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Sample records for anhydrous uranyl chloride

  1. Crystal field influence on vibration spectra: anhydrous uranyl chloride and dihydroxodiuranyl chloride tetrahydrate

    International Nuclear Information System (INIS)

    Perrin, Andre; Caillet, Paul

    1976-01-01

    Vibrational spectra of anhydrous uranyl chloride UO 2 Cl 2 and so called basic uranyl chloride: dihydroxodiuranyl chloride tetrahydrate /UO 2 (OH) 2 UO 2 /Cl 2 (H 2 O) 4 are reported. Factor group method analysis leads for the first time to complete and comprehensive interpretation of their spectra. Two extreme examples of crystal field influence on vibrational spectra are pointed out: for UO 2 Cl 2 , one is unable to explain spectra without taking into account all the elements of primitive crystalline cell, whilst for dihydroxodiuranyl dichloride tetrahydrate the crystal packing has very little effect on vibrational spectra [fr

  2. Study into complexing of anhydrous uranyl chloride with organic o-bases in nonaqueous media. Interaction with aliphatic sulfoxides

    Energy Technology Data Exchange (ETDEWEB)

    Kobets, L V; Buchikhin, E P; Klyshevich, R P; Belyachis, G F

    1982-01-01

    The methods of spectrophotometry, conductometry and calorimetry have been used to investigate interaction of uranyl chloride with dimethyl, diamil, dioctyl sulfoxides in the nonaqueous acetone media. Existence of complexes with 1:1, 1:2, 1:3 composition for dimethyl sulfoxide and with 1:1, 1:2 composition for diamil-, dioctyl sulfoxides is revealed. The constants of formation and dissociation of these complexes are calculated; the enthalpies of their formation in acetone are determined.

  3. Study into complexing of anhydrous uranyl chloride with organic o-bases in nonaqueous media. Interaction with aliphatic sulfoxides

    International Nuclear Information System (INIS)

    Kobets, L.V.; Buchikhin, E.P.; Klyshevich, R.P.; Belyachis, G.F.

    1982-01-01

    The methods of spectrophotometry, conductometry and calorimetry have been used to investigate interaction of uranyl chloride with dimethyl, diamil, dioctyl sulfoxides in the nonaqueous acetone media. Existence of complexes with 1:1, 1:2, 1:3 composition for dimethyl sulfoxide and with 1:1, 1:2 composition for diamil-, dioctyl sulfoxides is revealed. The constants of formation and dissociation of these complexes are calculated; the enthalpies of their formation in acetone are determined

  4. Preparation of pure anhydrous rare earth chlorides

    International Nuclear Information System (INIS)

    Bel'kova, N.L.; Slastenova, N.M.; Batyaev, I.M.; Solov'ev, M.A.

    1979-01-01

    A method has been suggested for obtaining extra-pure anhydrous REE chlorides by chloridizing corresponding oxalates by chlorine in a fluid bed, the chloridizing agents being diluted by an inert gas in a ratio of 2-to-1. The method is applicable to the manufacture of quality chlorides not only of light, but also of heavy REE. Neodymium chloride has an excited life of tau=30 μs, this evidencing the absence of the damping impurities

  5. Electrochemical behavior of uranyl in anhydrous polar organic media

    Energy Technology Data Exchange (ETDEWEB)

    Burn, Adam G.; Nash, Kenneth L. [Washington State Univ., Pullmann, WA (United States). Dept. of Chemistry

    2017-09-01

    Weak complexes between pentavalent and hexavalent actinyl cations have been reported to exist in acidic, non-complexing high ionic strength aqueous media. Such ''cation-cation complexes'' were first identified in the context of actinide-actinide redox reactions in acidic aqueous media relevant to solvent extraction-based separation systems, hence their characterization is of potential interest for advanced nuclear fuel reprocessing. This chemistry could be relevant to efforts to develop advanced actinide separations based on the upper oxidation states of americium, which are of current interest. In the present study, the chemical behavior of pentavalent uranyl was examined in non-aqueous, aprotic polar organic solvents (propylene carbonate and acetonitrile) to determine whether UO{sub 2}{sup +} cations generated at the reducing working electrode surface would interact with the UO{sub 2}{sup 2+} cations in the bulk phase to form cation-cation complexes in such media. In magnesium perchlorate media, the electrolyte adsorbed onto the working electrode surface and interfered with the uranyl reduction/diffusion process through an ECE (electron transfer/chemical reaction/electron transfer) mechanism. In parallel studies of uranyl redox behavior in tetrabutylammonium hexafluorophosphate solutions, an EC (electron transfer/chemical reaction) mechanism was observed in the cyclic voltammograms. Ultimately, no conclusive electrochemical evidence demonstrated uranyl cation-cation interactions in the non-aqueous, aprotic polar organic solvent solutions, though the results reported do not completely rule out the presence of UO{sub 2}{sup +}.UO{sub 2}{sup 2+} complexes.

  6. Multi-scale modelling of uranyl chloride solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Thanh-Nghi; Duvail, Magali, E-mail: magali.duvail@icsm.fr; Villard, Arnaud; Dufrêche, Jean-François, E-mail: jean-francois.dufreche@univ-montp2.fr [Institut de Chimie Séparative de Marcoule (ICSM), UMR 5257, CEA-CNRS-Université Montpellier 2-ENSCM, Site de Marcoule, Bâtiment 426, BP 17171, F-30207 Bagnols-sur-Cèze Cedex (France); Molina, John Jairo [Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103 (Japan); Guilbaud, Philippe [CEA/DEN/DRCP/SMCS/LILA, Marcoule, F-30207 Bagnols-sur-Cèze Cedex (France)

    2015-01-14

    Classical molecular dynamics simulations with explicit polarization have been successfully used to determine the structural and thermodynamic properties of binary aqueous solutions of uranyl chloride (UO{sub 2}Cl{sub 2}). Concentrated aqueous solutions of uranyl chloride have been studied to determine the hydration properties and the ion-ion interactions. The bond distances and the coordination number of the hydrated uranyl are in good agreement with available experimental data. Two stable positions of chloride in the second hydration shell of uranyl have been identified. The UO{sub 2}{sup 2+}-Cl{sup −} association constants have also been calculated using a multi-scale approach. First, the ion-ion potential averaged over the solvent configurations at infinite dilution (McMillan-Mayer potential) was calculated to establish the dissociation/association processes of UO{sub 2}{sup 2+}-Cl{sup −} ion pairs in aqueous solution. Then, the association constant was calculated from this potential. The value we obtained for the association constant is in good agreement with the experimental result (K{sub UO{sub 2Cl{sup +}}} = 1.48 l mol{sup −1}), but the resulting activity coefficient appears to be too low at molar concentration.

  7. Preparation and characterization of ABS/anhydrous cobalt chloride composites

    Science.gov (United States)

    Shao, Chengli; Shang, Peng; Mao, Yapeng; Li, Qiuying; Wu, Chifei

    2018-01-01

    Anhydrous cobalt chloride (CoCl2) particles filled acrylonitrile-butadiene-styrene (ABS) composites were successfully prepared and investigated. A strong interfacial interaction between CoCl2 particles and ABS matrix was generated by heat pressing at 190 °C for 15 min. SEM results demonstrated that the particles were dispersed uniformly in the matrix. Fourier transform infrared, x-ray photoelectron spectroscopy and electron spin resonance were used for the investigation of the coordination reaction. The interfacial interaction resulted from a solid-state coordination reaction between nitrile groups (-CN) and cobalt ions (Co2+), leading to an increase in mechanical properties and glass transition temperature. Moreover, heat deflection temperatures were measured and proved to achieve an improvement of 30.6 °C when the CoCl2 content was 7 wt%.

  8. Study of the transport characteristics of uranyl chloride in a highly concentrated aqueous solution of sodium chloride

    International Nuclear Information System (INIS)

    Murso, H.

    1986-01-01

    The purpose of this work was the study of the transport processes of uranyl chloride at various temperatures, in order to be able to estimate the danger potential of the intrusion of water during storage in salt form. For this the concentration dependency of the approximated principal diffusion coefficients of uranyl chloride in a table salt solution, which with a c(NaCl) = 5.2 mol/l is almost at the saturation point, was studied at 25, 40 and 50degC. The measurements were successful in the ternarian system UO 2 Cl 2 -NaCl-H 2 O with absorption optics. An unexpected temperature dependency of the diffusion coefficients was found, which reached its minimum at 40degC with UO 2 Cl 2 concentrations of less than 2x10 -2 mol/l. For comparison the diffusion coefficients were measured in the binary system UO 2 Cl 2 -H 2 O and compared with theoretical calculations. The cause for the poor correlation found here is thought to be the hydrolysis products, whose formation is strongly influenced by the foreign-electrolyte concentration (NaCl). For clarification, viscosity measurements and molar mass determinations (ultracentrifuge) will be done. Some pH-dependent hydrolysis equilibriums are being postulated and the equilibrium constants of uranyl hydroxo complexes are being determined by sedimentation analysis. (orig./RB) [de

  9. Raman spectroscopic study of uranyl complex in alkali chloride melts

    International Nuclear Information System (INIS)

    Fujii, Toshiyuki; Uda, Takeshi; Iwadate, Yasuhiko; Nagai, Takayuki; Uehara, Akihiro; Yamana, Hajimu

    2013-01-01

    Raman spectra of alkali chloride melts containing 3 mol% U(VI) were measured at 823 K. The complexation of UO 2 Cl 4 2- in binary mixtures of LiCl-KCl, LiCl-RbCl, and LiCl-CsCl was investigated. The spectrum of UO 2 Cl 4 2- obtained was characterized by Raman active vibration modes, that is, totally symmetric stretching vibrations A 1g (ν 1 : OUO) and A 1g (ν 2 : UCl 4 ), and bending vibration E g (ν 8: UO 2 Cl 2 ). The dependence of polarizing power of solvent cations on the vibrational frequencies was clarified. The ν 8 frequencies were insensitive to the change in the polarizing power. On the other hand, the ν 1 and ν 2 frequencies increased with the rise of polarizing power. The Raman shifts suggest that the square bipyramidal structure of UO 2 Cl 4 2- is kept in various binary alkali chlorides, while O 2− and Cl − around U(VI) are clearly polarized by the increase of polarizing power

  10. Voltammetry of uranyl chloride in the LiCl - KCl eutectic

    International Nuclear Information System (INIS)

    Fondanaiche, J.C.

    1965-01-01

    Spent UO 2 - PuO 2 fuels can be reprocessed in a molten salt media. Uranium dioxide can easily be dissolved as UO 2 Cl 2 in a molten salt bath using chlorine gas. A study of quantitative analysis of an uranyl chloride solution in the LiCl-KCl eutectic at 400 C has been performed here using voltammetry (a large area-graphite indicator electrode has been employed). The precision which is obtained is around 6 per cent for concentrations below 10 -2 M. Precision decreases slightly for more concentrated solutions. The study of polarization curves allowed to give a reduction mechanism for the UO 2 ++ ion. For dilute solutions, this reduction proceeds through the UO 2 + ion. But interpretation of current-potential curves is made difficult by the dismutation reaction of the UO 2 ion and by the fact that the surface of the indicator electrode is not renewed. (author) [fr

  11. Thermogravimetric method of estimation of uranyl cation state in melts of alkali metal chlorides and their mixtures

    International Nuclear Information System (INIS)

    Vorobej, M.P.; Desyatnik, V.N.

    1979-01-01

    The thermogravimetric method was used to study the chloridizing of uranium oxides in molten media. The study of the uranium oxide chloridizing served as a basis for evaluating comparatively, using the DTA method, the uranyl-cation state in a melt. Using the alkali metals as example, it was shown that the decomposition of the frozen uranium oxychlorides proceeds with the formation of intermediate chlorouranates. The final product of the thermolysis are uranates Me 2 U 2 O 7 (Me-Li, Na, K, Rb, Cs). The time and the conditions of the change of uranium oxides to the oxyanion [UO 2 Cl 4 ] 2- were determined as a function of the chloridizing agent. The method can be employed for evaluating uranyl-ions in molten media where they are used as electrolytes in the extraction of uranium dioxide

  12. Contribution to the study of the mechanism of extraction of uranyl chloride by long chain aliphatic amines

    International Nuclear Information System (INIS)

    Rubinstein, G.R.

    1965-06-01

    After having studied and developed the mechanisms which may 'a priori' explain the extraction process (co-ordination, ion association or intermediate mechanism), experience shows that ion association only should be taken into consideration. The structure of the organic complex of uranyl chloride has been defined on the basis of the study of the variation of the distribution coefficient of uranium between the two phases at the equilibrium as a function of successively the activity of Cl - ions in the aqueous phase, the concentration of amine salt in the organic phase and finally of the concentration of uranium in the aqueous phase. The plotting of the results in bi-logarithmic co-ordinates enables us to propose the following formula for the extracted compound: UO 2 Cl 4 -- (NR 3 H + ) 2 . The calculation of the equilibrium constant of formation of the organic compound of uranyl chloride has been possible in the case of diluted solutions of uranium only. (author) [fr

  13. Electrochemical Studies on Uranyl Chloride Complexes in 1-Butyl-3-methyl-imidazolium Based Ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Yasuhisa Ikeda; Katsuyuki Hiroe; Nobutaka Ohta; Masanobu Nogami; Atsushi Shirai [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology 2-12-1-N1-34 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan); Noriko Asanuma [Department of Energy Science and Engineering, Tokai University 1117 Kitakaname, Hiratsuka-shi, Kanagawa 259-1292 (Japan)

    2008-07-01

    Sample solutions were prepared by dissolving UO{sub 2}Cl{sub 2}-nH{sub 2}O or Cs{sub 2}UO{sub 2}Cl{sub 4} into 1-butyl-3-methyl-imidazolium chloride (BMICl). Their UV-visible absorption spectra showed that uranyl species in BMICl exist as [UO{sub 2}Cl{sub 4}]{sup 2-}. Cyclic voltammograms were measured using a glassy carbon working electrode, a platinum wire counter electrode, and an Ag/AgCl reference electrode with a liquid junction filled with BMIBF{sub 4} at 80 {+-} 1 deg. C in glove box under an Ar atmosphere. Peaks of one redox couple were observed at around -0.73 V and -0.65 V on both systems. Potential differences between two peaks ({delta}E{sub p}) at scan rates in the range of 10 to 50 mV/s are 70 - 80 mV, which are almost consistent with theoretical {delta}E{sub p} value (67 mV) for the reversible one electron transfer reaction at 80 deg. C. From these results, it is concluded that [UO{sub 2}Cl{sub 4}]{sup 2-} in BMICl is reduced quasi-reversibly to [UO{sub 2}Cl{sub 4}]{sup 3-}. (authors)

  14. Investigation of regularities of uranyl salts complexing with neutral bases in nonaqueous media

    International Nuclear Information System (INIS)

    Kobets, L.V.; Buchikhin, E.P.

    1986-01-01

    Anhydrous uranyl chloride complexing with neutral oxygen-containing organic bases (sulfoxides, organic phosphates, phosphinates, phosphinoxides, N-oxides) in the acetone medium depending on the donor capacity of neutral molecules is discussed. The constants of 1:1 complexes dissociation are shown to detect no correlation with the donor capacity of neutral bases. At the same time stability constants of complexes increase as the donor capacity of ligands grows. But the dependence is of a complex character and is determined by the nature of neutral molecules. Estimation of uranyl chloride and 0-donor contributions into the values of stability constants and complex formation heats is given

  15. Voltammetry of uranyl chloride in the LiCl - KCl eutectic; Voltammetrie du chlorure d'uranyle dans l'eutectique LiCl - KC1

    Energy Technology Data Exchange (ETDEWEB)

    Fondanaiche, J C [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1965-07-01

    Spent UO{sub 2} - PuO{sub 2} fuels can be reprocessed in a molten salt media. Uranium dioxide can easily be dissolved as UO{sub 2}Cl{sub 2} in a molten salt bath using chlorine gas. A study of quantitative analysis of an uranyl chloride solution in the LiCl-KCl eutectic at 400 C has been performed here using voltammetry (a large area-graphite indicator electrode has been employed). The precision which is obtained is around 6 per cent for concentrations below 10{sup -2} M. Precision decreases slightly for more concentrated solutions. The study of polarization curves allowed to give a reduction mechanism for the UO{sub 2}{sup ++} ion. For dilute solutions, this reduction proceeds through the UO{sub 2}{sup +} ion. But interpretation of current-potential curves is made difficult by the dismutation reaction of the UO{sub 2} ion and by the fact that the surface of the indicator electrode is not renewed. (author) [French] Le traitement des combustibles a base d'oxydes (UO{sub 2} - PUO{sub 2}) peut etre effectue au moyen des sels fondus. Le bioxyde d'uranium passe aisement en solution sous forme de UO{sub 2}Cl{sub 2} dans un bain de sels fondus par action du chlore. Nous avons etudie ici l'analyse quantitative d'une solution de chlorure d'uranyle dans l'eutectique LiCl - KCl a 400 C par voltammetrie (electrode indicatrice de graphite d'assez grande surface). La precision est d'environ 6 pour cent pour les concentrations inferieures a 10{sup -2} M; elle est legerement moins bonne pour les solutions plus concentrees. L'examen des courbes de polarisation a permis de donner un mecanisme de reduction de l'ion UO{sub 2}: pour les solutions diluees, cette reduction se fait par l'intermediaire de l'ion UO{sub 2}{sup +}. Mais l'interpretation des courbes intensite-potentiel est rendue delicate par la reaction de dismutation de l'ion UO{sub 2}{sup +} et par le fait que la surface de l'electrode indicatrice n'est pas renouvelee. (auteur)

  16. A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

    Science.gov (United States)

    Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; Runde, W.; Roback, R.; Williams-Jones, A. E.

    2018-02-01

    The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO22+, UO2Cl+, and UO2Cl2°. UO2Cl3- is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species show fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO2Cl42- and UO2Cl53- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T > 150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO2Cl2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO22+ + Cl- = UO2Cl+ are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO22+ + 2Cl- = UO2Cl2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.

  17. Contribution to the study of the mechanism of extraction of uranyl chloride by long chain aliphatic amines; Contribution a l'etude du mecanisme d'extraction du chlorure d'uranyle par les amines aliphatiques a longues chaines

    Energy Technology Data Exchange (ETDEWEB)

    Rubinstein, G R [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1965-06-01

    After having studied and developed the mechanisms which may 'a priori' explain the extraction process (co-ordination, ion association or intermediate mechanism), experience shows that ion association only should be taken into consideration. The structure of the organic complex of uranyl chloride has been defined on the basis of the study of the variation of the distribution coefficient of uranium between the two phases at the equilibrium as a function of successively the activity of Cl{sup -} ions in the aqueous phase, the concentration of amine salt in the organic phase and finally of the concentration of uranium in the aqueous phase. The plotting of the results in bi-logarithmic co-ordinates enables us to propose the following formula for the extracted compound: UO{sub 2}Cl{sub 4}{sup --}(NR{sub 3}H{sup +}){sub 2}. The calculation of the equilibrium constant of formation of the organic compound of uranyl chloride has been possible in the case of diluted solutions of uranium only. (author) [French] Apres avoir expose et developpe les mecanismes qui a priori pouvaient expliquer le processus d'extraction (coordination, association d'ions ou mecanisme intermediaire), le recours a l'experience a finalement permis de ne retenir que l'association d'ions. La structure du complexe organique de chlorure d'uranyle a ete definie a partir de l'etude de la variation du coefficient de partage de l'uranium entre les deux phases a l'equilibre en fonction successivement de l'activite des ions Cl{sup -} en phase aqueuse, de la concentration de sel d'amine en phase organique et enfin de la concentration d'uranium de la phase aqueuse. La representation bilogarithmique des resultats de ces essais a permis de proposer la formule suivante pour le compose extrait: UO{sub 2}Cl{sub 4}{sup --}(NR{sub 3}H{sup +}){sub 2}. Le calcul de la constante d'equilibre de formation du compose organique de chlorure d'uranyle a ete seulement possible pour les solutions diluees en uranium. (auteur)

  18. Volatile uranyl hexafluoroacetoacetonate complexes

    International Nuclear Information System (INIS)

    Dines, M.B.; Hall, R.B.; Kaldor, A.; Kramer, G.M.; Maas, E.T. Jr.

    1980-01-01

    A composition of matter is described, characterized by the formula UO 2 (CF 3 COCHCOCF 3 ).L where L is a ligand selected from isopropanol, ethanol, isobutanol, tert-butanol, methanol, tetrahydrofuran, acetone, dimethylformamide, n-propanol and ethyl acetate. A process for producing the complex comprises reacting uranyl chloride with a hexafluoroacetylacetonate dissolved in a ligand L: experimental details are given. (U.K.)

  19. Thermochemical investigations on uranyl phosphates and arsenates

    International Nuclear Information System (INIS)

    Barten, H.

    1986-11-01

    The results are described of a study of the thermochemical stability of anhydrous uranyl phosphates and arsenates. A number of aspects of chemical technological importance are indicated in detail. The synthesized anhydrous uranyl phosphates and arsenates were very hygroscopic, so that experiments on these compounds had to be carried out under moisture-free conditions. Further characterisation of these compounds are given, including a study of their thermal stabilities and phase relations. The uranyl phosphates reduced reversibly at temperatures of the order of 1100 to 1600 0 C. This makes it possible to express their relative stabilities quantitatively, in terms of the oxygen pressures of the reduction reactions. The thermal decomposition of uranyl arsenates did not occur by reduction, as for the phosphates, but by giving off arsenic oxide vapour. The results of measurements of enthalpies of solution led to the determination of the enthalpies of formation, heat capacity and the standard entropies of the uranyl arsenates. The thermochemical functions at high-temperatures could consequently be calculated. Attention is paid to the possible formation of uranium arsenates, whose uranium has a valency lower than six, hitherto not reported in literature. It was not possible to prepare arsenates of tetravalent uranium. However, three new compounds were observed, one of these, UAsO 5 , was studied in some detail. (Auth.)

