermal conditions result in the isolation of the neptunium(IV), neptunium(V), and neptunium(VI) iodates, Np(IO3)4, Np(IO3)4.nH2O.nHIO3, NpO2(IO3), NpO2(IO3)2(H2O), and NpO2(IO3)2.H2O, depending on both the pH and the amount of water present in the reactions. Reactions with less water and lower pH favor reduced products. Although the initial redox processes involved in the reactions between 237NpO2 or 242PuO2 and iodate are similar, the low solubility of Pu(IO3)4 dominates product formation in plutonium iodate reactions to a much greater extent than does Np(IO3)4 in the neptunium iodate system. UO2 reacts with iodate under these conditions to yield uranium(VI) iodates solely. The isotypic structures of the actinide(IV) iodates, An(IO3)4 (An=Np, Pu), are reported and consist of one-dimensional chains of dodecahedral An(IV) cations bridged by iodate anions. The structure of Np(IO3)4.nH2O.nHIO3 is constructed from NpO9 tricapped-trigonal prisms that are bridged by iodate into a polar three-dimensional framework structure. Second-harmonic-generation measurements on a polycrystalline sample of the Th analogue of Np(IO3)4.nH2O.nHIO3 reveal a response of approximately 12x that of alpha-SiO2. Single-crystal magnetic susceptibility measurements of Np(IO3)4 show magnetically isolated Np(IV) ions.

Three novel Th(IV) compounds containing heavy oxoanions, Th(SeO3)(SeO4) (1), Th(IO3)2(SeO4)(H2O)3·H2O (2), and Th(CrO4)(IO3)2 (3), have been synthesized under mild hydrothermal conditions. Each of these three distinct structures contain trigonal pyramidal and tetrahedral oxoanions. Compound 1 adopts a three-dimensional structure formed from ThO9 tricapped trigonal prisms, trigonal pyramidal selenite, SeO32–, anions containing Se(IV), and tetrahedral selenate, SeO42–, anions containing Se(VI). The structure of 2 contains two-dimensional porous sheets and occluded water molecules. The Th centers are found as isolated ThO9 tricapped trigonal prisms and are bound by four trigonal pyramidal iodate anions, two tetrahedral selenate anions, and three coordinating water molecules. In the structure of 3, the Th(IV) cations are found as ThO9 tricapped trigonal prisms. Each Th center is bound by six IO31– anions and three CrO42– anions forming a chiral three-dimensional structure. Second-harmonic generation of 532 nm light from 1064 nm radiation by a polycrystalline sample of 3 was observed. Crystallographic data (193 K, MoKα, λ=0.71073): 1; monoclinic, P21/c; a=7.0351(5)Å, b=9.5259(7)Å, c=9.0266(7)Å, β=103.128(1), Z=4, R(F)=2.47% for 91 parameters with 1462 reflections with I>2σ(I); 2, monoclinic, P21/n, a=7.4889(9)Å, b=8.002(1)Å, c=20.165(3)Å, β=100.142(2), Z=4, R(F)=4.71% for 158 parameters with 2934 reflections with I>2σ(I); 3, orthorhombic, P212121, a=7.3672(5)Å, b=9.3617(6)Å, c=11.9201(7)Å, Z=4, R(F)=2.04% for 129 parameters with 2035 reflections with I>2σ(I).

Na2[UO2(IO3)4(H2O)] has been synthesized under mild hydrothermal conditions. Its structure consists of Na+ cations and [UO2(IO3)4(H2O)](2-) anions. The [UO2(IO3)4(H2O)](2-) anions are formed from the coordination of a nearly linear uranyl, UO2(2+), cation by four monodentate IO(3-) anions and a coordinating water molecule to yield a pentagonal bipyramidal environment around the uranium center. The water molecules form intermolecular hydrogen bonds with the terminal oxo atoms of neighboring [UO2(IO3)4(H2O)](2-) anions to yield one-dimensional chains that extend down the b axis. There are two crystallographically unique iodate anions in the structure of Na2[UO2(IO3)4(H2O)]. One of these anions is aligned so that the lone-pair of electrons is also directed along the b axis. The overall structure is therefore polar, owing to the cooperative alignment of both the hydrogen bonds and the lone-pair of electrons on iodate. The polarity of the monoclinic space group C2 (a = 11.3810(12) A, b = 8.0547(8) A, c = 7.6515(8) A, beta = 90.102(2) degrees , Z = 2, T = 193 K) found for this compound is consistent with the structure. Second-harmonic generation of 532 nm light from a 1064 nm laser source yields a response of approximately 16x alpha-SiO2.

