32 Matching Results

Search Results

Advanced search parameters have been applied.

Directed synthesis of crystalline plutonium (III) and (IV) oxalates: accessing redox-controlled separations in acidic solutions

Description: Both binary and ternary solid complexes of Pu(III) and Pu(IV) oxalates have been previously reported in the literature. However, uncertainties regarding the coordination chemistry and the extent of hydration of some compounds remain mainly because of the absence of any crystallographic characterization. Single crystals of hydrated oxalates of Pu(III), Pu{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 6}{center_dot}3H{sub 2}O (I) and Pu(IV), KPu(C{sub 2}O{sub 4}){sub 2}(OH){center_dot}2.5H{sub 2}O (II), were synthesized under moderate hydrothermal conditions and characterized by single crystal X-ray diffraction studies. Compounds I and II are the first plutonium(III) or (IV) oxalate compounds to be structurally characterized via single crystal X-ray diffraction studies. Crystallographic data for I: monoclinic, space group P21/c, a = 11.246(3) A, b = 9.610(3) A, c = 10.315(3) A, Z = 4 and II: monoclinic, space group C2/c, a = 23.234(14) A, b = 7.502(4) A, c = 13.029(7) A, Z = 8.
Date: January 1, 2009
Creator: Runde, Wolfgang; Brodnax, Lia F; Goff, George S; Bean, Amanda C & Scott, Brian L
Partner: UNT Libraries Government Documents Department

Complexation of Plutonium (IV) With Sulfate At Variable Temperatures

Description: The complexation of plutonium(IV) with sulfate at variable temperatures has been investigated by solvent extraction method. A NaBrO{sub 3} solution was used as holding oxidant to maintain the plutonium(IV) oxidation state throughout the experiments. The distribution ratio of Pu(IV) between the organic and aqueous phases was found to decrease as the concentrations of sulfate were increased. Stability constants of the 1:1 and 1:2 Pu(IV)-HSO{sub 4}{sup -} complexes, dominant in the aqueous phase, were calculated from the effect of [HSO{sub 4}{sup -}] on the distribution ratio. The enthalpy and entropy of complexation were calculated from the stability constants at different temperatures using the Van't Hoff equation.
Date: October 5, 2006
Creator: Xia, Y.; Friese, J.I.; Moore, D.A>; Bachelor, P.P. & Rao, L.
Partner: UNT Libraries Government Documents Department

Actinide cation-cation complexes

Description: The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO{sub 2}{sup +}) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO{sub 2}{sup +}; therefore, cation-cation complexes indicate something unique about AnO{sub 2}{sup +} cations compared to actinide cations in general. The first cation-cation complex, NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO{sub 2}{sup +} species, the cation-cation complexes of NpO{sub 2}{sup +} have been studied most extensively while the other actinides have not. The only PuO{sub 2}{sup +} cation-cation complexes that have been studied are with Fe{sup 3+} and Cr{sup 3+} and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, NpO{sub 2}{sup +}{center_dot}Th{sup 4+}, PuO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, and PuO{sub 2}{sup +}{center_dot}Th{sup 4+} at an ionic strength of 6 M using LIPAS are 2.4 {plus_minus} 0.2, 1.8 {plus_minus} 0.9, 2.2 {plus_minus} 1.5, and {approx}0.8 M{sup {minus}1}.
Date: December 1994
Creator: Stoyer, N. J. & Seaborg, G. T.
Partner: UNT Libraries Government Documents Department

Plutonium (IV) complexation by nitrate in acid solutions of ionic strengths from 2 to 19 molal

Description: Titrations of Pu(IV) with HNO{sub 3} in a series of aqueous HClO{sub 4} solutions ranging in ionic strength from 2 to 19 molal were followed using absorption spectrophotometry. The Pu 5f-5f spectra in the visible and near IR range change with complex formation. At each ionic strength, a series of spectra were obtained by varying nitrate concentration. Each series was deconvoluted into spectra f Pu{sup 4+}(aq), Pu(NO{sub 3}){sup 3+} and Pu(NO{sub 3}){sub 2}{sup 2+} complexes, and simultaneously their formation constants were determined. When corrected for the incomplete dissociation of nitric acid, the ionic strength dependence of each formation constant can be described by two parameters, {beta}{sup 0} and {Delta}{var_epsilon} using the formulae of specific ion interaction theory. The difficulties with extending this analysis to higher nitrate coordination numbers are discussed.
Date: September 1, 1997
Creator: Berg, J.M.; Veirs, D.K.; Vaughn, R.B.; Cisneros, M.A. & Smith, C.A.
Partner: UNT Libraries Government Documents Department