  20. Contribution to the study of the mechanism of extraction of uranyl chloride by long chain aliphatic amines; Contribution a l'etude du mecanisme d'extraction du chlorure d'uranyle par les amines aliphatiques a longues chaines

    Energy Technology Data Exchange (ETDEWEB)

    Rubinstein, G.R. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1965-06-01

    After having studied and developed the mechanisms which may 'a priori' explain the extraction process (co-ordination, ion association or intermediate mechanism), experience shows that ion association only should be taken into consideration. The structure of the organic complex of uranyl chloride has been defined on the basis of the study of the variation of the distribution coefficient of uranium between the two phases at the equilibrium as a function of successively the activity of Cl{sup -} ions in the aqueous phase, the concentration of amine salt in the organic phase and finally of the concentration of uranium in the aqueous phase. The plotting of the results in bi-logarithmic co-ordinates enables us to propose the following formula for the extracted compound: UO{sub 2}Cl{sub 4}{sup --}(NR{sub 3}H{sup +}){sub 2}. The calculation of the equilibrium constant of formation of the organic compound of uranyl chloride has been possible in the case of diluted solutions of uranium only. (author) [French] Apres avoir expose et developpe les mecanismes qui a priori pouvaient expliquer le processus d'extraction (coordination, association d'ions ou mecanisme intermediaire), le recours a l'experience a finalement permis de ne retenir que l'association d'ions. La structure du complexe organique de chlorure d'uranyle a ete definie a partir de l'etude de la variation du coefficient de partage de l'uranium entre les deux phases a l'equilibre en fonction successivement de l'activite des ions Cl{sup -} en phase aqueuse, de la concentration de sel d'amine en phase organique et enfin de la concentration d'uranium de la phase aqueuse. La representation bilogarithmique des resultats de ces essais a permis de proposer la formule suivante pour le compose extrait: UO{sub 2}Cl{sub 4}{sup --}(NR{sub 3}H{sup +}){sub 2}. Le calcul de la constante d'equilibre de formation du compose organique de chlorure d'uranyle

  1. Thermochemical investigations on uranyl phosphates and arsenates

    International Nuclear Information System (INIS)

    Barten, H.

    1986-01-01

    Results are described of a study of the thermochemical stability of anhydrous phosphates and arsenates. The results of phase studies deal with compound formation and characterization, coexisting phases and limiting physical or chemical properties. The uranyl phosphates evolve oxygen at higher temperatures and the arsenates lose arsenic oxide vapour. These phenomena give the possibility to describe their thermodynamic stabilities. Thus oxygen pressures of uranyl phosphates have been measured using a static, non-isothermal method. Having made available the pure anhydrous compounds in the course of this investigation, molar thermodynamic quantities have been measured as well. These include standard enthalpies of formation from solution calorimetry and high-temperature heat-capacity functions derived from enthalpy increments measured. Some attention is given to compounds with uranium in valencies lower than six which have been met during the investigation. An evaluation is made of the thermodynamics of the compounds studied, to result in tabulized high-temperature thermodynamic functions. Relative stabilities within the systems are discussed and comparisons of the uranyl phosphates and the arsenates are made. (Auth.)

  2. Metal complex derivatives of hydrogen uranyl phosphate

    International Nuclear Information System (INIS)

    Grohol, D.; Blinn, E.L.

    1994-01-01

    Derivatives of hydrogen uranyl phosphate were prepared by incorporating transition metal complexes into the uranyl phosphate matrix. The transition metal complexes employed include bis(ethylenediamine)copper(II), bis(1,3-propanediamine)copper(II) chloride, (triethylenetetramine)copper(II), (1,4,8,11-tetraazacyclotetradecane)copper(II), (1,4,8,12-tetraazacyclopentadecane)copper(II), (1,4,8,11-tetraazacyclotetradecane)nickel(II) chloride, (triethylenetetramine)nickel(II) and others. The chemical analyses of these derivatives indicated that the incorporation of the transition metal complexes into the uranyl phosphate matrix via ion exchange was not stoichiometric. The extent of ion exchange is dependent on the size and structure of the transition metal complex. All complexes were characterized by X-ray powder diffractometry, electronic and infrared spectra, thermal analyses and chemical analysis. An attempt was made to correlate the degree of quenching of the luminescence of the uranyl ion to the spacing between the uranyl phosphate layers in the derivatives

  3. Investigation into complexing of anhydrons uranyl chloride with organic o-bases in nonaqueous media. Reaction with neutral organic phosphorus compounds

    International Nuclear Information System (INIS)

    Kobets, L.V.; Buchikhin, E.P.; Klyshevich, R.P.; Belyachis, G.F.

    1983-01-01

    The methods of spectrophotometry, conductometry and calorimetry have been used to investigate the uranylchloride inter ction with tributylphosphate, di-iso-amyl, dioctyl ethers of methylphosphonic acid, trioctylphosphinoxid and hexamethylphosphortriamide in anhydrous acetone medium. The existence of complexes of 1:1 and 1:2 composition is found, constants of formation and dissociation for these substances are calculated and enthalpies of their formation in acetone are determined. The dependence of equivalent electric conductivity of complexes on their concentration in acetone is studied. The analysis of the data obtained proves a regular growth of both complex formation constants and enthalpies of interaction with the growth of the value of donor number of bases. Dissociation constants of complexes do not practically depend on donor properties of phosphorogranic bases studied with the exception of HMFTA. This is most probably connected with the effect of steric factors, rather than the growth of basisity of compound

  4. Investigation into complexing of anhydrons uranyl chloride with organic o-bases in nonaqueous media. Reaction with neutral organic phosphorus compounds

    Energy Technology Data Exchange (ETDEWEB)

    Kobets, L V; Buchikhin, E P; Klyshevich, R P; Belyachis, G F

    1983-01-01

    The methods of spectrophotometry, conductometry and calorimetry have been used to investigate the uranylchloride interaction with tributylphosphate, di-iso-amyl, dioctyl ethers of methylphosphonic acid, trioctylphosphinoxide and hexamethylphosphortriamide in anhydrous acetone medium. The existence of complexes of 1:1 and 1:2 composition is found, constants of formation and dissociation for these substances are calculated and enthalpies of their formation in acetone are determined. The dependence of equivalent electric conductivity of complexes on their concentration in acetone is studied. The analysis of the data obtained proves a regular growth of both complex formation constants and enthalpies of interaction with the growth of the value of donor number of bases. Dissociation constants of complexes do not practically depend on donor properties of phosphorogranic bases studied with the exception of HMFTA. This is most probably connected with the effect of steric factors, rather than the growth of basisity of compound.

  5. The potentiometric and laser RAMAN study of the hydrolysis of uranyl chloride under physiological conditions and the effect of systematic and random errors on the hydrolysis constants

    International Nuclear Information System (INIS)

    Deschenes, L.L.; Kramer, G.H.; Monserrat, K.J.; Robinson, P.A.

    1986-12-01

    The hydrolysis of uranyl ions in 0.15 mol/L (Na)C1 solution at 37 degrees Celsius has been studied by potentiometric titration. The results were consistent with the formation of (UO 2 ) 2 (OH) 2 , (UO 2 ) 3 (OH) 4 , (UO 2 ) 3 (OH) 5 and (UO 2 ) 4 (OH) 7 . The stability constants, which were evaluated using a version of MINIQUAD, were found to be: log β 22 = -5.693 ± 0.007, log β 34 = -11.499 ± 0.024, log β 35 = -16.001 ± 0.050, log β 47 = -21.027 ± 0.051. Laser Raman spectroscopy has been used to identify the products including (UO 2 ) 4 (OH) 7 species. The difficulties in identifying the chemical species in solution and the effect of small errors on this selection has also been investigated by computer simulation. The results clearly indicate that small errors can lead to the selection of species that may not exist

  6. Potentiometric titrations in anhydrous acetic acid

    International Nuclear Information System (INIS)

    Le Port, L.

    1966-03-01

    The method used for studying anhydrous acetic acid is potentiometry with a glass electrode. We have in this way studied the titration of common inorganic acids (HClO 4 - HBr - H 2 SO 4 - HCl - HNO 3 - H 3 PO 4 ) and of some metallic salts. Furthermore we have shown that complex acids are formed between HCl and some metallic chlorides. An analysis of the titration curves for the inorganic acids against pyridinium chloride has made it possible to calculate a certain number of values for the dissociation pK of these acids and of the corresponding pyridinium salts. The titration of metallic perchlorates constitutes a method of studying the stability of acetates; we have thus been able to draw up a classification for some of these acetates. The metallic chlorides studied fall into two groups according to their behaviour in weak or strong acids. The differences have been explained on the basis of the role played by solvolysis. In the third part we have studied the acidic properties of mixtures of HCl with certain metallic chlorides. This work has demonstrated the existence, in certain cases, of acid complexes of the type (HCl) m MCl n . (author) [fr

  7. Study of alkaline-earth element complexes in anhydrous acetic acid

    International Nuclear Information System (INIS)

    Petit, N.

    1968-10-01

    We have studied the complexes of alkaline-earth elements in anhydrous acetic acid. Using glass-electrode potentiometry we have studied the titration of alkaline earth acetates with perchloric acid which is the strongest acid in anhydrous acetic acid. These titrations have shown that the basic strength of these acetates increases as follows: Mg 4 ); the mixed acetate-acid sulfate complex of barium: Ba (OAc)(HSO 4 ); the mixed acetate-chloride of barium: Ba (OAc)(Cl). (author) [fr

  8. Preparation and properties of uranyl bromate monohydrate

    International Nuclear Information System (INIS)

    Weigel, F.

    1983-01-01

    Uranyl bromate monohydrate UO 2 (BrO 3 ) 2 .H 2 O was obtained as a greenish-yellow solid by the metathesis of a uranyl sulfate solution with a stoichiometric amount of barium bromate solution. On evaporation of the supernatant of the precipitated BaSO 4 a greenish-yellow syrup was obtained which, on dehydration with anhydrous carbon tetrachloride, yielded a free-flowing greenish-yellow powder with stoichiometry UO 2 (BrO 3 ) 2 .H 2 O. Powder diffraction diagrams of UO 2 (BrO 3 ) 2 .H 2 O obtained using the Guinier method yielded an orthorhombic lattice (space group, Pbcn (no. 60)) with a = 8.533 +- 0.003 A, b = 7.639 +- 0.003 A and c = 12.293 +- 0.004 A; the X-ray density was 4.507 g cm -3 . The compound was characterized by chemical analysis, IR spectroscopy and differential thermal analysis. (Auth.)

  9. Harvesting Water from Air: Using Anhydrous Salt with Sunlight

    KAUST Repository

    Li, Renyuan

    2018-04-02

    Atmospheric water is abundant alternative water resource, equivalent to 6 times of water in all rivers on Earth. This work screens 14 common anhydrous and hydrated salt couples in terms of their physical and chemical stability, water vapor harvesting and release capacity under relevant application scenarios. Among the salts screened, copper chloride (CuCl2), copper sulfate (CuSO4) and magnesium sulfate (MgSO4) distinguish themselves and are further made into bi-layer water collection devices, with the top layer being photothermal layer while the bottom layer being salt-loaded fibrous membrane. The water collection devices are capable of capturing water vapor out of the air with low relative humidity (down to 15 %) and releasing water under regular and even weakened sunlight (i.e. 0.7 kW/m2). The work shines light on the potential use of anhydrous salt towards producing drinking water in water scarce regions.

  10. New chemistry of the uranyl ion in non aqueous media

    International Nuclear Information System (INIS)

    Siffredi, G.

    2008-12-01

    This work deals with new aspects of the chemistry of the uranyl(VI) ion {UO 2 } 2+ in anhydrous polar organic solvents such as the activation of the reputedly inert U-O yl bond and the controlled reduction of this species which represent a particularly active field of research that attracts much attention for both its fundamental aspects and applications. Treatment of uranyl(VI) compounds UO 2 X' 2 (X' = I, OTf, Cl) with Me 3 SiX (X = Cl, Br, I) reagents, in various anhydrous polar organic solvents, has been first considered. In most cases, reduction into tetravalent species with complete de-oxygenation of the uranyl {UO 2 } 2+ ion is observed. The reaction is particularly efficient in acetonitrile where the tetravalent [UX 4 (MeCN) 4 ] complexes, which are useful precursors in uranium chemistry, are isolated. In the course of these reactions, the influence of the solvent, the nature of X' and X in the UO 2 X' 2 precursor and the Me 3 SiX reagent are pointed out. Reaction of the uranyl(VI) UO 2 X 2 (X = I, Cl, OTf, NO 3 ) precursors with the anionic MC 5 R 5 (M = K, R = H, Me; M= Li, R = Me; M= Tl, R = H) reagents did not lead to the organometallic [(η 5 -C 5 R 5 ) n UO 2 X 2-n ] species (n = 1, 2) but to pentavalent uranyl(V) complexes. This method is a facile and rapid route towards the formation of stable pentavalent uranyl which offers promising sources for further U(V) chemical developments and for fundamental and applied interests. Their structure is strongly dependent on the nature of the solvent, the additional ligands X and of the M + cation. In pyridine, the {UO 2 (py) 5 } + ion appears to be an ubiquitous and a quite stable entity. The coordinating properties of the basic oxo groups, which coordinate easily to M + ions (M= Li, K, Tl), favour structural diversity with formation of hetero-polymetallic complexes such as [{UO 2 (py) 5 }{MX(py) 2 }] (M= Li, X I), [{UO 2 (py) 5 }{MX 2 (py) 2 }] ∞ (M= K, Tl, X= OTf; M= K, X= I), [{UO 2 (py) 5 }(M 2 X 3 )]

  11. Infrared studies on complexes between octaethyltetraamidepyrophosphate (OETAPP) and uranyl salts

    International Nuclear Information System (INIS)

    Grychowski, P.; Mikulski, J.; Moravets, Ya.; Shara, V.; Shourkova, L.

    1981-01-01

    Uranyl nitrate and uranyl chloride were extracted from the water phase with CHCl 3 solution of octaethyltetraamidepyrophosphate (OETAPP). Infrared spectra of the organic phases were recorded before and after the extraction. For both systems, the frequency of the P=O stretching mode of OETAPP after the extraction was lowered, which indicates for the formation of OETAPP UO 2 (NO 3 ) 2 and OETAPP UO 2 Cl 2 complexes. If uranyl nitrate was extracted with OETAPP in CCl 4 a precipitate was formed in the solution. From the analysis of the IR spectrum of the precipitate it was concluded that the complex OETAPP UO 2 (NO 3 ) 2 was formed also in this case, however, the complex was insoluble in CCl 4 . (author)

  12. On uranyl phosphites

    International Nuclear Information System (INIS)

    Avduevskaya, K.A.; Ragulina, N.B.; Rozanov, I.A.; Koval', E.M.

    1978-01-01

    The medium and single-substituted uranyl phosphites of the UO 2 HPO 3 x 3H 2 O and UO 2 (H 2 PO 3 ) 2 x3H 2 O composition were separated in crystal state for the first time. The medium phosphite is fully dehydrated above H 2 SO 4 , intermediate hydrates not being formed. Waterless phosphite decomposes at the temperature above 360 deg C into the mixture of uranium and uranyl phosphates, hydrogen being liberated. The thermal decomposition of single-substituted phosphite starts at the temperature above 150 deg C and is accompanied by the full reduction of uranium up to U(4). The product of calcination is identified as cubic UP 2 O 7

  13. Analysis Ratio of Uranyl/Urea and Uranyl/HMTA on the ComplexesUranyl-Urea and Uranyl-HMTA with Spectrophotometry Method

    International Nuclear Information System (INIS)

    Simbolon, Sahat

    2000-01-01

    Reaction between uranyl and urea and uranyl and HMTA was investigated atpH = 4 and room temperature. The result of the reaction was measured withspectrophotometer, each absorbance was pictured between mol fraction andabsorbance for uranyl - urea and uranyl - HMTA. The linear and horizontalcurve was found for reaction uranyl - urea, meanwhile S curve for thereaction uranyl and HMTA. It was found that reaction between uranyl and HMTAon mol fraction value less than 0.25 was complexes meanwhile on the range of0.25 and 0.5 the reaction between uranyl and HMTA was stoichiometries.(author)

  14. Production and Characterization of Desmalonichrome Relative Binding Affinity for Uranyl Ions in Relation to Other Siderophores

    Energy Technology Data Exchange (ETDEWEB)

    Mo, Kai-For; Dai, Ziyu; Wunschel, David S.

    2016-06-24

    Siderophores are Fe binding secondary metabolites that have been investigated for their uranium binding properties. Much of the previous work has focused on characterizing hydroxamate types of siderophores, such as desferrioxamine B, for their uranyl binding affinity. Carboxylate forms of these metabolites hold potential to be more efficient chelators of uranyl, yet they have not been widely studied and are more difficult to obtain. Desmalonichrome is a carboxylate siderophore which is not commercially available and so was obtained from the ascomycete fungus Fusarium oxysporum cultivated under Fe depleted conditions. The relative affinity for uranyl binding of desmalonichrome was investigated using a competitive analysis of binding affinities between uranyl acetate and different concentrations of iron(III) chloride using electrospray ionization mass spectrometry (ESI-MS). In addition to desmalonichrome, three other siderophores, including two hydroxamates (desferrioxamine B and desferrichrome) and one carboxylate (desferrichrome A) were studied to understand their relative affinities for the uranyl ion at two pH values. The binding affinities of hydroxymate siderophores to uranyl ion were found to decrease to a greater degree at lower pH as the concentration of Fe (III) ion increases. On the other hand, lowering pH has little impact on the binding affinities between carboxylate siderophores and uranyl ion. Desmalonichrome was shown to have the greatest relative affinity for uranyl at any pH and Fe(III) concentration. These results suggest that acidic functional groups in the ligands are critical for strong chelation with uranium at lower pH.

  15. 21 CFR 168.110 - Dextrose anhydrous.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 2 2010-04-01 2010-04-01 false Dextrose anhydrous. 168.110 Section 168.110 Food... Table Sirups § 168.110 Dextrose anhydrous. (a) Dextrose anhydrous is purified and crystallized D-glucose... solids content is not less than 98.0 percent m/m. (b) The name of the food is “Dextrose anhydrous” or...

  16. Uranyl Oxalate Solubility

    Energy Technology Data Exchange (ETDEWEB)

    Leturcq, G.; Costenoble, S.; Grandjean, S. [CEA Marcoule DEN/DRCP/SCPS/LCA - BP17171 - 30207 Bagnols sur Ceze cedex (France)

    2008-07-01

    The solubility of uranyl oxalate was determined at ambient temperature by precipitation in oxalic-nitric solutions, using an initial uranyl concentration of 0.1 mol/L. Oxalic concentration varied from 0.075 to 0.3 mol/L while nitric concentration ranged between 0.75 and 3 mol/L. Dissolution tests, using complementary oxalic-nitric media, were carried out for 550 hours in order to study the kinetic to reach thermodynamic equilibrium. Similar solubility values were reached by dissolution and precipitation. Using the results, it was possible to draw the solubility surface versus oxalic and nitric concentrations and to determine both the apparent solubility constant of UO{sub 2}C{sub 2}O{sub 4}, 3H{sub 2}O (Ks) and the apparent formation constant of the first uranyl-oxalate complex UO{sub 2}C{sub 2}O{sub 4} (log {beta}1), for ionic strengths varying between 1 and 3 mol/L. Ks and log {beta}1 values were found to vary from 1.9 10{sup -8} to 9.2 10{sup -9} and from 5.95 to 6.06, respectively, when ionic strength varied from 1 to 3 mol/L. A second model may fit our data obtained at an ionic strength of 3 mol/L suggesting as reported by Moskvin et al. (1959) that no complexes are formed for [H{sup +}] at 3 M. The Ks value would then be 1.3 10{sup -8}. (authors)

  17. 21 CFR 184.1193 - Calcium chloride.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Calcium chloride. 184.1193 Section 184.1193 Food... Specific Substances Affirmed as GRAS § 184.1193 Calcium chloride. (a) Calcium chloride (CaCl2·2H2O, CAS Reg. No. 10035-04-8) or anhydrous calcium chloride (CaCl2, CAS Reg. No. 10043-52-4) may be commercially...

  18. Uranyl sorption onto alumina

    International Nuclear Information System (INIS)

    Jacobsson, A.M.M.