AbstractFor Abstract see ChemInform Abstract in Full Text.

The rational design of ionic liquid-based metal ion separation systems requires either that the ion transfer properties of these systems be predictable from the known behavior of conventional organic solvents or that the mechanism(s) of ion transfer be understood at a fundamental level. With this in mind, we have examined the transfer of selected metal ions from acidic aqueous media into a series of N,N'-dialkylimidazolium-based room-temperature ionic liquids (RTILs) in the presence of crown ethers, neutral organophosphorus extradants, or β-diketones. The results obtained indicate that although certain aspects of metal ion extraction into RTILs parallel the behavior of conventional solvents, ionic liquids frequently play a more active role in the partitioning process, with ion exchange involving the cationic or anionic constituents of the ionic liquid comprising an important mode of ion transfer. The implications of this observation for the application of ILs as extraction solvents are described.

Insight into the factors that control the formation and size of heavy metal phosphate nanophases in vitreous silica has been gained by combining conventional and anomalous small angle x-ray scattering studies with powder x-ray diffraction and laser-induced fluorescence investigations. Europium, thorium, and uranyl ions were sorbed from aqueous solutions into a chemically functionalized porous silica (termed Diphosil). Aliquots of those samples were heated to a series of temperatures that spanned the pore collapse point. Loading with trivalent europium ions resulted in production of nanophases whose size corresponded to the average number of metal ions per pore. Thorium or uranyl ions resulted in retention of porosity to higher temperature with eventual pore collapse that evidently resulted in formation of nanophases whose size exceeded that determinable under the experimental conditions.

The unique physicochemical properties of room-temperature ionic liquids (RTILs) have led to intense interest in these materials as alternatives to conventional organic solvents in a range of synthetic, catalytic, and electrochemical applications. Recently, there has been growing interest in their potential use in various separation processes, among them the liquid-liquid extraction of metal ions. Although certain RTIL-extractant combinations (e.g., crown ethers in 1-alkyl-3-methylimidazolium bis[(trifluoromethylsulfonyl] imides) have been shown to provide extraction efficiencies far exceeding those observed with conventional solvents, recent work suggests that the utility of RTILs may be limited by solubilization losses and difficulties in recovering extracted metal ions. In this work, we demonstrate that these limitations arise, in part, from differences in the mechanism of metal ion partitioning in RTIL systems versus conventional organic diluents and consider approaches by which they might be overcome.

This project seeks to understand the microscopic effects of radiation damage in nuclear waste forms. The authors' approach to this challenge encompasses studies of ceramics and glasses containing short-lived alpha- and beta-emitting actinides with electron microscopy, laser and X-ray spectroscopic techniques, and computational modeling and simulations. In order to obtain information on long-term radiation effects on waste forms, much of the effort is to investigate {alpha}-decay induced microscopic damage in 18-year old samples of crystalline yttrium and lutetium orthophosphates that initially contained {approximately} 1(wt)% of the alpha-emitting isotope {sup 244}Cm (18.1 y half life). Studies also are conducted on borosilicate glasses that contain {sup 244}Cm, {sup 241}Am, or {sup 249}Bk, respectively. The authors attempt to gain clear insights into the properties of radiation-induced structure defects and the consequences of collective defect-environment interactions, which are critical factors in assessing the long-term performance of high-level nuclear waste forms.