Integration of advanced nuclear materials separation processes

Description: This is the final report of a two-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This project has examined the fundamental chemistry of plutonium that affects the integration of hydrothermal technology into nuclear materials processing operations. Chemical reactions in high temperature water allow new avenues for waste treatment and radionuclide separation.Successful implementation of hydrothermal technology offers the potential to effective treat many types of radioactive waste, reduce the storage hazards and disposal costs, and minimize the generation of secondary waste streams. The focus has been on the chemistry of plutonium(VI) in solution with carbonate since these are expected to be important species in the effluent from hydrothermal oxidation of Pu-containing organic wastes. The authors investigated the structure, solubility, and stability of the key plutonium complexes. Installation and testing of flow and batch hydrothermal reactors in the Plutonium Facility was accomplished. Preliminary testing with Pu-contaminated organic solutions gave effluent solutions that readily met discard requirements. A new effort in FY 1998 will build on these promising initial results.
Date: December 31, 1998
Creator: Jarvinen, G.D.; Worl, L.A.; Padilla, D.D.; Berg, J.M.; Neu, M.P.; Reilly, S.D. et al.
Partner: UNT Libraries Government Documents Department

Novel complexing agents for the efficient separation of actinides and remediation of actinide-contaminated sites

Description: Research into the coordination chemistry of transactinide elements should provide us with new fundamental knowledge about structure, geometry, and stability of these metal complexes. Our approach involves the design, synthesis, and characterization of {open_quotes}expanded porphyrin{close_quotes} macrocyclic ligands which coordinate the actinide metal cations with high thermodynamic affinity and kinetic stability. We can use the knowledge from understanding the fundamental coordination chemistry of these elements as a stepping stone to heavy metal detoxification, radioactive waste cleanup, and possibly radioactive isotope separation. The critical components of this research endeavor, along with the viability of metal complex formation, will be correlated to ring size and core geometry of the ligand and, the atomic radius, oxidation state, coordination geometry and coordination number of the transactinium metal ion. These chelating agents may have certain applications to the solution of some radioactive waste problems if they can be attached to polymer supports and used to chemically separate the radioactive components in waste.
Date: March 15, 1996
Creator: Baisden, P. & Kadkhodayan, B.
Partner: UNT Libraries Government Documents Department

Plutonium Speciation, Solubilization and Migration in Soils

Description: This report summarizes research completed in the first half of a three-year project. As outlined in the authors' proposal they are focusing on (1) characterizing the plutonium at an actinide contaminated site, RFETS, including determining the origin, dispersion, and speciation of the plutonium, (2) studying environmentally important plutonium complexes, primarily hydroxides and carbonates, and (3) examining the interactions of plutonium species with manganese minerals. In the first year the authors focused on site based studies. This year they continue to characterize samples from the RFETS, study the formation and structural and spectroscopic features of environmentally relevant Pu species, and begin modeling the environmental behavior of plutonium.
Date: June 1, 1999
Creator: Neu, M. & Runde, W.
Partner: UNT Libraries Government Documents Department