    1997-01-01

    The mechanism for the adsorption of uranyl onto alumina from aqueous solution was studied experimentally and the data were modeled using a triple layer surface complexation model. The experiments were carried out at low uranium concentrations (9 x 10 -11 --5 x 10 -8 M) in a CO 2 free environment at varying electrolyte concentrations (0.01--1 M) and pH (4.5--12). The first and second acid dissociation constants, pK a1 and pK a2 , of the alumina surface were determined from potentiometric titrations to be 7.2 ± 0.6 and 11.2 ± 0.4, respectively. The adsorption of uranium was found to be independent of the electrolyte concentration. The authors therefore conclude that the uranium binds as an inner sphere complex. The results were modeled using the code FITEQL. Two reactions of uranium with the surface were needed to fit the data, one forming a uranyl complex with a single surface hydroxyl and the other forming a bridged or bidentate complex reacting with two surface hydroxyls of the alumina. There was no evidence from these experiments of site heterogeneity. The constants used for the reactions were based in part on predictions made utilizing the Hard Soft Acid Base, HSAB, theory, relating the surface complexation constants to the hydrolysis of the sorbing metal ion and the acid dissociation constants of the mineral oxide surface

  19. Structure and spectroscopy of uranyl salicylaldiminate complexes

    Energy Technology Data Exchange (ETDEWEB)

    Tamasi, A.L.; Barnes, C.L.; Walensky, J.R. [Missouri Univ., Columbia, MO (United States). Dept. of Chemistry

    2013-07-01

    The synthesis of uranyl complexes coordinated to tridentate, monoanionic salicylaldiminate (Schiff base) ligands was achieved by the reaction of UO{sub 2}Cl{sub 2}(THF){sub 3}, 1, with one equivalent of the corresponding sodium salicylaldiminate salts affording [(C{sub 9}H{sub 6}N)N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 2, [(NC{sub 5}H{sub 4})N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 3, and [(C{sub 6}H{sub 4}SCH{sub 3})N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 4. These are uncommon examples of uranyl complexes with a monoanionic ancillary ligand to stabilize the coordination sphere and one chloride ligand. Compounds 2-4 have been characterized by {sup 1}H and {sup 13}C NMR spectroscopy as well as IR and UVVis spectroscopy and their structures determined by X-ray crystallography. (orig.)

  20. Barium uranyl diphosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, Anna-Gay D., E-mail: nelsoa@umich.edu [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Alekseev, Evgeny V. [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Juelich Wilhelm-Johnen-Strasse, Juelich 52428 (Germany); Ewing, Rodney C. [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Albrecht-Schmitt, Thomas E. [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States)

    2012-08-15

    Three Ba{sup 2+}/UO{sub 2}{sup 2+} methylenediphosphonates have been prepared from mild hydrothermal treatment of uranium trioxide, methylendiphosphonic acid (C1P2) with barium hydroxide octahydrate, barium iodate monohydrate, and small aliquots of HF at 200 Degree-Sign C. These compounds, Ba[UO{sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{center_dot}1.4H{sub 2}O (Ba-1), Ba{sub 3}[(UO{sub 2}){sub 4}(CH{sub 2}(PO{sub 3}){sub 2}){sub 2}F{sub 6}]{center_dot}6H{sub 2}O (Ba-2), and Ba{sub 2}[(UO{sub 2}){sub 2}(CH{sub 2}(PO{sub 3}){sub 2})F{sub 4}]{center_dot}5.75H{sub 2}O (Ba-3) all adopt layered structures based upon linear uranyl groups and disphosphonate molecules. Ba-2 and Ba-3 are similar in that they both have UO{sub 5}F{sub 2} pentagonal bipyramids that are bridged and chelated by the diphosphonate moiety into a two-dimensional zigzag anionic sheet (Ba-2) and a one-dimensional ribbon anionic chain (Ba-3). Ba-1, has a single crystallographically unique uranium metal center where the C1P2 ligand solely bridges to form [UO{sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{sup 2-} sheets. The interlayer space of the structures is occupied by Ba{sup 2+}, which, along with the fluoride ion, mediates the structure formed and maintains overall charge balance. - Graphical abstract: Illustration of the stacking of the layers in Ba{sub 3}[(UO{sub 2}){sub 4}(CH{sub 2}(PO{sub 3}){sub 2}){sub 2})F{sub 6}]{center_dot}6H{sub 2}O viewed along the c-axis. The structure is constructed from UO{sub 7} pentagonal bipyramidal units, U(1)O{sub 7}=gray, U(2)O{sub 7}=yellow, barium=blue, phosphorus=magenta, fluorine=green, oxygen=red, carbon=black, and hydrogen=light peach. Highlights: Black-Right-Pointing-Pointer The polymerization of the UO{sub 2}{sup 2+} sites to form uranyl dimers leads to structural variations in compounds. Black-Right-Pointing-Pointer Barium cations stitch uranyl diphosphonate anionic layers together, and help mediate structure formation. Black-Right-Pointing-Pointer HF acts as both a

  1. Contribution to the study of uranyl salts in butyl phosphate solutions

    International Nuclear Information System (INIS)

    Coulon, A.

    1965-06-01

    A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from ∼ 1270 cm -1 to ∼ 1180 cm -1 . A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [fr

  2. Anhydrous ethanol: A renewable source of energy

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Santosh; Singh, Neetu; Prasad, Ram [Department of Chemical Engineering, H. B. Technological Institute, Kanpur 208002 (India)

    2010-09-15

    Anhydrous ethanol is one of the biofuels produced today and it is a subset of renewable energy. It is considered to be an excellent alternative clean-burning fuel to gasoline. Anhydrous ethanol is commercially produced by either catalytic hydration of ethylene or fermentation of biomass. Any biological material that has sugar, starch or cellulose can be used as biomass for producing anhydrous ethanol. Since ethanol-water solution forms a minimum-boiling azeotrope of composition of 89.4 mol% ethanol and 10.6 mol% water at 78.2 C and standard atmospheric pressure, the dilute ethanol-water solutions produced by fermentation process can be continuously rectified to give at best solutions containing 89.4 mol% ethanol at standard atmospheric pressure. Therefore, special process for removal of the remaining water is required for manufacture of anhydrous ethanol. Various processes for producing anhydrous ethanol have been used/suggested. These include: (i) chemical dehydration process, (ii) dehydration by vacuum distillation process, (iii) azeotropic distillation process, (iv) extractive distillation processes, (v) membrane processes, (vi) adsorption processes and (vii) diffusion distillation process. These processes of manufacturing anhydrous ethanol have been improved continuously due to the increasingly strict requirements for quantity and quality of this product. The literature available on these processes is reviewed. These processes are also compared on the basis of energy requirements. (author)

  3. Complexes of uranyl with N-oxides of heterocyclic amines. Electron-vibrational absorption spectra

    International Nuclear Information System (INIS)

    Jezowska-Trzebiatowska, B.; Wieczorek, M.

    1977-01-01

    A number of coordination compounds formed by uranyl chloride and nitrate with N-oxides of heterocyclic amines have been prepared and characterized by spectral measurements in the absorption region 20000-50000 cm -1 . The electrons and vibronic transitions have been determined and discussed. (author)

  4. Investigation of uranyl-ion hydrolysis in uranyl pertechnetate and uranyl perchlorates solutions by two-phases potentiometric titration method

    International Nuclear Information System (INIS)

    Volk, V.I.; Belikov, A.D.

    1977-01-01

    The applicability of the method of two-phase potentiometric titration for studying hydrolysis of multi-charge ions has been shown. Hydrolysis of uranyl-ion has been investigated and hydrolysis constants in the solutions of uranyl pertechnetate and perchlorate have been calculated equal to (6.2+-0.15)x10 -5 and (9.25+-0.5)10 -5 , respectively. Infrared spectra of the initial crystallohydrates of uranyl pertechnetate and perchlorate has been analyzed. The data on hydrolysis of an uranyl-ion and IR spectra of crystallohydrates of the investigated salts have revealed the ability of pertechnetate ion to complexing with an uranyl group

  5. Synthesis and investigation of uranyl molybdate UO2MoO4

    International Nuclear Information System (INIS)

    Nagai, Takayuki; Sato, Nobuaki; Kitawaki, Shin-ichi; Uehara, Akihiro; Fujii, Toshiyuki; Yamana, Hajimu; Myochin, Munetaka

    2013-01-01

    In order to examine easily synthetic conditions of uranyl molybdate, UO 2 MoO 4 , used for the reprocessing process study of spent nuclear oxide fuels in alkaline molybdate melts, the uranium molybdate compounds were produced from U 3 O 8 powder and anhydrous MoO 3 reagent. The results of having investigated them in solid state by using X-ray diffractometry and Raman spectrometry, it was confirmed that UO 2 MoO 4 could be synthesized by heating mixed powder of U 3 O 8 and MoO 3 with stoichiometric mole ratio at 770 °C for 4 h under air atmosphere. Moreover, adding this UO 2 MoO 4 into Li 2 MoO 4 -Na 2 MoO 4 eutectic melt, most of the dissolved uranium species in the melt were observed as hexa–valent uranyl ions by absorption spectrophotometry

  6. Interfacial tension in systems involving TBP in dodecane, nitric acid, uranyl nitrate and water

    International Nuclear Information System (INIS)

    Kolarik, Z.; Pipkin, N.

    1982-08-01

    The interfacial tension was measured at 25 0 C in the systems TBP - n-dodecane/nitric acid - water and TBP - n-dodecane/nitric acid - uranyl nitrate - water. Empirical equations describing the interfacial tension as a function of the concentration of TBP in the starting organic phase and of uranium-(VI) and nitric acid in the equilibrium aqueous phase were suggested. In the absence of uranium (VI), the interfacial tension can also be correlated with the concentration of water in the equilibrium organic phase. Free TBP, hydrated or nonhydrated, and hydrated TBP solvates of nitric acid are interfacially active. Anhydrous TBP solvates of nitric acid and the TBP solvate of uranyl nitrate, which neither is hydrated, do not exhibit any visible interfacial activity. (orig.) [de

  7. Properties and thermal decomposition of the double salts of uranyl nitrate-ammonium nitrate

    International Nuclear Information System (INIS)

    Notz, K.J.; Haas, R.A.

    1989-01-01

    The formation of ammonium nitrate-uranyl nitrate double salts has important effects on the thermal denitration process for the preparation of UO 3 and on the physical properties of the resulting product. Analyses were performed, and properties and decomposition behavior were determined for three double salts: NH 4 UO 2 (NO 3 ) 3 , (NH 4 ) 2 UO 2 (NO 3 ) 4 , and (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O. The tinitrate salt decomposes without melting at 270-300 C to give a γ-UO 3 powder of ∼3-μm average size, with good ceramic properties for fabrication into UO 2 nuclear fuel pellets. The tetranitrate dihydrate melts at 48 C; it also dehydrates to the anhydrous salt. The anhydrous tetranitrate decomposes exothermically, without melting, at 170-270 C by losing one mole of ammonium nitrate to form the trinitrate salt

  8. Electrospray ionization of uranyl-citrate complexes

    Science.gov (United States)

    Somogyi, Árpád; Pasilis, Sofie P.; Pemberton, Jeanne E.

    2007-09-01

    Results presented here demonstrate the usefulness of electrospray ionization and gas-phase ion-molecule reactions to predict structural and electronic differences in complex inorganic ions. Electrospray ionization of uranyl citrate solutions generates positively and negatively charged ions that participate in further ion-molecule reactions in 3D ion trap and FT-ICR mass analyzers. Most ions observed are derived from the major solution uranyl-citrate complexes and involve species of {(UO2)2Cit2}2-, (UO2)3Cit2, and {(UO2)3Cit3}3-, where Cit indicates the citrate trianion, C6H5O73-. In a 3D ion trap operated at relatively high pressure, complex adducts containing solvent molecules, alkali and ammonium cations, and nitrate or chloride anions are dominant, and proton/alkali cation (Na+, K+) exchange is observed for up to six exchangeable protons in an excess of alkali cations. Adduct formation in a FT-ICR cell that is operated at lower pressures is less dominant, and direct detection of positive and negative ions of the major solution complexes is possible. Multiply charged ions are also detected, suggesting the presence of uranium in different oxidation states. Changes in uranium oxidation state are detected by He-CID and SORI-CID fragmentation, and certain fragments undergo association reactions in trapping analyzers, forming "exotic" species such as [(UO2)4O3]-, [(UO2)4O4]-, and [(UO2)4O5]-. Ion-molecule reactions with D2O in the FT-ICR cell indicate substantial differences in H/D exchange rate and D2O accommodation for different ion structures and charge states. Most notably, the positively charged ions [H2(UO2)2Cit2(H)]+ and [(UO2)2(Cit)]+ accommodate two and three D2O molecules, respectively, which reflects well the structural differences, i.e., tighter uranyl-citrate coordination in the former ion than in the latter. The corresponding negatively charged ions accommodate zero or two D2O molecules, which can be rationalized using suggested solution phase structures

  9. Contribution to the study of uranyl salts in butyl phosphate solutions; Contribution a l'etude des solutions de sels d'uranyle dans les phosphates butyliques

    Energy Technology Data Exchange (ETDEWEB)

    Coulon, A [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1965-06-01

    A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from {approx} 1270 cm{sup -1} to {approx} 1180 cm{sup -1}. A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [French] Une etude spectroscopique dans l'infrarouge moyen portant sur les associations: - phosphates trialcoyliques (tributylique - triethylique - trimethylique) - sels d'uranyle (nitrate, chlorure, acetate) a confirme l'existence d'une interaction entre le groupement phosphoryle et l'atome d'uranium, se manifestant par un deplacement de la bande d'absorption de la vibration de valence P = 0 de {approx} 1270 cm{sup -1} a {approx} 1180 cm{sup -1}. Une etude preparative, analytique et spectroscopique des solides obtenus par precipitation de sels d'uranyle par les phosphates butyliques acides a ete effectuee. La spectrophotomerie infrarouge met en evidence l'association, anterieure a toute introduction d'uranium, des phosphates tributylique et dibutylique dans des diluants non polaires. L'extraction de sels d'uranyle, d'une solution aqueuse acide par un melange dilue de phosphates tributylique et dibutylique, s'effectue suivant des processus differents a la nature de l'anion (nitrate ou chlorure). (auteur)

  10. Transport of anhydrous ammoniac - risk assessment

    International Nuclear Information System (INIS)

    Castellano, S.; Degrange, J.P.; Hubert, P.; Pages, P.; Lamblin, J.

    1989-12-01

    This risk analysis of anhydrous ammonia transport in France was done within a study initiated by the Department of dangerous goods of the Ministry of transport. The study deals with the road and rail transportation of bulk anhydrous ammonia. After analysis of transport system and traffic, the transport accident risks are estimated, as well as their distribution on the French territory. Finally after a synthesis of results, a number of safety measures to be undertaken were identified. This is a joint study of SMC-CEPN, with a specific role of SEMA-METRA-CONSEIL concerning the traffic frequency, and the center for risk evaluation concerning nuclear safety

  11. Anhydrous hydrogen fluoride electrolyte battery. [Patent application

    Science.gov (United States)

    Not Available

    1972-06-26

    It is an object of the invention to provide a primary cell or battery using ammonium fluoride--anhydrous hydrogen fluoride electrolyte having improved current and power production capabilities at low temperatures. It is operable at temperatures substantially above the boiling point of hydrogen fluoride. (GRA)

  12. 46 CFR 151.50-32 - Ammonia, anhydrous.

    Science.gov (United States)

    2010-10-01

    ... enclosed anhydrous ammonia tanks complies with the following chemical and physical properties: (1) Boiling... requirements of § 151.50-30 for compressed gases are also applicable to the shipment of anhydrous ammonia...

  13. Uranyl fluoride luminescence in acidic aqueous solutions

    International Nuclear Information System (INIS)

    Beitz, J.V.; Williams, C.W.

    1996-01-01

    Luminescence emission spectra and decay rates are reported for uranyl species in acidic aqueous solutions containing HF or added NaF. The longest luminescence lifetime, 0.269 ± 0.006 ms, was observed from uranyl in 1 M HF + 1 M HClO 4 at 296 K and decreased with increasing temperature. Based on a luminescence dynamics model that assumes equilibrium among electronically excited uranyl fluoride species and free fluoride ion, this long lived uranyl luminescence in aqueous solution is attributed primarily to UO 2 F 2 . Studies on the effect of added LiNO 3 or Na 2 WO 4 ·2H 2 O showed relatively weak quenching of uranyl fluoride luminescence which suggests that high sensitivity determination of the UF 6 content of WF 6 gas should be feasible via uranyl luminescence analysis of hydrolyzed gas samples of impure WF 6

  14. EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

    Science.gov (United States)

    Furman, N.H.; Mundy, R.J.

    1957-12-10

    An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.

  15. Chemistry of the uranyl group

    International Nuclear Information System (INIS)

    Zarli, B.; Dall'olio, G.; Sindellari, L.

    1976-01-01

    Some uranyl complexes with hexamethylphosphoramide (HMPA) and urea were prepared and characterized. The compounds with the former ligand have the general formula UO 2 X 2 .HMPA (where X = (C 2 H 5 ) 2 NCSe 2 - , (C 2 H 5 ) 2 NCS 2 - or CH 3 COO - ). For the acetato derivatives a dimeric acetato-bridged structure is suggested. Some properties of UO 2 (NO 3 ) 2 .2(HMPA) are also described. With the latter ligand, in addition to the complexes UO 2 (NO 3 ) 2 .2urea and [UO 2 (urea) 4 (H 2 0)](NO 3 ) 2 already known, the novel complexes UO 2 (pycrate) 2 .4urea and [UO 2 (CH 3 COO) 2 .urea]sub(n) (where n is probably 2) have been prepared. All attempts to obtain urea complexes of uranyl diethyldithio- or diethyldiselenocarbamate failed and only adducts of unsatisfactory stoichiometry were isolated. (author)

  16. THz characterization of hydrated and anhydrous materials

    Science.gov (United States)

    Sokolnikov, Andre

    2011-06-01

    The characterization of anhydrous and hydrated forms of materials is of great importance to science and industry. Water content poses difficulties for successful identification of the material structure by THz radiation. However, biological tissues and hydrated forms of nonorganic substances still may be investigated by THz radiation. This paper outlines the range of possibilities of the above characterization, as well as provides analysis of the physical mechanism that allows or prevents penetration of THz waves through the substance. THz-TDS is used to measure the parameters of the characterization of anhydrous and hydrated forms of organic and nonorganic samples. Mathematical methods (such as prediction models of time-series analysis) are used to help identifying the absorption coefficient and other parameters of interest. The discovered dependencies allow designing techniques for material identification/characterization (e.g. of drugs, explosives, etc. that may have water content). The results are provided.

  17. Thermal analysis studies of ammonium uranyl carbonate

    International Nuclear Information System (INIS)

    Cao Xinsheng; Ma Xuezhong; Wang Fapin; Liu Naixin; Ji Changhong

    1988-01-01

    The simultaneous thermogravimetry and differential thermal analysis of the ammonium uranyl carbonate powder were performed with heat balance in the following atmosphers: Air, Ar and Ar-8%H 2 . The thermogravimetry and differential thermal analysis curves of the ammonium uranyl carbonate powder obtained from different source were reported and discussed

  18. Electrochemistry of acid-base reactions in anhydrous hydrogen fluoride

    International Nuclear Information System (INIS)

    Masson, J.P.; Devynck, J.; Tremillon, B.

    1975-01-01

    Electrochemical studies were made in following media: water-HF mixtures, anhydrous HF and KF solutions in HF, solutions of the SbF5 type in HF. The acidity level of these solutions was evaluated using the R(H) functions based on the strehlow hypotheses. From the pH measurement in anhydrous HF, it was possible to get acid-base titration curves and pH buffers. The behavior of quinones in anhydrous HF is presented [fr

  19. Sorption of uranyl ions on hydrous oxides

    International Nuclear Information System (INIS)

    Gupta, A.R.; Venkataramani, B.

    1988-01-01

    Sorption of uranyl ions on hydrous titanium oxide (HTiO), magnetite (MAG), and hydrous thorium oxide (HThO) has been studied as a function of pH. Hydrous oxides have been characterized by their pH-titration curves, intrinsic dissociation constants (pK ai * ) and point of zero charge (pH pzc ). The fraction of protonated surface hydroxyl groups as well as the surface pH (pH surf ) as a function of solution pH have been computed. The distribution of various hydrolyzed species of uranyl ions with solution pH have been compared with uranyl sorption isotherm on these oxides. Sorption edge in all the cases occurs when free hydroxyl groups are available on the surface and pH surf is sufficiently high to favor the formation of dimer-like species on the surface. A new model for the sorption process, called surface hydrolysis model, which explains these and other features of uranyl sorption on hydrous oxides has been proposed. The model visualizes the sorption process as linking of uranyl ions with two adjacent free surface hydroxyl groups without deprotonation (provided the surface pH is high for the hydrolysis of uranyl ions) and formation of dimer-like structures on the surface. The new model has been successfully applied to the present and other available data on uranyl ion sorption on hydrous oxides. (author)

  20. 46 CFR 98.25-5 - How anhydrous ammonia may be carried.

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 4 2010-10-01 2010-10-01 false How anhydrous ammonia may be carried. 98.25-5 Section 98... Anhydrous Ammonia in Bulk § 98.25-5 How anhydrous ammonia may be carried. (a) Anhydrous ammonia shall be..., except as otherwise provided in paragraph (b) of this section. (b) When anhydrous ammonia is to be...

  1. The dehydration of uranyl nitrate hexahydrate

    International Nuclear Information System (INIS)

    Badalov, A.; Kamalov, D.D.; Khamidov, B.O.; Mirsaidov, I.U.; Eshbekov, N.R.

    2010-01-01

    Present article is devoted to study of dehydration process of uranyl nitrate hexahydrate. The dehydration process of uranyl nitrate hexahydrate was studied by means of tensimeter method with membrane zero-manometer. The research was carried out under equilibrium conditions. It was defined that in studied temperature ranges (300-450 K) the dehydration process of UO_2(NO_3)_2 has a three stage character.

  2. Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF α mediators

    International Nuclear Information System (INIS)

    Orona, N.S.; Tasat, D.R.

    2012-01-01

    Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO 3 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO 3 . We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O 2 − ). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O 2 − may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O 2 − may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through all the range of doses tested.

  3. PVC membrane based potentiometric sensor for uranyl ion using thenoyl trifluoro acetone as ionophore

    International Nuclear Information System (INIS)

    Nanda, D.; Chouhan, H.P.S.; Maiti, B.

    2004-01-01

    Uranyl ion selective electrode based on thenoyl trifluoro acetone (TTA) incorporated into a polyvinyl chloride (PVC) membrane has been developed where dibutyl phthalate and sodium tetraphenyl borate have been used as plasticizer and anion excluder respectively. The PVC membrane containing the active ionophore, TTA, and the other ingredients has been directly cast a graphite electrode. The electrode shows near Nernstian response to UO 2 2+ in the concentration range of 10 -1 to 10 -6 mol. L -1 an average slope of 30 mV/decade. Alkali and alkaline earth ions do not interfere with the determination of uranyl ion. Interference of transition metal ions and Th (IV) is eliminated using EDTA. (author)

  4. Photochemical reduction of uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Duerksen, W.K.

    1993-10-20

    The photochemical reduction of uranyl nitrate solutions to tetravalent uranium was investigated as a means of producing uranium dioxide feed for the saltless direct oxide reduction (SDOR) process. At high uranium concentrations, reoxidation of U{sup +4} occurs rapidly. The kinetics of the nitric oxidation of tetravalent uranium depend on the concentrations of hydrogen ion, nitrate ion, nitrous acid, and tetravalent uranium in the same manner as was reported elsewhere for the nitrate oxidation of PU{sup +3}. Reaction rate data were successfully correlated with a mechanism in which nitrogen dioxide is the reactive intermediate. Addition of a nitrous acid scavenger suppresses the reoxidation reaction. An immersion reactor employing a mercury vapor lamp gave reduction times fast enough for routine production usage. Precipitation techniques for conversion of aqueous U(NO{sub 3}){sub 4} to hydrous UO{sub 2} were evaluated. Prolonged dewatering times tended to make the process time consuming. Use of 3- to 4-M aqueous NaOH gave the best dewatering times observed. Reoxidation of the UO{sub 2} by water of hydration was encountered, which required the drying process to be carried out under a reducing atmosphere.

  5. Photochemical reduction of uranyl ion with triphenylphosphine

    International Nuclear Information System (INIS)

    Brar, A.S.; Sidhu, M.S.; Sandhu, S.S.

    1981-01-01

    Photochemical reduction of uranyl ion with triphenylphosphine has been studied in acetone-water medium in the presence of sulphuric acid at 346nm, 400nm and 434nm wavelengths. The photochemical reduction is of second order and increases with increase in hydrogen ion concentration. Absorption spectra of uranyl ion in acidic medium and uranyl ion with triphenylphosphine do not show any ground state complex formation. The value of quantum yield increases with the wavelength of the radiation increase from 346 to 434nm. Plots of reciprocal of quantum yield for the formation of U(IV) versus reciprocal [triphenylphosphine] are linear. Products characterized by UV and visible, IR and TLC show the formation of U(IV) and triphenylphosphine oxide. On the basis of above observations mechanism of the photochemical reduction has been proposed. (author)

  6. Harvesting Water from Air: Using Anhydrous Salt with Sunlight

    KAUST Repository

    Li, Renyuan; Shi, Yusuf; Shi, Le; Alsaedi, Mossab.; Wang, Peng

    2018-01-01

    Atmospheric water is abundant alternative water resource, equivalent to 6 times of water in all rivers on Earth. This work screens 14 common anhydrous and hydrated salt couples in terms of their physical and chemical stability, water vapor

  7. Infrared Spectroscopy of Discrete Uranyl Anion Complexes

    International Nuclear Information System (INIS)

    Groenewold, G. S.; Gianotto, Anita K.; McIIwain, Michael E.; Van Stipdonk, Michael J.; Kullman, Michael; Moore, David T.; Polfer, Nick; Oomens, Jos; Infante, Ivan A.; Visscher, Lucas; Siboulet, Bertrand; De Jong, Wibe A.

    2008-01-01

    The Free-Electron Laser for Infrared Experiments (FELIX) w 1 as used to study the wavelength-resolved multiple photon photodissociation of discrete, gas phase uranyl (UO2 2 2+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was either hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands, and are comparable to solution phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm-1 higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data, and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity

  8. Thermal decomposition of uranyl sulphate hydrate

    International Nuclear Information System (INIS)

    Sato, T.; Ozawa, F.; Ikoma, S.

    1980-01-01

    The thermal decomposition of uranyl sulphate hydrate (UO 2 SO 4 .3H 2 O) has been investigated by thermogravimetry, differential thermal analysis, X-ray diffraction and infrared spectrophotometry. As a result, it is concluded that uranyl sulphate hydrate decomposes thermally: UO 2 SO 4 .3H 2 O → UO 2 SO 4 .xH 2 O(2.5 = 2 SO 4 . 2H 2 O → UO 2 SO 4 .H 2 O → UO 2 SO 4 → α-UO 2 SO 4 → β-UO 2 SO 4 → U 3 O 8 . (author)

  9. Extraction of uranyl sulfate with primary amine

    International Nuclear Information System (INIS)

    Mrnka, M.; Bizek, V.; Nekovar, P.; Cizevska, S.; Schroetterova, D.

    1984-01-01

    PRIMENE JM-T was used for extraction. Its composition was found to approach the general formula C 21 H 43 NH 2 . It was found that the extraction of uranyl sulfate is lower in case of a higher steady-state concentration of sulfuric acid in the aqueous phase. Extraction is accompanied with coextraction of water. The results obtained showed that uranyl sulfate passes into the organic phase by two mechanisms: extraction with amine sulfate and extraction with free amine. A mathematical description of the process was made based on the obtained results. (E.S.)

  10. Splitting of the luminescent excited state of the uranyl ion

    International Nuclear Information System (INIS)

    Flint, C.D.; Sharma, P.; Tanner, P.A.

    1982-01-01

    The luminescence spectra of some uranyl compounds has been studied. It has been proposed that the splitting of the luminescent excited state of the uranyl ion is due to a descent in symmetry experienced by the uranyl ion when it is placed in a crystal field. In recent years there has been developed a highly successful model of the electronic structure of the uranyl ion. In this paper the authors use this model to interpret the luminescence spectra of a variety of uranyl compounds

  11. Luminescence enhancement of uranyl ion by benzoic acid in acetonitrile

    International Nuclear Information System (INIS)

    Satendra Kumar; Maji, S.; Joseph, M.; Sankaran, K.

    2014-01-01

    Uranyl ion is known for its characteristic green luminescence and therefore luminescence spectroscopy is a suitable technique for characterizing different uranyl species. In aqueous medium, luminescence of uranyl ion is generally weak due to its quenching by water molecules and therefore in order to enhance the luminescence of uranyl ion in aqueous medium, luminescence enhancing reagents such as H 3 PO 4 , H 2 SO 4 , HCIO 4 have been widely used. The other method to enhance the uranyl luminescence is by ligand sensitized luminescence, a method well established for lanthanides. In this work, luminescence of uranyl ion is found to be enhanced by benzoic acid in acetonitrile medium. In aqueous medium benzoic acid does not enhance the uranyl luminescence although it forms 1:1 and 1:2 complexes with uranyl ion. Luminescence spectra of uranyl benzoate revealed that enhancement is due to sensitization of uranyl luminescence by benzoate ions. UV-Vis spectroscopy has been utilized to characterize the specie formed in the in acetonitrile medium. UV-Vis spectroscopy along with luminescence spectra revealed that the specie to be tribenzoate complex of uranyl (UO 2 (C 6 H 5 COO) 3 ) - having D 3 h symmetry. (author)

  12. Chloride Test

    Science.gov (United States)

    ... metabolic acidosis ) or when a person hyperventilates (causing respiratory alkalosis ). A decreased level of blood chloride (called hypochloremia) ... disease , emphysema or other chronic lung diseases (causing respiratory ... metabolic alkalosis). An increased level of urine chloride can indicate ...

  13. Uranyl tris-beta-diketonate complexes

    International Nuclear Information System (INIS)

    Sidorenko, G.V.; Adamov, V.M.; Shcherbakova, L.L.; Suglubov, D.N.

    1986-01-01

    Uranyl tris-pivaloyltrifluoroacetonates (M/IOTA/UO 2 L 3 ; M/IOTA/ = Na, K, Cs, 1/2Ba, NR 4 ; R = C 8 H 17 ) and tris-dipivaloylmethanate (M/IOTA/UO 2 L/IOTA/ 3 , M/IOTA/ = K) have been synthesized for the first time. The compounds were characterized by chemical analysis and IR, NMR, and mass spectra. NaUO 2 L 3 , KUO 2 L 3 , CsUO 2 L 3 and Ba(UO 2 ) 2 L 6 sublime in high vacuum with partial decomposition. Specifically, decomposition gives UL 4 , identified by mass spectrometry. All the tris-complexes except those with outer-sphere NR 4 cation are characterized by an asymmetric structure of the uranyl group, recorded by IR spectroscopy using isotopic substitution of 18 O in uranyl. NMR spectra of the tris-complexes indicate the equivalence of all beta-diketonate groups, i.e., a coordination number of six for uranyl

  14. Photochemical reduction of uranyl ion with amides

    International Nuclear Information System (INIS)

    Brar, A.S.; Chander, R.; Sandhu, S.S.

    1981-01-01

    The photochemical reduction of uranyl ion by formamide, acetamide, propionamide, butyramide, iso butyramids, n-methylformamide, N, N-dimethylformamide and N, N-diethylformamide in aqueous medium using radiation >= 380 nm from a medium pressure mercury vapour lamp has been investigated. The reduction with the said amides has been found to obey pseudo first order kinetics. The magnitude of the rate of reduction for the simple amides has been found to follow the following order formamide > isobutyramide approx. butyramide > propionamide > acetamide while the rate order for N-alkylformamides compared with that of the formamide has been found to be formamide > N-methylformamide > N,N-diethylformamide approx. N,N-dimethylformamide. The pseudo first order rate constants and quenching constants have been found from the kinetic data. It has been found that physical and chemical quenching compete with each other. Plots of reciprocal of quantum yields versus reciprocal [amide] have been found to be linear with intercepts on the ordinate axis. Absorption spectra of uranyl ion in doubly distilled water, in the presence of acid and in the presence of acid and amide reveal that there is no ground state interaction between uranyl ion and the amide. A mechanism of photoreduction of uranyl ion with amides has been proposed. (author)

  15. Treatment of uranyl nitrate and flouride solutions

    International Nuclear Information System (INIS)

    Rodrigo Otero, A.; Rodrigo Vilaseca, F.; Morales Calvo, G.

    1977-01-01

    A theoretical study on the fluoride complexes contained in uranyl and aluminium solutions has been carried out. Likewise concentration limits and Duhring diagrams for those solutions have been experimentally established. As a result, the optimum operation conditions for concentration by evaporation in the treatment plant, have been deduced. (Author) 12 refs

  16. The γ-irradiation stability of anhydrous ethylenediamine

    International Nuclear Information System (INIS)

    Zhong Zhijing; Long Suqun; Fu Yibei; Xu Yunshu

    2005-01-01

    Anhydrous Ethylenediamine (AEDA) was irradiated in air or nitrogen at ambient temperatures by 60 Co γ-rays. The radiation degradation products were analyzed by means of GC, GC/MS, MS and FT-IR, etc. Notable gaseous products such as hydrogen, methane, ethylene, ammonia, and some volatile liquid state radiolysis products as well, were examined, and many kinds of polymerized products were detected in the liquid remain sample. It was found that under certain conditions both the hydrogen and methane contents of the products increased with dose. Remarkable effects of radiation degradation and radiation polymerization were observed, and even severe effects were found in nitrogen ambience. Therefore, a worse γ-irradiation stability of anhydrous ethylenediamine was demonstrated. The radiation polymerization of anhydrous ethylenediamine was not reported before. (authors)

  17. Separation of uranyl ion using polyaniline

    International Nuclear Information System (INIS)

    Jayshree Ramkumar; Chandramouleeswaran, S.

    2013-01-01

    Polyaniline (Pani) was synthesized by the chemical oxidation of aniline. The use of persulphate instead of dichromate was desired in order to avoid the incorporation of chromium in the polymer matrix. The presence of chromium in the matrix, when dichromate was used as an oxidant, was confirmed by various techniques. The batch mode experiments showed that Pani could be used for separation of different metal ions. These ions were converted into their anionic complexes using suitable complexing agents. It was found that EDTA was used as a suitable reagent for the separation of Cu 2+ from Zn 2+ whereas the uranyl ion uptake could be increased to about 95 % when carbonate was used instead of EDTA as complexing agent. A possible application of the above exchange system to preconcentration of uranyl ion from seawater has also been examined. (author)

  18. Micro-SHINE Uranyl Sulfate Irradiations at the Linac

    Energy Technology Data Exchange (ETDEWEB)

    Youker, Amanda J. [Argonne National Lab. (ANL), Argonne, IL (United States); Kalensky, Michael [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey [Argonne National Lab. (ANL), Argonne, IL (United States); Schneider, John [Argonne National Lab. (ANL), Argonne, IL (United States); Byrnes, James [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2016-08-01

    Peroxide formation due to water radiolysis in a uranyl sulfate solution is a concern for the SHINE Medical Technologies process in which Mo-99 is generated from the fission of dissolved low enriched uranium. To investigate the effects of power density and fission on peroxide formation and uranyl-peroxide precipitation, uranyl sulfate solutions were irradiated using a 50-MeV electron linac as part of the micro-SHINE experimental setup. Results are given for uranyl sulfate solutions with both high and low enriched uranium irradiated at different linac powers.

  19. Cyanex based uranyl sensitive polymeric membrane electrodes.

    Science.gov (United States)

    Badr, Ibrahim H A; Zidan, W I; Akl, Z F

    2014-01-01

    Novel uranyl selective polymeric membrane electrodes were prepared using three different low-cost and commercially available Cyanex extractants namely, bis(2,4,4-trimethylpentyl) phosphinic acid [L1], bis(2,4,4-trimethylpentyl) monothiophosphinic acid [L2] and bis(2,4,4-trimethylpentyl) dithiophosphinic acid [L3]. Optimization and performance characteristics of the developed Cyanex based polymer membrane electrodes were determined. The influence of membrane composition (e.g., amount and type of ionic sites, as well as type of plasticizer) on potentiometric responses of the prepared membrane electrodes was studied. Optimized Cyanex-based membrane electrodes exhibited Nernstian responses for UO₂(2+) ion over wide concentration ranges with fast response times. The optimized membrane electrodes based on L1, L2 and L3 exhibited Nernstian responses towards uranyl ion with slopes of 29.4, 28.0 and 29.3 mV decade(-1), respectively. The optimized membrane electrodes based on L1-L3 showed detection limits of 8.3 × 10(-5), 3.0 × 10(-5) and 3.3 × 10(-6) mol L(-1), respectively. The selectivity studies showed that the optimized membrane electrodes exhibited high selectivity towards UO₂(2+) ion over large number of other cations. Membrane electrodes based on L3 exhibited superior potentiometric response characteristics compared to those based on L1 and L2 (e.g., widest linear range and lowest detection limit). The analytical utility of uranyl membrane electrodes formulated with Cyanex extractant L3 was demonstrated by the analysis of uranyl ion in different real samples for nuclear safeguards verification purposes. The results obtained using direct potentiometry and flow-injection methods were compared with those measured using the standard UV-visible and inductively coupled plasma spectroscopic methods. © 2013 Published by Elsevier B.V.

  20. Studies on conductance of uranyl soaps

    International Nuclear Information System (INIS)

    Mehrotra, K.N.; Sharma, M.; Gahlaut, A.S.

    1987-01-01

    Specific conductance of uranyl soaps in dimethylformamide indicates two critical micelle concentrations CMC(I) and CMC(II). The value of CMC(II) decreases with the increase in chain length of the soap, whereas CMC(I) does not vary at all. The results show that the soaps behave as simple electrolyte. The major conductance at infinite dilution (μsub(o)) and dissociation constant (K) of these soaps have been evaluated. (author). 12 refs

  1. Thermal decomposition kinetics of ammonium uranyl carbonate

    International Nuclear Information System (INIS)

    Kim, E.H.; Park, J.J.; Park, J.H.; Chang, I.S.; Choi, C.S.; Kim, S.D.

    1994-01-01

    The thermal decomposition kinetics of AUC [ammonium uranyl carbonate; (NH 4 ) 4 UO 2 (CO 3 ) 3 [ in an isothermal thermogravimetric (TG) reactor under N 2 atmosphere has been determined. The kinetic data can be represented by the two-dimensional nucleation and growth model. The reaction rate increases and activation energy decreases with increasing particle size and precipitation time which appears in the particle size larger than 30 μm in the mechano-chemical phenomena. (orig.)

  2. The bare uranyl(2+) ion, UO22+

    International Nuclear Information System (INIS)

    Cornehl, H.H.; Heinemann, C.; Marcalo, J.; Pires de Matos, A.; Schwarz, H.

    1996-01-01

    Ion-molecule reactions between U 2+ and oxygen donors or charge-stripping collisions between singly charged UO 2 2 ions and O 2 collision partners generate uranyl(2+) ions in the gas phase. These do not readily dissociate into singly charged fragments. The standard enthalpy of formation for UO 2 2+ is estimated to be 371±60 kcal mol -1 , in accord with the results of ab initio calculations. (orig.)

  3. Process for obtaining ammonium uranyl tri carbonate

    International Nuclear Information System (INIS)

    Santos, L.R. dos; Riella, H.G.

    1992-01-01

    The procedure adopted for obtaining Ammonium Uranyl Carbonate (AUC) from uranium hexafluoride (U F 6 ) in a aqueous solutions of ammonium hydrogen carbonate is described in this work. The precipitation is made in temperature and pH controlled. This process consists of three steps: evaporation of U F 6 , AUC precipitation and filtration of the AUC slurry. An attempt is made of correlate the parameters involved in the precipitation process of AUC with its and U O 2 characteristics. (author)

  4. The spectroscopy and structure of some lanthanide chlorides in amide solutions

    International Nuclear Information System (INIS)

    Legendziewicz, J.; Bukietynska, K; Jezowsky-Trzebiatowska, B.

    1974-01-01

    The absorption spectra of Pr, Nd, Ho, and Er anhydrous and hydrated chlorides in formamide, methyl-, dimethyl-, and diethylformamide solutions have been investigated in the range of 8000 - 4200 cm -1 . By the Judd-Oefelt method of intensity analysis and by calculating the nepheloauxetic effect, the first coordination sphere of lanthanide ions and the approximate symmetry of amide solvates of anhydrous and hydrated lanthanide chlorides were determined. A difference between symmetry and coordination numbers for light and heavy lanthanide solvates has been found. Some considerations regarding the structure of lanthanide solvates and structure of amide molecules have been made. (B.T.)

  5. Spectroscopic characterization of alkaline earth uranyl carbonates

    International Nuclear Information System (INIS)

    Amayri, Samer; Reich, Tobias; Arnold, Thuro; Geipel, Gerhard; Bernhard, Gert

    2005-01-01

    A series of alkaline uranyl carbonates, M[UO 2 (CO 3 ) 3 ].nH 2 O (M=Mg 2 , Ca 2 , Sr 2 , Ba 2 , Na 2 Ca, and CaMg) was synthesized and characterized by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS) after nitric acid digestion, X-ray powder diffraction (XRD), and thermal analysis (TGA/DTA). The molecular structure of these compounds was characterized by extended X-ray absorption fine-structure (EXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). Crystalline Ba 2 [UO 2 (CO 3 ) 3 ].6H 2 O was obtained for the first time. The EXAFS analysis showed that this compound consists of (UO 2 )(CO 3 ) 3 clusters similar to the other alkaline earth uranyl carbonates. The average U-Ba distance is 3.90+/-0.02A.Fluorescence wavelengths and life times were measured using time-resolved laser-induced fluorescence spectroscopy (TRLFS). The U-O bond distances determined by EXAFS, TRLFS, XPS, and Raman spectroscopy agree within the experimental uncertainties. The spectroscopic signatures observed could be useful for identifying uranyl carbonate species adsorbed on mineral surfaces

  6. Magnetic biosorbent for removal of uranyl ions

    International Nuclear Information System (INIS)

    Yamamura, Amanda P.G.; Yamaura, Mitiko; Costa, Caroline H.

    2009-01-01

    In this work magnetic biosorbent, which consisted of sugarcane bagasse as polymeric matrix with magnetite nanoparticles, was prepared. This magnetic composite has the purpose to remove uranyl ions from aqueous effluents. The magnetite was synthetized by simultaneous precipitation by addition a solution of NaOH to the aqueous solution containing Fe2+ and Fe3+. This magnetic bagasse biosorbent have presented superparamagnetic properties, that is, it have showed a high magnetization of saturation without hysteresis. The magnetic biosorbent was utilized to remove uranyl ions from water. Radioactive uranium waste is generated in hospitals, universities and it is used as fuel for nuclear power plants. Variables of adsorption process of uranyl ions by magnetic biosorbent in nitric solutions were investigated, such as, time required for the uranium-magnetic bagasse biosorbent equilibrium in the interval from 20 to 90 min, pH in the intervals from 2 to 5 and 10, stirring speed from 240 to 500 r.p.m. and biosorbent dose from 2 to 25 g.L-1 were investigated. Equilibrium isotherm was verified according to the Langmuir and Freundlich adsorption isotherm models. The highest adsorption capacity reached 17 mg.g-1. The Gibbs free energy indicated to be spontaneous adsorption. This work updates the paper was presented on the 2007 INAC.