Automated spectrophotometer for plutonium and uranium determination

Description: The automated spectrophotometer described is the first in a planned series of automated instruments for determining plutonium and uranium in nuclear fuel cycle materials. It has a throughput rate of 5 min per sample and uses a highly specific method of analysis for these elements. The range of plutonium and uranium measured is 0.5 to 14 mg and 1 to 14 mg, respectively, in 0.5 ml or less of solution with an option to pre-evaporate larger volumes. The precision of the measurements is about 0.02 mg standard deviation over the range corresponding to about 2 rel percent at the 1-mg level and 0.2 rel percent at the 10-mg level. The method of analysis involves the extraction of tetrapropylammonium plutonyl and uranyl trinitrate complexes into 2-nitropropane and the measurement of the optical absorbances in the organic phase at unique peak wavelengths. Various aspects of the chemistry associated with the method are presented. The automated spectrophotometer features a turntable that rotates as many as 24 samples in tubes to a series of stations for the sequential chemical operations of reagent addition and phase mixing to effect extraction, and then to a station for the absorbance measurement. With this system, the complications of sample transfers and flow-through cells are avoided. The absorbance measurement system features highly stable interference filters and a microcomputer that controls the timing sequence and operation of the system components. Output is a paper tape printout of three numbers: a four-digit number proportional to the quantity of plutonium or uranium, a two-digit number that designates the position of the tube in the turntable, and a one-digit number that designates whether plutonium or uranium was determined. Details of the mechanical and electrical components of the instrument and of the hardware and software aspects of the computerized control system are provided.
Date: September 1, 1975
Creator: Jackson, D.D.; Hodgkins, D.J.; Hollen, R.M. & Rein, J.E.
Partner: UNT Libraries Government Documents Department

Preliminary results on the hydrolysis and carbonate complexation of dioxoplutonium(V)

Description: The hydrolysis and carbonate complexation reactions of dioxoplutonium (V) were studied in near neutral aqueous systems. These experiments involved the addition of hydroxide or carbonate to Pu(V) in a perchorate medium. Change in the electronic adsorption spectra provided information about the chemical properties of Pu(V). The results indicate the Pu(V) does not hydrolyze below pH 7.15. In the carbonate complexation studies, log {beta}{sub 11} was measured to be 4.4 +- 0.7. 5 figs., 3 tabs.
Date: November 1, 1987
Creator: Bennett, D.A.; Hoffman, D.C.; Nitsche, H. & Silva, R.J.
Partner: UNT Libraries Government Documents Department

Stability constants important to the understanding of plutonium in environmental waters, hydroxy and carbonate complexation of PuO{sub 2}{sup +}

Description: The formation constants for the reactions PuO{sub 2}{sup +} + H{sub 2}O = PuO{sub 2}(OH) + H{sup +} and PuO{sub 2}{sup +} + CO{sub 3}{sup 2} = PuO{sub 2}(CO{sub 3}){sup {minus}} were determined in aqueous sodium perchlorate solutions by laser-induced photoacoustic spectroscopy. The molar absorptivity of the PuO{sub 2}{sup +} band at 569 nm decreased with increasing hydroxide concentration. Similarly, spectral changes occurred between 540 and 580 nm as the carbonate concentration was increased. The absorption data were analyzed by the non-linear least-squares program SQUAD to yield complexation constants. Using the specific ion interaction theory, both complexation constants were extrapolated to zero ionic strength. These thermodynamic complexation constants were combined with the oxidation-reduction potentials of Pu to obtain Eh versus pH diagrams. 120 refs., 35 figs., 12 tabs.
Date: April 20, 1990
Creator: Bennett, D.A.
Partner: UNT Libraries Government Documents Department

Actinide-specific complexing agents: their structural and solution chemistry

Description: The synthesis of a series of tetracatecholate ligands designed to be specific for Pu(IV) and other actinide(IV) ions has been achieved. Although these compounds are very effective as in vivo plutonium removal agents, potentiometric and voltammetric data indicate that at neutral pH full complexation of the Pu(IV) ion by all four catecholate groups does not occur. Spectroscopic results indicate that the tetracatecholates, 3,4,3-LICAMS and 3,4,3-LICAMC, complex Am(III). The Am(IV)/(III)-catecholate couple (where catecholate = 3,4,3-LICAMS or 3,4,3-LICAMC) is not observed, but may not be observable due to the large currents associated with ligand oxidation. However, within the potential range where ligand oxidation does not occur, these experiments indicate that the reduction potential of free Am(IV)/(III) is probably greater than or equal to + 2.6 V vs NHE or higher. Proof of the complexation of americium in the trivalent oxidation state by 3,4,3-LICAMS and 3,4,3-LICAMC elimates the possibility of tetracatholates stabilizing Am(IV) in vivo.
Date: July 1, 1983
Creator: Raymond, K.N.; Freeman, G.E. & Kappel, M.J.
Partner: UNT Libraries Government Documents Department