  7. Uranyl sulfate irradiations at the Van de Graaff: A means to combat uranyl peroxide precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Youker, Amanda J. [Argonne National Lab. (ANL), Argonne, IL (United States); Kalensky, Michael [Argonne National Lab. (ANL), Argonne, IL (United States); Quigley, Kevin J. [Argonne National Lab. (ANL), Argonne, IL (United States); Brossard, Thomas [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey D. [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2017-05-01

    As part of an effort to support SHINE Medical Technologies in developing a process to produce Mo-99 by neutron-induced fission, a series of irradiation experiments was performed with a 3 MeV Van de Graaff accelerator to generate high radiation doses in 0.5–2 mL uranyl sulfate solutions. The purpose was to determine what conditions result in uranyl peroxide precipitation and what can be done to prevent its formation. The effects of temperature, dose rate, uranium concentration, and the addition of known catalysts for the destruction of peroxide were determined.

  8. Determination of uranyl ion by potentiometric titration using an uranyl-selective electrode

    International Nuclear Information System (INIS)

    Nassory, N.S.

    1990-01-01

    A potentiometric titration of uranyl ion is described using an uranyl selective electrode based on a membrane containing a complex of UO 2 -bis[di-4-(1,1,3,3-tetramethylbutyl)phenyl phosphate] as an ion-exchanger and tritolyl phosphate as a solvent mediator. The titrations were carried out with various titrants: Sodium hydroxide, potassium fluoride and sodium salts of acetate, oxalate and citrate. The equivalence points were determined by Gran's method. Good results were obtained by using sodium oxalate as a titrant for the determination of uranium in several samples of ammonium diuranate. The results were quite comparable with those obtained by X-ray fluorescence spectrometry. (orig.)

  9. Interaction of Ketotifen Fumarate with Anhydrous Theophylline in ...

    African Journals Online (AJOL)

    Purpose: The purpose of the present study was to investigate interaction between ketotifen fumarate and anhydrous theophylline in aqueous media of various pH. Methods: By using Job's continuous-variation analysis and Ardon's spectrophotomeric methods, the values of stability constants of theophylline with ketotifen ...

  10. Effect of anhydrous magnesium sulphate fertilizer and cutting ...

    African Journals Online (AJOL)

    Effect of anhydrous magnesium sulphate fertilizer on Panicum maximum yield and chemical composition of the resultant herbage harvested at 3, 4 and 5 weeks of age was investigated. The treatments were labeled T1 to T6. T1 was fertilized and harvested at 3 weeks cutting interval, T2 was fertilized and harvested at 4 ...

  11. Anhydrous Ammonia Training Module. Trainer's Package. Participant's Package.

    Science.gov (United States)

    Beaudin, Bart; And Others

    This document contains a trainer's and a participant's package for teaching employees on site safe handling procedures for working with anhydrous ammonia, especially on farms. The trainer's package includes the following: a description of the module; a competency; objectives; suggested instructional aids; a training outline (or lesson plan) for…

  12. Process for the production of sodium carbonate anhydrate

    NARCIS (Netherlands)

    Oosterhof, H.; Van Rosmalen, G.M.; Witkamp, G.J.; De Graauw, J.

    2000-01-01

    The invention is directed to a process for the production of sodium carbonate-anhydrate having a bulk density of at least 800 kg/m<3>, said process comprising: providing a suspension of solid sodium carbonate and/or solid sodium bicarbonate and/or solid double salts at least comprising one of sodium

  13. Contribution to the study of uranyl salts in butyl phosphate solutions; Contribution a l'etude des solutions de sels d'uranyle dans les phosphates butyliques

    Energy Technology Data Exchange (ETDEWEB)

    Coulon, A. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1965-06-01

    A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from {approx} 1270 cm{sup -1} to {approx} 1180 cm{sup -1}. A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [French] Une etude spectroscopique dans l'infrarouge moyen portant sur les associations: - phosphates trialcoyliques (tributylique - triethylique - trimethylique) - sels d'uranyle (nitrate, chlorure, acetate) a confirme l'existence d'une interaction entre le groupement phosphoryle et l'atome d'uranium, se manifestant par un deplacement de la bande d'absorption de la vibration de valence P = 0 de {approx} 1270 cm{sup -1} a {approx} 1180 cm{sup -1}. Une etude preparative, analytique et spectroscopique des solides obtenus par precipitation de sels d'uranyle par les phosphates butyliques acides a ete effectuee. La spectrophotomerie infrarouge met en evidence l'association, anterieure a toute introduction d'uranium, des phosphates tributylique et dibutylique dans des diluants non polaires. L'extraction de sels d'uranyle, d'une solution aqueuse acide par un melange dilue de phosphates tributylique et dibutylique, s'effectue suivant des processus differents a la

  14. 49 CFR 173.195 - Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution).

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Hydrogen cyanide, anhydrous, stabilized... Hazardous Materials Other Than Class 1 and Class 7 § 173.195 Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution). (a) Hydrogen cyanide, anhydrous, stabilized, must be packed in...

  15. Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF α mediators

    Energy Technology Data Exchange (ETDEWEB)

    Orona, N.S. [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); Tasat, D.R., E-mail: deborah.tasat@unsam.edu.ar [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); School of Dentistry, University of Buenos Aires, M. T. de Alvear 2142 (1122), Buenos Aires (Argentina)

    2012-06-15

    Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO{sub 3} 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO{sub 3}. We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O{sub 2}{sup −}). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O{sub 2}{sup −} may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O{sub 2}{sup −} may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through

  16. Can uranyl complexes encapsulate to carbon nanotubes? A ...

    Indian Academy of Sciences (India)

    K SRINIVASU

    We find that uranyl-aqua complex ([UO2(H2O)5]2+) binds stronger as compared to uranyl-hydroxo-complex .... until the maximum Hellmann–Feynman force on each atom ..... porters and near-infrared agents for selective cancer cell.

  17. Uranyl ion recovery from waste waters by microbiological collectors

    International Nuclear Information System (INIS)

    Cecal, Alexandru; Palamaru, Iliana; Navrotescu, Tinca

    1995-01-01

    This study deals with the bioaccumulation of uranyl ions from radioactive effluents by Scenedesmus quadricauda alga. From the experimental data one can observe a greater retaining capacity of uranyl ions after four days of contact time. Filtered uranium and alga content was determined by the arsenazo III spectrophotometric method. The colored compound was determined by using wavelength λ=665 nm. (authors)

  18. New insights into the acid mediated disproportionation of pentavalent uranyl

    Energy Technology Data Exchange (ETDEWEB)

    Mougel, Victor; Biswas, Biplab; Pecaut, Jacques; Mazzanti, Marinella [Laboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E 3 CEA-UJF FRE 3200 CNRS, INAC, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cedex 09 (France)

    2010-07-01

    The reaction of benzoic acid with the uranyl(V) complex [(UO{sub 2}Py{sub 5})(KI{sub 2}Py{sub 2})] in pyridine leads to immediate disproportionation with formation of a hexa-nuclear U(IV) benzoate cluster, a bis-benzoate complex of uranyl(VI) and water. (authors)

  19. Densities concentrations of aqueous of uranyl nitrate solutions

    International Nuclear Information System (INIS)

    Rodrigo Otero, A.; Rodriguez Hernandez, B.; Fernandez Rodriguez, L.

    1966-01-01

    The ratio density-concentration of aqueous uranyl nitrate solutions expressed as U 3 O 8 grams/liter, U grams/liter and hexahydrate uranyl nitrate weight percent at different temperatures, are established. Experimental values are graphically correlated and compared whit some published data. (Author) 2 refs

  20. Quantification of uranyl in presence of citric acid

    International Nuclear Information System (INIS)

    Garcia G, N.; Barrera D, C.E.; Ordonez R, E.

    2007-01-01

    To determine the influence that has the organic matter of the soil on the uranyl sorption on some solids is necessary to have a detection technique and quantification of uranyl that it is reliable and sufficiently quick in the obtaining of results. For that in this work, it intends to carry out the uranyl quantification in presence of citric acid modifying the Fluorescence induced by UV-Vis radiation technique. Since the uranyl ion is very sensitive to the medium that contains it, (speciation, pH, ionic forces, etc.) it was necessary to develop an analysis technique that stands out the fluorescence of uranyl ion avoiding the out one that produce the organic acids. (Author)

  1. Infrared spectra of volatile adduct of uranyl pivaloyltrifluoroacetonate with hexamethylphosphorotriamide

    International Nuclear Information System (INIS)

    Bukhmarina, V.N.; Dushin, R.B.; Sidorenko, G.V.; Suglobov, D.N.

    1983-01-01

    Adduct of uranyl pivaloyltrifluoroacetonate with hexamethylphosphortriamide (1), sublimated without decomposition and characterized by a high thermal stability, has been synthesized, as well as adducts of uranyl dipivaloylmethanate with hexamethylphosphortriamide (2) and dimethyl sulfoxide (3), sublimated with partial dissociation. IR spectra of crystalline adducts 1-3, their solutions in benzene; gaseous and matrix-isolated adduct 1 have been measured. It is shown that in gaseous phase 1 exists practically completely in non-dissociated form. It is detected that uranyl group in crystalline 1 and 2 and in matrix-isolated 1 in contrast to crystalline 3 and previously studied adducts of uranyl β-diketonates has an asymmetric structure. Strength constants of uranyl group in crystalline 1-3 and matrix-isolated 1 are determined

  2. Specific capture of uranyl protein targets by metal affinity chromatography

    International Nuclear Information System (INIS)

    Basset, C.; Dedieu, A.; Guerin, P.; Quemeneur, E.; Meyer, D.; Vidaud, C.

    2008-01-01

    To improve general understanding of biochemical mechanisms in the field of uranium toxicology, the identification of protein targets needs to be intensified. Immobilized metal affinity chromatography (IMAC) has been widely developed as a powerful tool for capturing metal binding proteins from biological extracts. However uranyl cations (UO 2 2+ ) have particular physico-chemical characteristics which prevent them from being immobilized on classical metal chelating supports. We report here on the first development of an immobilized uranyl affinity chromatography method, based on the cation-exchange properties of amino-phosphonate groups for uranyl binding. The cation distribution coefficient and loading capacity on the support were determined. Then the stability of the uranyl-bonded phase under our chromatographic conditions was optimized to promote affinity mechanisms. The successful enrichment of uranyl binding proteins from human serum was then proven using proteomic and mass spectral analysis. (authors)

  3. Uranyl oxalate hydrates: structures and IR spectra

    International Nuclear Information System (INIS)

    Giesting, P.A.; Porter, N.J.; Burns, P.C.

    2006-01-01

    The novel compound (UO 2 ) 2 C 2 O 4 (OH) 2 (H 2 O) 2 (UrOx2A) and the previously studied compound UO 2 C 2 O 4 (H 2 O) 3 (UrOx3) have been synthesized by mild hydrothermal methods. Single crystal diffraction data collected at 125 K using MoK α radiation and a CCD-based area detector were used to solve and refine the crystal structures by full-matrix least-squares techniques to agreement indices (UrOx2A, UrOx3) wR 2 = 0.037, 0.049 for all data, and R1 0.015, 0.024 calculated for 1285, 2194 unique reflections respectively. The compound UrOx2A is triclinic, space group P1, Z = 1, a = 5.5353(4), b 6.0866(4), c = 7.7686(6) Aa, α = 85.6410(10) , β = 89.7740(10) , γ = 82.5090(10) , V = 258.74(3) Aa 3 . The compound UrOx3 is monoclinic, space group P2 1 /c, Z = 4, a = 5.5921(4), b = 16.9931(13), c = 9.3594(7) Aa, β = 99.5330(10) , V = 877.11(11) Aa 3 . The structures consist of chains of uranyl pentagonal bipyramids connected by oxalate groups and, in UrOx2A, hydroxyl groups; UrOx2A is also notable for its high (2:1) ratio of uranyl to oxalate groups, higher than any observed in other published structures of uranyl oxalates. The structure determined for UrOx3, previously studied by Jayadevan and Chackraburtty (1972); Mikhailov et al. (1999) is in agreement with the previous results; however, the increased precision of the present low-temperature structure refinement allows for the assignment of H atom positions based on the difference Fourier map of electron density. The infrared spectra of these two materials collected at room temperature are also presented and compared with previous work on uranyl oxalate systems. (orig.)

  4. Glass transition of anhydrous starch by fast scanning calorimetry.

    Science.gov (United States)

    Monnier, Xavier; Maigret, Jean-Eudes; Lourdin, Denis; Saiter, Allisson

    2017-10-01

    By means of fast scanning calorimetry, the glass transition of anhydrous amorphous starch has been measured. With a scanning rate of 2000Ks -1 , thermal degradation of starch prior to the glass transition has been inhibited. To certify the glass transition measurement, structural relaxation of the glassy state has been investigated through physical aging as well as the concept of limiting fictive temperature. In both cases, characteristic enthalpy recovery peaks related to the structural relaxation of the glass have been observed. Thermal lag corrections based on the comparison of glass transition temperatures measured by means of differential and fast scanning calorimetry have been proposed. The complementary investigations give an anhydrous amorphous starch glass transition temperature of 312±7°C. This estimation correlates with previous extrapolation performed on hydrated starches. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Process for the production of sodium carbonate anhydrate

    OpenAIRE

    Oosterhof, H.; Van Rosmalen, G.M.; Witkamp, G.J.; De Graauw, J.

    2000-01-01

    The invention is directed to a process for the production of sodium carbonate-anhydrate having a bulk density of at least 800 kg/m, said process comprising: providing a suspension of solid sodium carbonate and/or solid sodium bicarbonate and/or solid double salts at least comprising one of sodium carbonate and sodium bicarbonate, in a mixture containing water and an organic, water miscible or partly water miscible solvent, which solvent influences the transition temperature below which sodium...

  6. Computer simulation of uranyl uptake by the rough lipopolysaccharide membrane of Pseudomonas aeruginosa.

    Science.gov (United States)

    Lins, Roberto D; Vorpagel, Erich R; Guglielmi, Matteo; Straatsma, T P

    2008-01-01

    Heavy metal environmental contaminants cannot be destroyed but require containment, preferably in concentrated form, in a solid or immobile form for recycling or final disposal. Microorganisms are able to take up and deposit high levels of contaminant metals, including radioactive metals such as uranium and plutonium, into their cell wall. Consequently, these microbial systems are of great interest as the basis for potential environmental bioremediation technologies. The outer membranes of Gram-negative microbes are highly nonsymmetric and exhibit a significant electrostatic potential gradient across the membrane. This gradient has a significant effect on the uptake and transport of charged and dipolar compounds. However, the effectiveness of microbial systems for environmental remediation will depend strongly on specific properties that determine the uptake of targeted contaminants by a particular cell wall. To aid in the design of microbial remediation technologies, knowledge of the factors that determine the affinity of a particular bacterial outer membrane for the most common ionic species found in contaminated soils and groundwater is of great importance. Using our previously developed model for the lipopolysaccharide (LPS) membrane of Pseudomonas aeruginosa, this work presents the potentials of mean force as the estimate of the free energy profile for uptake of sodium, calcium, chloride, uranyl ions, and a water molecule by the bacterial LPS membrane. A compatible classical parameter set for uranyl has been developed and validated. Results show that the uptake of uranyl is energetically a favorable process relative to the other ions studied. At neutral pH, this nuclide is shown to be retained on the surface of the LPS membrane through chelation with the carboxyl and hydroxyl groups located in the outer core.

  7. Behind adhesion of uranyl onto montmorillonite surface: A molecular dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Yang, W.; Zaoui, A., E-mail: azaoui@polytech-lille.fr

    2013-10-15

    Highlights: • We investigated the adsorption of uranyl onto Montmorillonite surface. • We studied the surface energy between layered Montmorillonite sheets. • We studied the work of adhesion between radionuclide and charged Montmorillonite. -- Abstract: We have performed molecular dynamics simulations to investigate the adsorption of radionuclide elements species onto substituted Montmorillonite (001) surface in the presence of different counterions. The structure and the dynamics of uranyl ion as well as its aquo, chloride ion, and carbonate complexes are analyzed. In addition, we have studied the surface energy between layered Montmorillonite sheets and the work of adhesion between radionuclide and charged Montmorillonite. The clay model used here is a Wyoming-type Montmorillonite with 0.75e negative charge per unit cell resulting from substitutions in Octahedral and Tetrahedral sheets. The system model was constructed based on CLAYFF force field potential model. To evaluate the thermodynamic work of adhesion, each surface and clay layer regions are converted to a thin film model. One and two species of radionuclide elements (UO{sub 2}(H{sub 2}O){sub 5},UO{sub 2}CO{sub 3}(H{sub 2}O){sub 5}, and UO{sub 2}Cl{sub 2}(H{sub 2}O){sub 5}) were deposited near the clay surface in a pseudo-two-dimensional periodic cell. Analysis shows that the uranyl ion structure is preserved with two axial oxygen atoms detected at 1.8 Å. Radial distribution functions results indicate that average U-O{sub w} distances are 2.45–2.61 Å, and 2.29–2.40 Å for U-O{sub c} distance. Average U-Cl distances are 2.78–3.08 Å, which is relatively larger than that of Uranium atom-Oxygen atom because of electrostatic factors.

  8. Dry fumes purifying system using anhydrous baking soda; Procede chimique d`epuration des fumees au bicarbonate de soude anhydre

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    1998-04-01

    UNISYSTEMS has developed the industrial implementation of the chemical process using anhydrous backing soda, patented by SOLVAY, for purifying fumes containing inorganic salts and sulphur oxides as polluting agents. The system can be applied to industrial processes releasing this type of polluting agents in the fumes at a temperature over 160 deg C, as it is specially indicated in purifying fumes coming from ceramic firing kilns. (authors)

  9. Uranyl soaps - thermal, electronic and infrared spectral study

    International Nuclear Information System (INIS)

    Solanki, A.K.; Bhandari, A.M.

    1981-01-01

    The electronic and infrared spectra and TGA thermogram of uranyl soaps (laurate, mystrate, palmitate and stearate) have been studied. The environment about the UO 2+ 2 ion would comprise two 'short bite' bidentate carboxylate groups and oxygen atoms bridging from adjacent carboxylic molecules. The uranyl soaps have UO 2+ 2 vibronic absorption (approx. equal to 22730 cm -1 ) in the range found for eight coordinate uranyl complexes. The greater resistance to thermal degradation (approx. equal to 300 0 C) of these soaps and their stepwise thermal degradation infer strong metal-ligand interaction. (orig.) [de

  10. Thermal decomposition of ammonium diuranate, uranyl nitrate hexahydrate and uranyl peroxide

    International Nuclear Information System (INIS)

    Yulianto, T.; Mutiara, E.

    2011-01-01

    The behaviors of three types of starting powder had been investigated during their thermal decomposition processes in nitrogen, air, and hydrogen. The powder types were the products of uranyl nitrate precipitation, i.e. ADU (ammonium diuranate), UNH (uranyl nitrate hexahydrate), and UPO (uranyl peroxide). The objective of the investigation was to find out the best atmosphere that would result in good quality powder in a thermal decomposition process with the lowest temperature and the shortest period of time in order to reduce the cost of UO 2 powder preparation. Before the thermal decomposition process was initiated, all powder types were characterized for their crystal structures. The investigation was conducted by TG-DTA instrument at temperature up to 800°C and the heating rate of 10°C/minute. The crystal structures were identified by X-Ray Diffractometer with Cu-Ka radiation. The specific surface area of the powder was also observed using BET method, especially for the powder that underwent the process in hydrogen heated up to 800°C. The Results showed that the process took place faster in hydrogen, and UNH required lower thermal decomposition temperature in relations with other types of powder. (author)

  11. Quasirelativistic pseudopotential study of species isoelectronic to uranyl and the equatorial coordination of uranyl

    International Nuclear Information System (INIS)

    Pyykkoe, P.; Li, J.; Runeberg, N.

    1994-01-01

    The calculated trends of geometries and vibrational frequencies of several uranyl isoelectronic species, like the known NUN and CUO, and the unknown CUN - , NUO + , and NUF 2+ , are reported. The NUN and CUO results support the matrix spectroscopic assignments. The simplest example of equatorial coordination to uranyl is the C 2d species UO 3 . Its calculated vibrational frequencies also support matrix spectroscopic ones. We earlier suggested that the large range of uranyl bond lengths in UO 6 6- -type systems could be interpreted in terms of a open-quotes frozen, soft e g vibrational modeclose quotes. Further studies on UF 6 , U(OH) 6 , [(OUO)(F eq ) n ] (n-2) -, [(OUO)(NO 3 ) 3 ] - , and [(OUO)(CO 3 ) 3 ] 4- show only small variation of R ax as function of R eq . Thus, the all-oxide case is a special one, where all ligands are capable of single and multiple bonding. 44 refs., 10 figs., 7 tabs

  12. Solid solutions of hydrogen uranyl phosphate and hydrogen uranyl arsenate. A family of luminescent, lamellar hosts

    International Nuclear Information System (INIS)

    Dorhout, P.K.; Rosenthal, G.L.; Ellis, A.B.

    1988-01-01

    Hydrogen uranyl phosphate, HUO 2 PO 4 x 4H 2 O (HUP), and hydrogen uranyl arsenate, HUO 2 AsO 4 x 4H 2 O (HUAs), form solid solutions of composition HUO 2 (PO 4 ) 1-x (AsO 4 )x (HUPAs), representing a family of lamellar, luminescent solids that can serve as hosts for intercalation chemistry. The solids are prepared by aqueous precipitation reactions from uranyl nitrate and mixtures of phosphoric and arsenic acids; thermogravimetric analysis indicates that the phases are tetrahydrates, like HUP and HUAs. Powder x-ray diffraction data reveal the HUPAs solids to be single phases whose lattice constants increase with X, in rough accord with Vegard's law Spectral shifts observed for the HUPAs samples. Emission from the solids is efficient (quantum yields of ∼ 0.2) and long-lived (lifetimes of ∼ 150 μs), although the measured values are uniformly smaller than those of HUP and HUAs; unimolecular radiative and nonradiative rate constants for excited-state decay of ∼ 1500 and 5000 s -1 , respectively, have been calculated for the compounds. 18 refs., 5 figs., 2 tabs

  13. Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O and anhydrous Rb[UO2(AsO3OH)(AsO2(OH)2)

    Science.gov (United States)

    Yu, Na; Klepov, Vladislav V.; Villa, Eric M.; Bosbach, Dirk; Suleimanov, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.; Alekseev, Evgeny V.

    2014-07-01

    The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O (α-, β-RbUAs) and the anhydrous phase Rb[UO2(AsO3OH)(AsO2(OH)2)] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions.

  14. Colorimetric peroxidase mimetic assay for uranyl detection in sea water

    KAUST Repository

    Zhang, Dingyuan; Chen, Zhuo; Omar, Haneen; Deng, Lin; Khashab, Niveen M.

    2015-01-01

    Uranyl (UO2 2+) is a form of uranium in aqueous solution that represents the greatest risk to human health because of its bioavailability. Different sensing techniques have been used with very sensitive detection limits especially the recently

  15. Uranyl phosphate mineral in Gapyeong area

    International Nuclear Information System (INIS)

    Chung, S.J.

    1980-01-01

    An uranyl phosphate crystal from Gapeong area is studied by means of single crystal x-ray diffraction and electron microscopic qualitative analysis of chemical contents. The crystal is identified as meta-ankoleite which has a unit cell of super structure with a=b=6.99 A, c=17.69 A and space group P4 2 22. There exists some indication in the total fluorescent spectrum of the sample that potassium may be partially substituted by calcium. The chemical formula of this meta-ankoleite may be expressed by Ksub(1-2x)Casub(x)(UO 2 PO 4 ) (H 2 O)sub(3-x). (Author)

  16. Glutathione attenuates uranyl toxicity in Lactococcus lactis

    Energy Technology Data Exchange (ETDEWEB)

    Fahmy, Karim; Oertel, Jana [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biophysics; Obeid, M. [Technische Univ. Dresden (Germany); Solioz, M. [Bern Univ. (Switzerland)

    2017-06-01

    We investigated the role of intracellular glutathione (GSH), which in a large number of taxa plays a role in the protection against the toxicity of heavy metals. Anaerobically grown Lactococcus lactis containing an inducible GSH synthesis pathway was used as a model organism allowing the study of GSH-dependent uranyl detoxification without interference from additional reactive oxygen species. Microcalorimetric measurements of the metabolic heat showed that intracellular GSH attenuates the toxicity of uranium at a concentration in the range of 10-150 μM. Isothermal titration calorimetry revealed the endothermic binding of U(VI) to the carboxyl group(s) of GSH. The data indicate that the primary detoxifying mechanism is the intracellular sequestration of carboxyl-coordinated U(VI) into an insoluble complex with GSH.

  17. Glutathione attenuates uranyl toxicity in Lactococcus lactis

    International Nuclear Information System (INIS)

    Fahmy, Karim; Oertel, Jana; Solioz, M.

    2017-01-01

    We investigated the role of intracellular glutathione (GSH), which in a large number of taxa plays a role in the protection against the toxicity of heavy metals. Anaerobically grown Lactococcus lactis containing an inducible GSH synthesis pathway was used as a model organism allowing the study of GSH-dependent uranyl detoxification without interference from additional reactive oxygen species. Microcalorimetric measurements of the metabolic heat showed that intracellular GSH attenuates the toxicity of uranium at a concentration in the range of 10-150 μM. Isothermal titration calorimetry revealed the endothermic binding of U(VI) to the carboxyl group(s) of GSH. The data indicate that the primary detoxifying mechanism is the intracellular sequestration of carboxyl-coordinated U(VI) into an insoluble complex with GSH.

  18. Thermodynamics of dehydration process of uranyl nitrate pentahydrate of thorium

    International Nuclear Information System (INIS)

    Khamidov, F.A.; Mirsaidov, I.U.; Nazarov, K.M.; Nasriddinov, S.K.; Badalov, A.B.

    2010-01-01

    Present article is devoted to thermodynamics of dehydration process of uranyl nitrate pentahydrate of thorium. The results of researches of dehydration process of uranyl nitrate pentahydrate of thorium Th(NO_3)_4·5H_2O were considered. The researches were carried out by means of tensimeter method with membrane zero-manometer under equilibrium conditions and at 300-450 K temperature ranges. The thermodynamic characteristics of dehydration process of initial crystalline hydrate was defined.

  19. Radiolysis studies of uranyl nitrate solution in nitric acid medium

    International Nuclear Information System (INIS)

    Siri, Sandra; Mondino, Angel V.

    2005-01-01

    The radiolysis of acidic uranyl nitrate solutions was investigated using Co-60 gamma radiation. Hydrogen peroxide was determined as a function of increasing dose. The UV-vis absorption spectra of the irradiated solutions were measured and the spectral changes were analyzed. The increasing dose increases the absorbance intensities, possibly by an increment in nitrate concentration produced by radiolysis, which can originate the formation of different uranyl complexes in solution. (author)

  20. Thermal decomposition of anhydrous zinc and cadmium salicylates

    International Nuclear Information System (INIS)

    Kharitonov, Yu.Ya.; Tujebakhova, Z.K.

    1984-01-01

    On the basis of studying thermograms, thermogravigrams, IR absorption spectra, X-rayograms of anhydrous znc and cadmium salicylate complexes of the M(HSal) 2 composition, (where M=Zn, Cd; HSal is an anion of once deprotonated salicyclic acid H 2 Sal) and products of their thermal transformations, the processes are characterized of stage-by-stage thermal decomposition of these compounds under continuous heating in the air from room temperature to approximately 1000 deg C. It is shown that the Cd(HSal) 2 pyrolysis proceeds with the formation of CdSal at 170-250 deg C and CdO - at 320-460 deg C

  1. Crystallo-chemistry of boric anhydride and of anhydrous borates

    International Nuclear Information System (INIS)

    Bernardin, Jacques

    1968-01-01

    After an overview of various aspects related to the atomic structure of boron and of its three-bind and four-bind compounds, this report briefly presents the different forms of boric anhydride (in solid, liquid, glassy and gaseous state), presents and comments the structure of these different forms, and addresses the molten boric anhydride which is used as oxide solvent. The next part addresses the structure of anhydrous borates. It presents some generalities on their structure, and describes examples of known structures: dimers, trimers, polymers with a degree higher than three like calcium metaborate, caesium tri-borate, lithium tetraborate, or potassium pentaborate

  2. A New Thickener for CO2 Anhydrous Fracturing Fluid

    Directory of Open Access Journals (Sweden)

    Zhang Jian

    2015-01-01

    Full Text Available CO2 dry fracturing technology is well-known for its advantages. Little water is used in this technology, which is able to ease the pressure of consumption on water resources. Many abroad theoretical researches, laboratory experiments and field tests have been taken to explore the yield mechanism, the adaptability and the technology of pure liquid CO2 fracturing. These achievements have been applied to a variety of reservoirs transformation and improven the effectiveness of stimulation treatment in a degree. The researches and studies in the domestic didn’t get popular until recent years. Thus, this article firstly introduces the main development and application about pure CO2 anhydrous fracturing technology, and sums up the effect and evaluation of its fluid through application examples both in the domestic and abroad. However, although this technology has many excellent qualities, but systematic studies indicate that its proppant-carrying capacity is less competitive because of the low viscosity of pure CO2 liquid and other reasons. In a consequence, it is necessary to develop an appropriate thickener for CO2 anhydrous fracturing fluid to improve its carrying capacity. Then this article describes some studies of previous scholars about CO2 thickener. Then we put forward our own research ideas and transform it into actual experiments. Thanks to the valid performances of these tests, we successfully develop a thickener X and cosolvent B.

  3. Anhydrous crystals of DNA bases are wide gap semiconductors.

    Science.gov (United States)

    Maia, F F; Freire, V N; Caetano, E W S; Azevedo, D L; Sales, F A M; Albuquerque, E L

    2011-05-07

    We present the structural, electronic, and optical properties of anhydrous crystals of DNA nucleobases (guanine, adenine, cytosine, and thymine) found after DFT (Density Functional Theory) calculations within the local density approximation, as well as experimental measurements of optical absorption for powders of these crystals. Guanine and cytosine (adenine and thymine) anhydrous crystals are predicted from the DFT simulations to be direct (indirect) band gap semiconductors, with values 2.68 eV and 3.30 eV (2.83 eV and 3.22 eV), respectively, while the experimentally estimated band gaps we have measured are 3.83 eV and 3.84 eV (3.89 eV and 4.07 eV), in the same order. The electronic effective masses we have obtained at band extremes show that, at low temperatures, these crystals behave like wide gap semiconductors for electrons moving along the nucleobases stacking direction, while the hole transport are somewhat limited. Lastly, the calculated electronic dielectric functions of DNA nucleobases crystals in the parallel and perpendicular directions to the stacking planes exhibit a high degree of anisotropy (except cytosine), in agreement with published experimental results.

  4. Standard test methods for chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    1999-01-01

    1.1 These test methods cover procedures for the chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solution to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Determination of Uranium 7 Specific Gravity by Pycnometry 15-20 Free Acid by Oxalate Complexation 21-27 Determination of Thorium 28 Determination of Chromium 29 Determination of Molybdenum 30 Halogens Separation by Steam Distillation 31-35 Fluoride by Specific Ion Electrode 36-42 Halogen Distillate Analysis: Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 43 Determination of Chloride and Bromide 44 Determination of Sulfur by X-Ray Fluorescence 45 Sulfate Sulfur by (Photometric) Turbidimetry 46 Phosphorus by the Molybdenum Blue (Photometric) Method 54-61 Silicon by the Molybdenum Blue (Photometric) Method 62-69 Carbon by Persulfate Oxidation-Acid Titrimetry 70 Conversion to U3O8 71-74 Boron by ...

  5. Investigations in anhydrous liquid ammonia. Reaction of group 2, 4, 5, 11 metal and actinoids compounds

    International Nuclear Information System (INIS)

    Woidy, Patrick

    2014-01-01

    compounds led to the characterization of pentaammine complexes of the dioxidouranium cation which also was shown to form di-, tetra- or octanuclear networks via oxygen bridges. In the tetra- and octanuclear compounds, penta- and hexavalent uranyl cations seem to be present in one compound. The reactions of TiCl 3 and UF 4 and the reaction of Cs[UO 2 (NO 3 ) 3 ] and CuF 2 , yielded the new compounds [UF(NH 3 ) 8 ]Cl 3 . 3,5 NH 3 and Cs[UO 2 F 3 (NH 3 ) 2 ], respectively. Both compounds demonstrated on the one hand the possibility of the exchange of halides and on the other hand the ability to accept fluoride ions. Additionally, a new method for the synthesis of uranyl chloride is presented. Experiments regarding the solubility of metal halides of group 2, 4, and 5 of the periodic table yielded the ammonia complexes of [Ca(NH 3 ) 8 ]X 2 (X = Br and I), [Ti(NH 3 ) 8 ]Cl 3 . 6 NH 3 , and mer-[VF 3 (NH 3 ) 3 ]. Instead of the expected tetragonal antiprism for the eightfold coordinated Ca 2+ ion, a coordination polyhedron best described as a twofold capped trigonal prism and for the Ti 3+ ion an untypical eightfold coordination can be observed. Characterization of the novel compounds was carried out by single crystal and powder X-ray diffraction, infrared and Raman spectroscopy, thermogravimetry and mass spectrometry.

  6. Functional polyterthiophene-appended uranyl-salophen complex: electropolymerization and ion-selective response for monohydrogen phosphate.

    Science.gov (United States)

    Kim, Junghwan; Kang, Dong Min; Shin, Sung Chul; Choi, Myong Yong; Kim, Jineun; Lee, Shim Sung; Kim, Jae Sang

    2008-04-28

    We have synthesized a bis(terthiophene)-appended uranyl-salophen complex, comprising N,N'-bis[4-(5,2':5',2''-terthiophen-3'-yl)salicylidene]-1,2-ethanediamine-uranyl complexes (TUS), and used it as a monomer for the electrochemical polymerizations (poly-TUS) on glassy carbon surfaces to prepare functionalized conducting polymer (CP) films. The poly-TUS films prepared from propylene carbonate/0.1 M tetrabutyl ammonium perchlorate (TBAP) on a glassy carbon electrode have both the functionality of ion-to-electron transducers (solid contact) and Lewis-acidic binding sites for a monohydrogen phosphate (MHP) ion-selective electrode (ISE). The CP/poly-TUS sensor showed a linear range between 1.0 x 10(-1) and 1.0 x 10(-4.5) M with a near-Nernstian behavior (-30.4 mV decade(-1)) at a pH of 8.2. The detection limit of the electrode was 10(-5.0) M and the response time was improved (polyvinyl chloride (PVC) liquid membrane with or without tridodecylmethylammonium chloride (TDMACl) as an additive was also constructed and its performance as an MHP-ISE were studied. The superior selectivity and sensitivity of the CP/poly-TUS sensor enabled the direct measurement of MHP in a wide variety of applications.

  7. Polyvinyl chloride resin

    International Nuclear Information System (INIS)

    Kim, Hong Jae

    1976-06-01

    This book contains polyvinyl chloride resin industry with present condition such as plastic industry and polyvinyl chloride in the world and Japan, manufacture of polyvinyl chloride resin ; suspension polymerization and solution polymerization, extruding, injection process, hollow molding vinyl record, vacuum forming, polymer powders process, vinyl chloride varnish, vinyl chloride latex, safety and construction on vinyl chloride. Each chapter has descriptions on of process and kinds of polyvinyl chloride resin.

  8. Structural basis for the transformation pathways of the sodium naproxen anhydrate-hydrate system

    DEFF Research Database (Denmark)

    Bond, Andrew; Cornett, Claus; Larsen, Flemming Hofmann

    2014-01-01

    to the monohydrate (MH) and anhydrate (AH) structures, provide a basis to rationalize the observed transformation pathways in the sodium (S)-naproxen anhydrate-hydrate system. All structures contain Na(+)/carboxylate/H2O sections, alternating with sections containing the naproxen molecules. The structure of DH...

  9. Influence of nitric acid on the kinetic of complexation of uranyl nitrate extracted by TBP

    International Nuclear Information System (INIS)

    Pushlenkov, M.F.; Zimenkov, V.V.

    1982-02-01

    The effect of nitric acid on the solvatation rate of uranyl nitrate with tributyl phosphate is studied. In the process of mass transfer, it is shown that nitric acid enables the extraction of uranyl nitrate, therefore its concentration in the organic phase exceeds that in equilibrium solution. Subsequently uranyl nitrate ''displaces'' nitric acid. The presence of the acid in aqueous and organic phases affects in a complicated manner the rate of solvatation of uranyl nitrate with tributyl phosphate [fr

  10. Orientational order and dynamics of water in bulk and in aqueous solutions of uranyl ions

    International Nuclear Information System (INIS)

    Chopra, Manish; Choudhury, Niharendu

    2014-01-01

    Molecular dynamics simulations in canonical ensemble of aqueous solutions of uranyl nitrate and bulk water at ambient condition have been carried out to investigate orientational order and dynamics of water. The orientational distributions of water around a central water molecule in bulk water and around a uranyl ion in an aqueous uranyl solution have been calculated. Orientational dynamics of water in bulk and in aqueous uranyl nitrate solution have also been analysed. (author)

  11. Photochemical reduction of uranyl ion by acetonitrile and propionitrile

    International Nuclear Information System (INIS)

    Brar, A.S.; Chander, R.; Sandhu, S.S.

    1979-01-01

    The photochemical reduction of uranyl ion by acetonitrile, propionitrile, benzonitrile, phenylacetonitrile, cyanoacetic acid and malononitrile in aqueous or aq. acetone medium using radiations >= 400 nm from a medium pressure mercury vapour lamp has been investigated. Except acetonitrile and propionitrile all other nitriles fail to bring about the reduction of uranyl ion. The reduction with aceto- and propionitriles has been found to obey pseudo-first order kinetics. The magnitude of rate of reduction with propionitrile is higher than that with acetonitrile. The pseudo-first order rate constants and quenching constant have been calculated from the kinetic data. It has been found that physical and chemical quenching compete with each other. The plot of reciprocal of quantum yield versus reciprocal (nitrile) is linear with a small intercept on the ordinate axis. Absorption spectra of uranyl ion in pure water, in the presence of acid and in the presence of acid+nitrile reveal that there is no ground state interaction between uranyl ion and the nitrile. A mechanism of photochemical reduction of uranyl ion based on α-hydrogen abstraction from the nitrile has been proposed. (auth.)

  12. Benchmarking uranyl peroxide capsule chemistry in organic media

    Energy Technology Data Exchange (ETDEWEB)

    Neal, Harrison A.; Nyman, May [Department of Chemistry, Oregon State University, Corvallis, OR (United States); Szymanowski, Jennifer; Fein, Jeremy B.; Burns, Peter C. [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN (United States)

    2017-01-03

    Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X-ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post-extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Benchmarking uranyl peroxide capsule chemistry in organic media

    International Nuclear Information System (INIS)

    Neal, Harrison A.; Nyman, May; Szymanowski, Jennifer; Fein, Jeremy B.; Burns, Peter C.

    2017-01-01

    Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X-ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post-extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Chemistry of the uranyl group. VI. Complexes of uranyl with hexamethylphosphoramide and urea

    Energy Technology Data Exchange (ETDEWEB)

    Zarli, B; Dall' olio, G; Sindellari, L [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi

    1976-01-01

    Some uranyl complexes with hexamethylphosphoramide (HMPA) and urea were prepared and characterized. The compounds with the former ligand have the general formula UO/sub 2/X/sub 2/.HMPA (where X = (C/sub 2/H/sub 5/)/sub 2/NCSe/sub 2//sup -/, (C/sub 2/H/sub 5/)/sub 2/NCS/sub 2//sup -/ or CH/sub 3/COO/sup -/). For the acetato derivatives a dimeric acetato-bridged structure is suggested. Some properties of UO/sub 2/(NO/sub 3/)/sub 2/.2(HMPA) are also described. With the latter ligand, in addition to the complexes UO/sub 2/(NO/sub 3/)/sub 2/.2urea and (UO/sub 2/(urea)/sub 4/(H/sub 2/0))(NO/sub 3/)/sub 2/ already known, the novel complexes UO/sub 2/(pycrate)/sub 2/.4urea and (UO/sub 2/(CH/sub 3/COO)/sub 2/.urea)sub(n) (where n is probably 2) have been prepared. All attempts to obtain urea complexes of uranyl diethyldithio- or diethyldiselenocarbamate failed and only adducts of unsatisfactory stoichiometry were isolated.

  15. Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

    International Nuclear Information System (INIS)

    Kubatko, K.; Helean, K.; Navrotsky, A.; Burns, P.C.

    2005-01-01

    The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO 2 ) 4 O(OH) 6 ](H 2 O) 5 , metaschoepite; β-UO 2 (OH) 2 ; CaUO 4 ; Ca(UO 2 ) 6 O 4 (OH) 6 (H 2 O) 8 , becquerelite; Ca(UO 2 ) 4 O 3 (OH) 4 (H 2 O) 2 ; Na(UO 2 )O(OH), clarkeite; Na 2 (UO 2 ) 6 O 4 (OH) 6 (H 2 O) 7 , the sodium analogue of compreignacite and Pb 3 (UO 2 ) 8 O 8 (OH) 6 (H 2 O) 2 , curite. The enthalpy of formation from the binary oxides, ΔH f-ox , at 298 K was calculated for each compound from the respective drop solution enthalpy, ΔH ds . The standard enthalpies of formation from the elements, ΔH f o , at 298 K are -1791.0 ± 3.2, -1536.2 ± 2.8, -2002.0 ± 3.2, -11389.2 ± 13.5, -6653.1 ± 13.8, -1724.7 ± 5.1, -10936.4 ± 14.5 and -13163.2 ± 34.4 kJ mol -1 , respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments

  16. Comparison of Intermolecular Forces in Anhydrous Sorbitol and Solvent Cocrystals.

    Science.gov (United States)

    Dierks, Teresa M; Korter, Timothy M

    2017-08-03

    The hygroscopicity of solid sorbitol is important for its utilization as a sweetener in the pharmaceutical and food industries. The molecular foundations of sorbitol hydration characteristics are explored here using two solvated cocrystals, sorbitol-water and sorbitol-pyridine. In this work, solid-state density functional theory and terahertz time-domain spectroscopy were used to evaluate the relative stabilities of these cocrystals as compared to anhydrous sorbitol in terms of conformational and cohesive energies. The modification of the hydrogen-bonding network in crystalline sorbitol by solvent molecules gives new insight into the origins of the notable stability of sorbitol-water as compared to similar solids such as mannitol-water. In particular, the energy analysis reveals that the relative instability of the mannitol hydrate is based primarily in the lack of water-water interactions which provide considerable stabilization in the sorbitol-water crystal.