Electrorecovery of actinides at room temperature

Description: There are a large number of purification and processing operations involving actinide species that rely on high-temperature molten salts as the solvent medium. One such application is the electrorefining of impure actinide metals to provide high purity material for subsequent applications. There are some drawbacks to the electrodeposition of actinides in molten salts including relatively low yields, lack of accurate potential control, maintaining efficiency in a highly corrosive environment, and failed runs. With these issues in mind we have been investigating the electrodeposition of actinide metals, mainly uranium, from room temperature ionic liquids (RTILs) and relatively high-boiling organic solvents. The RTILs we have focused on are comprised of 1,3-dialkylimidazolium or quaternary ammonium cations and mainly the {sup -}N(SO{sub 2}CF{sub 3}){sub 2} anion [bis(trif1uoromethylsulfonyl)imide {equivalent_to} {sup -}NTf{sub 2}]. These materials represent a class of solvents that possess great potential for use in applications employing electrochemical procedures. In order to ascertain the feasibility of using RTILs for bulk electrodeposition of actinide metals our research team has been exploring the electron transfer behavior of simple coordination complexes of uranium dissolved in the RTIL solutions. More recently we have begun some fundamental electrochemical studies on the behavior of uranium and plutonium complexes in the organic solvents N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO). Our most recent results concerning electrodeposition will be presented in this account. The electrochemical behavior of U(IV) and U(III) species in RTILs and the relatively low vapor pressure solvents NMP and DMSO is described. These studies have been ongoing in our laboratory to uncover conditions that will lead to the successful bulk electrodeposition of actinide metals at a working electrode surface at room temperature or slightly elevated temperatures. The RTILs we have focused on thus far are based on 1,3-dialkylimidazolium or quaternary ammonium cations and {sup -}N(SO{sub 2}CF{sub 3}){sub 2} anions. Our results ...
Date: January 1, 2008
Creator: Stoll, Michael E; Oldham, Warren J & Costa, David A
Partner: UNT Libraries Government Documents Department

Bulk solubility and speciation of plutonium(VI) in phosphate-containing solutions

Description: The solubility and speciation of Pu(VI) with phosphate as a function of pH was investigated to determine the ability of phosphate to act as an actinide getter. The general properties were first investigated and are reported here with the goal of performing more quantitative experiments in the future. Solubility was approached from oversaturation at initial pH = 4, 10 and 13.4. Absorption spectra were recorded, the solution filtered and the filtrate counted. Absorption spectra were obtained at varying phosphate concentrations and at pH of 2.7 to 11.9. The effect of complexation on the 833 mn Pu(VI) band was characterized. Evidence for three phosphate complexes was obtained for pH < 10 which have absorption bands at 842, 846 and 849 mn. Evidence for colloid formation was observed but is not conclusive. The possibility of colloids prevents accurate analysis of the solubility experiments. A concentration of 10[sup [minus]5] to 10[sup [minus]6] M Pu(VI) was measured in the filtrate at pH [le] 10 that were passed through a 50 mn filter. Pu(VI) complexes with phosphate over hydroxide at pH [le] 11.6, but at pH [ge] 11.9, only hydrolyzed Pu(VI) was detected. At pH = 12, the concentration of Pu(VI) was as high as 10[sup [minus]4] M.
Date: January 1, 1992
Creator: Weger, H.T.; Okajima, S.; Cunnane, J.C. & Reed, D.T.
Partner: UNT Libraries Government Documents Department

Secondary recovery of plutonium and americium from process waste streams by solvent extraction

Description: A solvent extraction process is being evaluated for the secondary recovery of plutonium and americium from Rocky Flats waste streams. The bidentate organophosphorus compounds dihexyl-N,N-diethylcarbamylmethylene phosphonate and its dibutyl analogue have been shown to be selective extractants for the actinides from solutions of nitric acid. The results from laboratory test runs in which the organophosphorus extractants were used for processing secondary waste solutions will be presented. Solvent extractant properties and purification procedures are discussed.
Date: January 16, 1978
Creator: Hagan, P. G. & Navratil, J. D.
Partner: UNT Libraries Government Documents Department