  17. Anhydrous proton conductor based on composites of PEO and ATMP

    Energy Technology Data Exchange (ETDEWEB)

    Sun Baoying [Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084 (China); Qiu Xinping, E-mail: qiuxp@tsinghua.edu.c [Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084 (China); Zhu Wentao [Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084 (China)

    2011-04-15

    A new type anhydrous PEM material based on Poly (ethylene oxide) (PEO)/Amino Trimethylene Phosphonic Acid (ATMP) composite was prepared. In this study, PEO assumed to 'grab' protons via hydrogen bond between PEO and ATMP. Based on this point, the PEO/ATMP composites were prepared firstly as the preliminary study to verify this proton conducting system. Then, PVDF was added to enhance the membrane's stability. The PVDF/PEO/ATMP composite membranes were thermally stable up to 200 {sup o}C in the studied composition ranges. The membrane had relatively compact structure by SEM images. Proton conductivity of 59% PVDF/29% PEO/12% ATMP was up to 6.71 x 10 {sup -3} S cm{sup -1} at 86 {sup o}C after doping with 7.9 wt% phosphoric acid without extra humidification.

  18. Anhydrous proton conductor based on composites of PEO and ATMP

    International Nuclear Information System (INIS)

    Sun Baoying; Qiu Xinping; Zhu Wentao

    2011-01-01

    A new type anhydrous PEM material based on Poly (ethylene oxide) (PEO)/Amino Trimethylene Phosphonic Acid (ATMP) composite was prepared. In this study, PEO assumed to 'grab' protons via hydrogen bond between PEO and ATMP. Based on this point, the PEO/ATMP composites were prepared firstly as the preliminary study to verify this proton conducting system. Then, PVDF was added to enhance the membrane's stability. The PVDF/PEO/ATMP composite membranes were thermally stable up to 200 o C in the studied composition ranges. The membrane had relatively compact structure by SEM images. Proton conductivity of 59% PVDF/29% PEO/12% ATMP was up to 6.71 x 10 -3 S cm -1 at 86 o C after doping with 7.9 wt% phosphoric acid without extra humidification.

  19. Complex formation reactions of uranyl(VI) with neutral N-donors in dimethyl sulfoxide. Influence of small amounts of water

    International Nuclear Information System (INIS)

    Cassol, A.; Di Bernardo, P.; Zanonato, P.; Portanova, R.; Tolazzi, M.

    1990-01-01

    Quantitative information about the existence and thermodynamic stability of uranyl(VI) ion complexes based solely upon nitrogen coordination has been obtained in the solvent dimethyl sulfoxide. Calorimetric, potentiometric, and FT-IR investigations, under controlled anhydrous conditions, show that the uranyl(VI) ion can form both mono and bis chelates with the ethylenediamine ligand and only a mono chelate of rather low stability with propylenediamine. With the monodentate ligand n-butylamine only a very weak metal-ligand interaction has been detected. The stability constants and the enthalpy and entropy changes have been calculated for the identified coordinated species. All data refer to 25.0 degree C and a tetraethylammonium perchlorate medium of ionic strength 0.1 M. All the complexes are enthalpy stabilized whereas the entropy contributions oppose the complex formation. Calorimetric and FT-IR measurements carried out to investigate the effects of small amounts of water present show that a very low water concentration, comparable to that of the coordinating metal ion, can give rise to hydrolysis reactions that may compete with complex formation. This is due to the combined action of different factors that are discussed. 39 refs., 6 figs., 1 tab

  20. Spectroscopy and DFT studies of uranyl carbonate, rutherfordine, UO2CO3: a model for uranium transport, carbon dioxide sequestration, and seawater species

    Science.gov (United States)

    Kalashnyk, N.; Perry, D. L.; Massuyeau, F.; Faulques, E.

    2017-12-01

    Several optical microprobe experiments of the anhydrous uranium carbonate—rutherfordine—are presented in this work and compared to periodic density functional theory results. Rutherfordine is the simplest uranyl carbonate and constitutes an ideal model system for the study of the rich uranium carbonate family relevant for environmental sustainability. Micro-Raman, micro-reflectance, and micro-photoluminescence (PL) spectroscopy studies have been carried out in situ on native, micrometer-sized crystals. The sensitivity of these techniques is sufficient to analyze minute amounts of samples in natural environments without using x-ray analysis. In addition, very intense micro-PL and micro-reflectance spectra that were not reported before add new results on the ground and excited states of this mineral. The optical gap value determined experimentally is found at about 2.6-2.8 eV. Optimized geometry, band structure, and phonon spectra have been calculated. The main vibrational lines are identified and predicted by this theoretical study. This work is pertinent for optical spectroscopy, for identification of uranyl species in various environmental settings, and for nuclear forensic analysis.

  1. Hydrothermal Phase Relations Among Uranyl Minerals at the Nopal I Analog Site

    International Nuclear Information System (INIS)

    Murphy, William M.

    2007-01-01

    Uranyl mineral paragenesis at Nopal I is an analog of spent fuel alteration at Yucca Mountain. Petrographic studies suggest a variety of possible hydrothermal conditions for uranium mineralization at Nopal I. Calculated equilibrium phase relations among uranyl minerals show uranophane stability over a broad range of realistic conditions and indicate that uranyl mineral variety reflects persistent chemical potential heterogeneity. (author)

  2. Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O and anhydrous Rb[UO2(AsO3OH)(AsO2(OH)2)

    International Nuclear Information System (INIS)

    Yu, Na; Klepov, Vladislav V.; Villa, Eric M.; Bosbach, Dirk; Suleimanov, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.; Alekseev, Evgeny V.

    2014-01-01

    The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO 2 (AsO 3 OH)(AsO 2 (OH) 2 )]·H 2 O (α-, β-RbUAs) and the anhydrous phase Rb[UO 2 (AsO 3 OH)(AsO 2 (OH) 2 )] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions. - Graphical abstract: Three different layer geometries observed in the structures of Rb[UO 2 (AsO 3 OH)(AsO 2 (OH) 2 )] and α- and β- Rb[UO 2 (AsO 3 OH)(AsO 2 (OH) 2 )]·H 2 O. Two different coordination environments of uranium polyhedra (types I and II) are shown schematically on the top of the figure. - Highlights: • Three new uranyl arsenates were synthesized from the hydrothermal reactions. • The phases consist of the topologically identical but geometrically different layers. • Topotactic transitions were observed in the processes of mono-hyrates dehydration

  3. Preparation of working calibration and test materials: uranyl nitrate solution

    International Nuclear Information System (INIS)

    Yamamura, S.S.; Spraktes, F.W.; Baldwin, J.M.; Hand, R.L.; Lash, R.P.

    1977-05-01

    Reliable working calibration and test materials (WCTMs) are essential to a meaningful analytical measurements quality assurance program. This report describes recommended methods for the preparation of uranyl nitrate solution WCTMs for testing analytical methods, for calibrating methods, and for testing personnel. Uranyl nitrate solution WCTMs can be synthesized from characterized starting materials or prepared from typical plant materials by thorough characterization with reference to primary or secondary reference calibration and test materials (PRCTMs or SRCTMs). Recommended starting materials are described along with detailed procedures for (a) preparing several widely-used types of uranyl nitrate solution WCTMs, (b) packaging the WCTMs, (c) analyzing the WCTMs to establish the reference values or to confirm the synthesis, and (d) statistically evaluating the analytical data to assign reference values and to assess the accuracy of the WCTMs

  4. A study of precipitation from pure solutions of uranyl nitrate

    International Nuclear Information System (INIS)

    Decrop, J.; Holder, J.; Sauteron, J.

    1961-01-01

    After its purification by extraction of the uranyl nitrate from the organic solvent, uranium has to be converted into solid form again: uranium trioxide (UO 3 ). It can be done either by thermal decomposition of uranyl nitrate or by precipitation of uranium, followed by filtration and calcination. Only the second method has been studied for now at the Bouchet plant. This paper reports the bench-scale and pilot-scale experiments of the studies of the precipitation of pure solutions of uranyl nitrate using ammonia (gaseous or in solution) or ammonium carbonate. These have been carried out at the Bouchet plant. It investigates the chemical aspect (pH, precipitates chemical composition) and the technical aspect of the different ways of precipitation (conditions of precipitation, decantation and filtration of precipitates). (M.P.)

  5. Uranyl Sulfate Nanotubules Templated by N-phenylglycine

    Directory of Open Access Journals (Sweden)

    Oleg I. Siidra

    2018-04-01

    Full Text Available The synthesis, structure, and infrared spectroscopy properties of the new organically templated uranyl sulfate Na(phgH+7[(UO26(SO410](H2O3.5 (1, obtained at room temperature by evaporation from aqueous solution, are reported. Its structure contains unique uranyl sulfate [(UO26(SO410]8− nanotubules templated by protonated N-phenylglycine (C6H5NH2CH2COOH+. Their internal diameter is 1.4 nm. Each of the nanotubules is built from uranyl sulfate rings sharing common SO4 tetrahedra. The template plays an important role in the formation of the complex structure of 1. The aromatic rings are stacked parallel to each other due to the effect of π–π interaction with their side chains extending into the gaps between the nanotubules.

  6. Separation of chloride and fluoride from uranium compounds and their determination by ion selective electrodes

    International Nuclear Information System (INIS)

    Pires, M.A.F.; Abrao, A.

    1982-01-01

    Fluoride and chloride must be rigorously controlled in uranium compounds, especially in ceramic grade UO 2 . Their determination is very difficult without previous uranium separation, particularly when both are at a low concentration. A simple procedure is described for this separation using a strong cationic resin to retain the uranyl ion. Both anions are determined in the effluent solution. Uranium compounds of nuclear fuel cycle, especially ammonium diuranate, ammonium uranyl tricarbonate, sodium diuranate, uranium trioxide and dioxide and uranium peroxide are dissolved in nitric acid and the solutions are percolated through the resin column. Chloride and fluoride are determined in the effluent by selective electrodes, the detection limits being 0.02 μg F - /ml and 1.0 μg Cl - /ml. The dissolution of the sample, the acidity of the solution, the measurement conditions and the sensitivity of the method are discussed. (Author) [pt

  7. DNA conformational analysis in solution by uranyl mediated photocleavage

    DEFF Research Database (Denmark)

    Nielsen, Peter E.; Møllegaard, N E; Jeppesen, C

    1990-01-01

    Uranyl mediated photocleavage of double stranded DNA is proposed as a general probing for DNA helix conformation in terms of minor groove width/electronegative potential. Specifically, it is found that A/T-tracts known to constitute strong distamycin binding sites are preferentially photocleaved ......, uranyl photocleavage of the internal control region (ICR) of the 5S-RNA gene yields a cleavage modulation pattern fully compatible with that obtained by DNase I which also--in a more complex way--senses DNA minor groove width....

  8. Critical experiment study on uranyl nitrate solution experiment facility

    International Nuclear Information System (INIS)

    Zhu Qingfu; Shi Yongqian; Wang Jinrong

    2005-01-01

    The Uranyl Nitrate Solution Experiment Facility was constructed for the research on nuclear criticality safety. In this paper, the configuration of the facility is introduced; a series of critical experiments on uranyl nitrate solution is described later, which were performed for various uranium concentrations under different conditions, i.e. with or without neutron absorbers in the core and with or without water-reflector outside the core. Critical volume and the minimum 235U critical mass for different uranium concentrations are presented. Finally, theoretical analysis is made on the experimental results. (authors)

  9. Molecular approach of uranyl/mineral surfaces: theoretical approach

    International Nuclear Information System (INIS)

    Roques, J.

    2009-01-01

    As migration of radio-toxic elements through the geosphere is one of the processes which may affect the safety of a radioactive waste storage site, the author shows that numerical modelling is a support to experimental result exploitation, and allows the development of new interpretation and prediction codes. He shows that molecular modelling can be used to study processes of interaction between an actinide ion (notably a uranyl ion) and a mineral surface (a TiO 2 substrate). He also reports the predictive theoretical study of the interaction between an uranyl ion and a gibbsite substrate

  10. Uranyl peroxide enhanced nuclear fuel corrosion in seawater.

    Science.gov (United States)

    Armstrong, Christopher R; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E; Burns, Peter C; Navrotsky, Alexandra

    2012-02-07

    The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances.

  11. Electronic structure and properties of uranyl compounds. Problems of electron-donor conception

    International Nuclear Information System (INIS)

    Glebov, V.A.

    1982-01-01

    Comparison of the series of the ligand mutual substitution in the uranyl compounds with the ligand series of d-elements and with the uranyl ''covalent model'', is made. The data on ionization potentials of the ligand higher valent levels and on the structure of some uranyl nitrate compounds are considered. It is concluded that the mechanism of the ligand effect on the properties of uranyl grouping is more complex, than it is supposed in the traditional representations on the nature of electron-donor interactions in the uranyl compounds

  12. The interaction of uranyl ions with inorganic pyrophosphatase from baker's yeast

    International Nuclear Information System (INIS)

    Bienwald, B.; Heitmann, P.

    1978-01-01

    The interaction of uranyl ions with inorganic pyrophosphatase from baker's yeast was investigated by measurement of their effect on the protein fluorescence. Fluorescence titrations of the native enzyme with uranyl nitrate show that there is a specific binding of uranyl ions to the enzyme. It was deduced that each subunit of the enzyme binds one uranyl ion. The binding constant was estimated to be in the order of 10 7 M -1 . The enzyme which contains a small number of chemically modified carboxyl groups was not able to bind uranyl ions specifically. The modification of carboxyl groups was carried out by use of a water soluble carbodiimide and the nucleophilic reagent N-(2,4-dinitro-phenyl)-hexamethylenediamine. The substrate analogue calcium pyrophosphate displaced the uranyl ions from their binding sites at the enzyme From the results it is concluded that carboxyl groups of the active site are the ligands for the binding of uranyl ions. (author)

  13. Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

    Energy Technology Data Exchange (ETDEWEB)

    K. Kubatko; K. Helean; A. Navrotsky; P.C. Burns

    2005-05-11

    The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO{sub 2}){sub 4}O(OH){sub 6}](H{sub 2}O){sub 5}, metaschoepite; {beta}-UO{sub 2}(OH){sub 2}; CaUO{sub 4}; Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 8}, becquerelite; Ca(UO{sub 2}){sub 4}O{sub 3}(OH){sub 4}(H{sub 2}O){sub 2}; Na(UO{sub 2})O(OH), clarkeite; Na{sub 2}(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 7}, the sodium analogue of compreignacite and Pb{sub 3}(UO{sub 2}){sub 8}O{sub 8}(OH){sub 6}(H{sub 2}O){sub 2}, curite. The enthalpy of formation from the binary oxides, {Delta}H{sub f-ox}, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}H{sub ds}. The standard enthalpies of formation from the elements, {Delta}H{sub f}{sup o}, at 298 K are -1791.0 {+-} 3.2, -1536.2 {+-} 2.8, -2002.0 {+-} 3.2, -11389.2 {+-} 13.5, -6653.1 {+-} 13.8, -1724.7 {+-} 5.1, -10936.4 {+-} 14.5 and -13163.2 {+-} 34.4 kJ mol{sup -1}, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

  14. Solvent extraction of uranyl nitrate (1962); Extraction du nitrate d'uranyle par solvant (1962)

    Energy Technology Data Exchange (ETDEWEB)

    Talmont, X; Regnaut, P [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires; Durandet, J; Renault, Ph; Gladel, Y L [Institut Francais du Petrole (IFP), Dept. de Physico-Chimie Appliquee, 92 - Rueil-Malmaison (France)

    1962-07-01

    The transfer of uranyl nitrate from an aqueous acid phase into a solvent (dilute tributylphosphate) is attended by nitric acid transfer. In these conditions, equilibrium data cannot be represented by a plane curve, which complicates the determination of the efficiency of the extractor used, i.e. the calculation of either the number of theoretical plates or the number of transfer units equivalent to the apparatus. The authors are presenting a simple method for estimating the efficiency of a column, based upon either uranium or acid transfer. This method can be used when the profile of uranium and acid concentrations in a phase circulating in the equipment bas been previously determined. On another hand, it enables to study the variation of local efficiency, i.e. the efficiency of different sections of the column. (authors) [French] Le transfert du nitrate d'uranyle d'une phase aqueuse acide dans un solvant (phosphate de tributyle dilue) s'accompagne d'un transfert d'acide nitrique. Dans ces conditions, les donnees d'equilibre ne sont pas representees par une courbe plane, ce qui complique la determination de l'efficacite de l'extracteur utilise, c'est-a-dire le calcul, soit du nombre d'etages theoriques, soit du nombre d'unites de transfert auquel l'appareil est equivalent. Les auteurs presentent une methode simple d'evaluation de l'efficacite d'une colonne basee, soit sur le transfert d'uranium, soit sur celui d'acide. Cette methode est utilisable lorsqu'en a determine au prealable le profil des concentrations en uranium et en acide d'une phase circulant dans l'appareil. Elle permet, d'autre part, d'etudier la variation de l'efficacite locale, c'est-a-dire l'efficacite de differentes sections de la colonne. (auteurs)

  15. Automated thin-film analyses of anhydrous interplanetary dust particles in the analytical electron microscope

    Science.gov (United States)

    Bradley, J. P.; Germani, M. S.; Brownlee, D. E.

    1989-01-01

    An AEM apparatus equipped with digital beam control has obtained quantitative point-count analyses of thin sections taken from eight anhydrous chondritic interplanetary dust particles (IDPs); between 200 and 500 X-ray analyses were collected from each thin section and analyzed for Mg, Al, Si, S, Ca, Cr, Mn, Fe, and Ni. Two types of anhydrous chondritic aggregates were observed in the eight IDPs: one highly porous, the other less so. The eight anhydrous IDPs are characterizable as mixtures of fine- and coarse-grained aggregates, large mineral grains, glass, and carbonaceous materials. Their elemental concentrations follow those of solar abundances, suggesting that they are unperturbed by aqueous alteration.

  16. Sorption of uranyl ions on hydrous silicon dioxide

    International Nuclear Information System (INIS)

    Lieser, K.H.; Quandt-Klenk, S.; Thybusch, B.

    1992-01-01

    Sorption of uranyl ions on SiO 2 .χH 2 O (silica gel) is investigated in absence and in presence of carbonate as function of pH. The curves obtained are very similar to those observed for sorption of uranyl ion on TiO 2 .χH 2 O, indicating the dominating influence of the uranium species in solution. Between pH 2 and 5 the sorption ratio R s increases with hydrolysis of uranyl ions (formation of UO 2 OH + ), around pH 7 it is nearly independent of pH, and at higher pH it decreases again. The equilibrium constants are calculated for these ranges. In presence of carbonate R s decreases drastically above pH 6, due to the formation of carbonato complexes in solution. Sorption of uranyl ions on SiO 2 .χH 2 O, on TiO 2 .χH 2 O, and on cryst. SiO 2 and Al 2 O 3 is compared. The problems of 'surface complexation' modelling are discussed. (orig.)

  17. Synthesis of pyrimidine carboxamide derivatives catalyzed by uranyl

    African Journals Online (AJOL)

    2014-09-02

    (Received September 2, 2014; revised January 1, 2016). ABSTRACT. An efficient and simple method was developed for the synthesis pyrimidine-5-carboxamides using. UO2(NO3)2.6H2O catalyst under conventional and microwave irradiation. The synthesis of dihydropyrimidine using uranyl nitrate had shown many ...

  18. Density functional study of uranyl (VI) amidoxime complexes

    International Nuclear Information System (INIS)

    Chi Fang-Ting; Xiong Jie; Hu Sheng; Xia Xiu-Long; Wang Xiao-Lin; Li Peng; Gao Tao

    2012-01-01

    Uranyl (VI) amidoxime complexes are investigated using relativistic density functional theory. The equilibrium structures, bond orders, and Mulliken populations of the complexes have been systematically investigated under a generalized gradient approximation (GGA). Comparison of (acet) uranyl amidoxime complexes ([UO 2 (AO) n ] 2−n , 1 ≤ n ≤ 4) with available experimental data shows an excellent agreement. In addition, the U−O(1), U−O(3), C(1)−N(2), and C(3)−N(4) bond lengths of [UO 2 (CH 3 AO) 4 ] 2− are longer than experimental data by about 0.088, 0.05, 0.1, and 0.056 Å. The angles of N(3)−O(3)−U, O(2)−N(1)−C(1), N(3)−C(3)−N(4), N(4)−C(3)−C(4), and C(4)−C(3)−N(3) are different from each other, which is due to existing interaction between oxygen in uranyl and hydrogen in amino group. This interaction is found to be intra-molecular hydrogen bond. Studies on the bond orders, Mulliken charges, and Mulliken populations demonstrate that uranyl oxo group functions as hydrogen-bond acceptors and H atoms in ligands act as hydrogen-bond donors forming hydrogen bonds within the complex

  19. Studying of the dehydration process of uranyl nitrate hexahydrate (Unh)

    International Nuclear Information System (INIS)

    Badalov, A.; Kamalov, J.J.; Homidov, B.J.; Mirsaidov, I.U.; Eshbekov, N.R.

    2005-01-01

    By the tensimeteric method is studying the dehydration process of uranyl nitrate hexahydrate (Unh). It is shown, that the temperature interval 300-400 K in equilibrium conditions the dehydration process of Unh runs in three stages. According to the equations of dependence of saturated steam pressure from temperature, the thermodynamic characteristics of each stage of the dehydration process of Unh are calculated

  20. Colorimetric peroxidase mimetic assay for uranyl detection in sea water

    KAUST Repository

    Zhang, Dingyuan

    2015-03-04

    Uranyl (UO2 2+) is a form of uranium in aqueous solution that represents the greatest risk to human health because of its bioavailability. Different sensing techniques have been used with very sensitive detection limits especially the recently reported uranyl-specific DNAzymes systems. However, to the best of our knowledge, few efficient detection methods have been reported for uranyl sensing in seawater. Herein, gold nanoclusters (AuNCs) are employed in an efficient spectroscopic method to detect uranyl ion (UO2 2+) with a detection limit of 1.86 ÎM. In the absence of UO2 2+, the BSA-stabilized AuNCs (BSA-AuNCs) showed an intrinsic peroxidase-like activity. In the presence of UO2 2+, this activity can be efficiently restrained. The preliminary quenching mechanism and selectivity of UO2 2+ was also investigated and compared with other ions. This design strategy could be useful in understanding the binding affinity of protein-stabilized AuNCs to UO2 2+ and consequently prompt the recycling of UO2 2+ from seawater.

  1. Structure and dynamics of aqueous solution of uranyl ions

    International Nuclear Information System (INIS)

    Chopra, Manish; Choudhury, Niharendu

    2014-01-01

    The present work describes a molecular dynamics simulation study of structure and dynamics of aqueous solution of uranyl ions in water. Structural properties of the system in terms of radial distribution functions and dynamical characteristics as obtained through velocity autocorrelation function and mean square displacements have been analyzed. The results for radial distribution functions show the oxygen of water to form the first solvation shell at 2.4 Å around the uranium atom, whereas the hydrogen atoms of water are distributed around the uranium atom with the major peak at around 3.0 Å. Analyses of transport behaviors of ions and water through MSD indicates that the diffusion of the uranyl ion is much less as compared to that of the water molecules. It is also observed that the dynamical behavior of water molecules gets modified due to the presence of uranyl ion. The effect of increase in concentration of uranyl ions on the structure and dynamics of water molecules is also studied

  2. Synthesis and characterization of heterometallic uranyl pyridinedicarboxylate compounds

    Science.gov (United States)

    Jayasinghe, Ashini S.; Payne, Maurice K.; Forbes, Tori Z.

    2017-10-01

    The incorporation of transition metals into hybrid uranyl materials can result in more diverse structural topologies and variations in physical and chemical properties. To explore the impact of transition metals on the uranyl cation, five uranium containing bimetallic chain compounds, [(UO2)M(PDC)2(H2O)4]·4(H2O) (PDC = 2,6 pyridinedicarboxylate; M = Ni2+, Co2+, Fe2+, Zn2+, and Cu2+) were synthesized by evaporation of aqueous solutions at room temperature. The uranyl cation is complex by two PDC ligands and the transition metal cations bond to the complex to form a one-dimensional chain topology. The presence of the transition metal leads to the presence of a stronger uranyl oxo bonds as shown by the single-crystal X-ray diffraction data and the Raman spectra. Solid state diffuse reflectance UV/Visible spectra confirmed the presence of the transition metals in the structure by the broad bands that appeared at relevant wavelengths.

  3. The influence of cement type and temperature on chloride binding in cement paste

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede; Korzen, Migge Sofie Hoffmann; Skibsted, Jørgen

    1998-01-01

    This paper describes effects of cement type and temperature on chloride binding in cement paste, which is an important subject in relation to life-time modelling of reinforced concrete structures. The influence of cement type on chloride binding is investigated by substituting cement with pure...... cement clinker. Both theoretical considerations and experimental data for chloride binding in cement pastes are presented. A physico-chemically based model to describe the influence of temperature on physical binding of chloride is presented. Solid-state 27Al and 29Si magic-angle spinning (MAS) nuclear...... magnetic resonance (NMR) spectroscopy has been used for quantification of the anhydrous and hydrated aluminate and silicate phases in the chloride exposed cement pastes. The 27Al isotropic chemical shift and nuclear quadrupole coupling is reported for a synthetic sample of Friedel's salt, Ca2Al(OH)6Cl×2H2O....

  4. Interaction of alcohols with the anhydrous silico-12-molybdic acid

    International Nuclear Information System (INIS)

    Pinchuk, I.N.; Chuvaev, V.F.; Ovchinnikova, N.S.; Zhuravlev, L.T.; Spitsyn, V.I.

    1984-01-01

    A study was made on interaction of methanol, ethanol and isopropanol with silico-12-molybdic acid (H 4 SiMo 12 O 40 (SMA). It was revealed that anhydrous SMA at room temperature adds a sufficient amount of alcohol from gaseous phase with formation of solvates of the following compositions: H 4 SiMo 12 O 40 x3CH 3 OH, H 4 SiMo 12 O 40 x5C 2 H 5 OH and H 4 SiMo 12 O 40 x3C 3 H 7 OH. Thermal decomposition of SMA solvates was studied and the mechanism of solid-phase heteropolyacid interaction with alcohols was suggested. Temperature ranges of separate catalytic and redox processes were established. Specificity of activity and peculiarities of heteropolyacid transformation in the course of reaction were investigated. It was shown that formation of deprotonated phases of SiMosub(12)Osub(38-y/2) or Csub(n)SiMosub(12)Osub(38-x) type during SMA interaction with alcohol can't be probably reduced to the simple succession of reduction and dehydration reactions

  5. Growth of uranyl hydroxide nanowires and nanotubes with electrodeposition method

    International Nuclear Information System (INIS)

    Wang Lin; Yuan Liyong; Chai Zhifang; Shi Weiqun

    2013-01-01

    Actinides nanomaterials have great potential applications in fabrication of novel nuclear fuel and spent fuel reprocessing in advanced nuclear energy system. However, the relative research so far still lacks systematic investigation on the synthetic methods for actinides nanomaterials. In this work, we use track-etched membranes as hard templates to synthesize uranium based nanomaterials with novel structures by electrodeposition method. Through electrochemical behavior investigations and subsequent product characterizations such as energy dispersive spectrometer (EDS), fourier transform infrared spectroscopy (FTIR), the chemical composition of deposition products have been confirmed as the uranyl hydroxide. More importantly, accurate control of morphology and structures (nanowires and nanotubes) could be achieved by carefully adjusting the growth parameters such as deposition time and deposition current density. It was found that the preferred morphology of electrodeposition products is nanowire when a low current density was applied, whereas nanotubes could be formed only under conditions of high current density and the short deposition time. The mechanism for the formation of nanowires in track-etched membranes is based on the precipitation of uranyl hydroxide from uranyl nitrate solution, according to the previous researches about obtaining nanostructures of hydroxides from nitrate salt solutions. And we have concluded that the formation of nanotubes is attributed to the hydrogen bubbles generated by water electrolysis under the condition of over-potential electro-reduction. The conveying of hydrogen bubbles plays the role of dynamic template which can prevent the complete filling of uranyl hydroxide in the channels. Additionally, we transform the chemical composition of deposition products from uranyl hydroxide to triuranium octoxide by calcining them at 500 and 800 degree centigrade, respectively, and SEM results show the morphologies of nanowires and

  6. Transport of anhydrous ammoniac - risk assessment; Le transport de l'ammoniac anhydre - analyse et estimation des risques: rapport de synthese

    Energy Technology Data Exchange (ETDEWEB)

    Castellano, S; Degrange, J P; Hubert, P; Pages, P; Lamblin, J

    1989-12-01

    This risk analysis of anhydrous ammonia transport in France was done within a study initiated by the Department of dangerous goods of the Ministry of transport. The study deals with the road and rail transportation of bulk anhydrous ammonia. After analysis of transport system and traffic, the transport accident risks are estimated, as well as their distribution on the French territory. Finally after a synthesis of results, a number of safety measures to be undertaken were identified. This is a joint study of SMC-CEPN, with a specific role of SEMA-METRA-CONSEIL concerning the traffic frequency, and the center for risk evaluation concerning nuclear safety.

  7. Dehydration Behaviour of Borax Pentahydrate to Anhydrous Borax by Multi-Stage Heating in a Fluidized

    OpenAIRE

    ŞAHİN, Ömer

    2002-01-01

    In order to optimize the anhydrous borax process in a fluidized bed calcinator, it is absolutely necessary to study the dehydration behaviour of borax pentahydrate. It was found that the basic feature of the dehydration of borax pentahydrate to anhydrous borax is concerned with the conditions employed. The bulk density and sodium borate content of the end product were determined to be a function of number of stages of temperature of the dehydration period in the fluidized bed. It...

  8. The Effect of Compaction Force on the Transition to Hydrate of Anhydrous Aripiprazole.

    Science.gov (United States)

    Togo, Taichiro; Taniguchi, Toshiya; Nakata, Yoshitaka

    2018-01-01

    Aripiprazole (APZ) is used to treat schizophrenia and is administered as a tablet containing the anhydrous form of APZ. In this study, the effect of compaction force on the crystal form transition was investigated. The crystalline state was observed by X-ray diffraction (XRD). APZ Anhydrous Form II was compacted into tablets. The XRD intensity of anhydrous APZ became lower with higher compressive force. The degree of crystallinity decreased with the compaction force. The powder and the compacted tablets of anhydrous APZ were stored for one week under 60°C and 75% relative humidity. The powder showed no crystal form transition after storage. For the tablets, however, XRD peaks of APZ hydrate were observed after storage. The tablets compacted with higher force showed the higher XRD diffraction intensity of hydrate form. We concluded that the crystallinity reduction of APZ Anhydrous Form II by compaction caused and accelerated the transition to hydrate under high temperature and humidity conditions. In order to manufacture crystallographically stable tablets containing anhydrous APZ, it is important to prevent this crystallinity reduction during compaction.

  9. Water in Nominally Anhydrous Minerals from Nakhlites and Shergottites

    Science.gov (United States)

    Peslier, Anne H.

    2013-01-01

    Estimating the amount of water in the interior of terrestrial planets has tremendous implications on our understanding of solar nebula evolution, planet formation and geological history, and extraterrestrial volcanism. Mars has been a recent focus of such enquiry with complementary datasets from spacecrafts, rovers and martian meteorite studies. In planetary interiors, water can be dissolved in fluids or melts and hydrous phases, but can also be locked as protons attached to structural oxygen in lattice defects in nominally anhydrous minerals (NAM) such as olivine, pyroxene, or feldspar [1-3]. Measuring water in Martian meteorite NAM is challenging because the minerals are fragile and riddled with fractures from impact processes that makes them break apart during sample processing. Moreover, curing the sample in epoxy causes problems for the two main water analysis techniques, Fourier transform infrared spectrometry (FTIR) and secondary ionization mass spectrometry (SIMS). Measurements to date have resulted in a heated debate on how much water the mantle of Mars contains. SIMS studies of NAM [4], amphiboles [5], and apatites [6-8] from Martian meteorites report finding enough water in these phases to infer that the martian mantle is as hydrous as that of the Earth. On the other hand, a SIMS study of glass in olivine melt inclusions from shergottites concludes that the Martian mantle is much drier [9]. The latter interpretation is also supported by the fact that most martian hydrous minerals generally have the relevant sites filled with Cl and F instead of H [10,11]. As for experimental results, martian basalt compositions can be reproduced using water as well as Cl in the parent melts [12,13]. Here FTIR is used to measure water in martian meteorite minerals in order to constrain the origin of the distribution of water in martian meteorite phases.

  10. A spectroscopic study of uranium species formed in chloride melts

    International Nuclear Information System (INIS)

    Volkovich, Vladimir A.; Bhatt, Anand I.; May, Iain; Griffiths, Trevor R.; Thied, Robert C.

    2002-01-01

    The chlorination of uranium metal or uranium oxides in chloride melts offers an acceptable process for the head-end of pyrochemical reprocessing of spent nuclear fuels. The reactions of uranium metal and ceramic uranium dioxide with chlorine and with hydrogen chloride were studied in the alkali metal chloride melts, NaCl-KCl at 973K, NaCl-CsCl between 873 and 923K and LiCl-KCl at 873K. The uranium species formed therein were characterized from their electronic absorption spectra measured in situ. The kinetic parameters of the reactions depend on melt composition, temperature and chlorinating agent used. The reaction of uranium dioxide with oxygen in the presence of alkali metal chlorides results in the formation of alkali metal uranates. A spectroscopic study, between 723 and 973K, on their formation and their solutions was undertaken in LiCl, LiCl-KCl eutectic and NaCl-CsCl eutectic melts. The dissolution of uranium dioxide in LiCl-KCl eutectic at 923K containing added aluminium trichloride in the presence of oxygen has also been investigated. In this case, the reaction leads to the formation of uranyl chloride species. (author)

  11. The extraction of uranyl nitrate and chloride in octaethyltetraamidopyrophosphate (OETAPP)-HCl, HNO3 systems

    International Nuclear Information System (INIS)

    Jankowska, M.; Kulawik, J.; Mikulski, J.

    1975-01-01

    The extraction of uranium was studied in the system of 0.1 M OETAPP in CHCl 3 /HCl or HNO 3 . The distribution coefficients of HCl and HNO 3 were calculated as a function of OETAPP concentration. The amount of OETAPP in the aqueous phase containing HCl and HNO 3 was found from the measurements of surface tension of this phase. The distribution of HCl or HNO 3 between the organic and aqueous phases was studied as a function of the concentration of the acid used in the aqueous phase. The solvation energy of the extracted complexes was calculated from the measured potential differences. Cohesion and adhesion energies of the studied systems are also given. (author)

  12. Transformation of human osteoblast cells to the tumorigenic phenotype by depleted uranium-uranyl chloride.

    OpenAIRE

    Miller, A C; Blakely, W F; Livengood, D; Whittaker, T; Xu, J; Ejnik, J W; Hamilton, M M; Parlette, E; John, T S; Gerstenberg, H M; Hsu, H

    1998-01-01

    Depleted uranium (DU) is a dense heavy metal used primarily in military applications. Although the health effects of occupational uranium exposure are well known, limited data exist regarding the long-term health effects of internalized DU in humans. We established an in vitro cellular model to study DU exposure. Microdosimetric assessment, determined using a Monte Carlo computer simulation based on measured intracellular and extracellular uranium levels, showed that few (0.0014%) cell nuclei...

  13. Np Incorporation into Uranyl Alteration Phases: A Quantum Mechanical Approach

    International Nuclear Information System (INIS)

    L.C. Huller; R.C. Win; U.Ecker

    2006-01-01

    Neptunium is a major contributor to the long-term radioactivity in a geologic repository for spent nuclear fuel (SNF) due to its long half-life (2.1 million years). The mobility of Np may be decreased by incorporation into the U 6+ phases that form during the corrosion of SNF. The ionic radii of Np (0.089nm) and U (0.087nm) are similar, as is their chemistry. Experimental studies have shown Np can be incorporated into uranyl phases at concentrations of ∼ 100 ppm. The low concentration of Np in the uranyl phases complicates experimental detection and presents a significant challenge for determining the incorporation mechanism. Therefore, we have used quantum mechanical calculations to investigate incorporation mechanisms and evaluate the energetics of Np substituting for U. CASTEP, a density functional theory based code that uses plane waves and pseudo-potentials, was used to calculate optimal H positions, relaxed geometry, and energy of different uranyl phases. The incorporation energy for Np in uranyl alteration phases was calculated for studtite, [(UO 2 )O 2 (H 2 O) 2 ](H 2 ) 2 , and boltwoodite, HK(UO 2 )(SiO 4 )* 1.5(H 2 O). Studtite is the rare case of a stable uranyl hydroxyl-peroxide mineral that forms in the presence of H 2 O 2 from the radiolysis of H 2 O. For studtite, two incorporation mechanisms were evaluated: (1) charge-balanced substitution of Np 5+ and H + for one U 6+ , and (2) direct substitution of Np 6+ for U 6+ . For boltwoodite, the H atomic positions prior to Np incorporation were determined, as well as the Np incorporation mechanisms and the corresponding substitution energies. The preferential incorporation of Np into different structure types of U 6+ minerals was also investigated. Quantum mechanical substitution energies have to be derived at Np concentrations higher than the ones found in experiments or expected in a repository. However, the quantum mechanical results are crucial for subsequent empirical force-field and Monte

  14. Functional polyterthiophene-appended uranyl-salophen complex: Electropolymerization and ion-selective response for monohydrogen phosphate

    International Nuclear Information System (INIS)

    Kim, Junghwan; Kang, Dong Min; Shin, Sung Chul; Choi, Myong Yong; Kim, Jineun; Lee, Shim Sung; Kim, Jae Sang

    2008-01-01

    We have synthesized a bis(terthiophene)-appended uranyl-salophen complex, comprising N,N'-bis[4-(5,2':5',2''-terthiophen-3'-yl)salicylidene] -1,2-ethanediamine-uranyl complexes (TUS), and used it as a monomer for the electrochemical polymerizations (poly-TUS) on glassy carbon surfaces to prepare functionalized conducting polymer (CP) films. The poly-TUS films prepared from propylene carbonate/0.1 M tetrabutyl ammonium perchlorate (TBAP) on a glassy carbon electrode have both the functionality of ion-to-electron transducers (solid contact) and Lewis-acidic binding sites for a monohydrogen phosphate (MHP) ion-selective electrode (ISE). The CP/poly-TUS sensor showed a linear range between 1.0 x 10 -1 and 1.0 x 10 -4.5 M with a near-Nernstian behavior (-30.4 mV decade -1 ) at a pH of 8.2. The detection limit of the electrode was 10 -5.0 M and the response time was improved (<10 s) compared to that of conventional ISEs (<20 s). For comparison, a conventional ISE (with an internal aqueous solution) based on a TUS monomer/o-nitrophenyl octylether (o-NPOE)/polyvinyl chloride (PVC) liquid membrane with or without tridodecylmethylammonium chloride (TDMACl) as an additive was also constructed and its performance as an MHP-ISE were studied. The superior selectivity and sensitivity of the CP/poly-TUS sensor enabled the direct measurement of MHP in a wide variety of applications

  15. IR spectra and structure of uranyl pivaloyltrifluoroacetylacetonate isolated in argon matrix

    International Nuclear Information System (INIS)

    Belyaeva, A.A.; Dushin, R.B.; Sidorenko, G.V.; Suglobov, D.N.

    1985-01-01

    When studying IR absorption spectra of a number of isotopomers of uranyl pivaloyl trifluoroacetonate (UPTFA), isolated in the matrix of argon and dissolved in benzene, and comparing them with the spectra of uranyl hexafluoroacetylacetonate (UHFA) vapours, it has been ascertained, that UPTFA vapours consist of monomers and dimers, and UPTFA solution in benzene - of dimers.It is shown, that the dimers have T-shaped structure, at that, the bond inside the dimer is realized by yl-atom of oxygen of an uranyl ion, included in the equatorial coordination sphere of another uranyl ion. Proofs of the dimer T-like structure distortion in gaseous or matrix-isolated state, as a result of which the difference of the angles between uranyl axes from 90 deg is observed, are given. In the framework of approximated model of isolated uranyl-ion the force constants for all the compounds investigated are calaculted

  16. Probing uranyl(VI) speciation in the presence of amidoxime ligands using electrospray ionization mass spectrometry.

    Science.gov (United States)

    Mustapha, Adetayo M; Pasilis, Sofie P

    2013-10-15

    Extraction processes using poly(acrylamidoxime) resins are being developed to extract uranium from seawater. The main complexing agents in these resins are thought to be 2,6-dihydroxyiminopiperidine (DHIP) and N(1),N(5)-dihydroxypentanediimidamide (DHPD), which form strong complexes with uranyl(VI) at the pH of seawater. It is important to understand uranyl(VI) speciation in the presence of these and similar amidoxime ligands to understand factors affecting uranyl(VI) adsorption to the poly(acrylamidoxime) resins. Experiments were carried out in positive ion mode on a quadrupole ion trap mass spectrometer equipped with an electrospray ionization source. The ligands investigated were DHIP, DHPD, and N(1),N(2)-dihydroxyethanediimidamide (DHED). DHED and DHPD differ only in the number of carbons separating the oxime groups. The effects on the mass spectra of changes in uranyl(VI):ligand ratio, pH, and ligand type were examined. DHIP binds uranyl(VI) more effectively than DHPD or DHED in the pH range investigated, forming ions derived from solution-phase species with uranyl(VI):DHIP stoichiometries of 1:1, 1:2, and 2:3. The 2:3 uranyl(VI):DHIP complex appears to be a previously undescribed solution species. Ions related to uranyl(VI):DHPD complexes were detected in very low abundance. DHED is a more effective complexing agent for uranyl(VI) than DHPD, forming ions having uranyl(VI):DHED stoichiometries of 1:1, 1:2, 1:3, and 2:3. This study presents a first look at the solution chemistry of uranyl(VI)-amidoxime complexes using electrospray ionization mass spectrometry. The appearance of previously undescribed solution species suggests that the uranyl-amidoxime system is a rich and relatively complex one, requiring a more in-depth investigation. Copyright © 2013 John Wiley & Sons, Ltd.

  17. The state of uranyl ions in water-dioxane solvent mixtures

    International Nuclear Information System (INIS)

    Geipel, G.; Nebel, D.; Baraniak, L.

    1985-01-01

    A comparison of the spectra of uranyl ions in HCl and dioxane solutions leads to the conclusion that dioxane promotes complex formation. The investigation of spectra showed that taking into account the hydrolysis of uranyl ions in dioxane containing solutions, two successive equilibrium reactions take place. The formation constants were determined. Conductivity measurements confirmed the spectrophotometrically determined equilibria. In solutions containing up to 60 % dioxane there is no incorporation of dioxane in the solvating envelope of the uranyl ion. (author)

  18. Uranyl oxo activation and functionalization by metal cation coordination

    International Nuclear Information System (INIS)

    Arnold Polly, L.; Pecharman, A. F.; Hollis, E.; Parsons, S.; Love, J. B.; Yahia, A.; Maron, L.; Yahia, A.; Maron, L.

    2010-01-01

    The oxo groups in the uranyl ion [UO 2 ] 2+ - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

  19. Uranyl oxo activation and functionalization by metal cation coordination

    Energy Technology Data Exchange (ETDEWEB)

    Arnold Polly, L; Pecharman, A F; Hollis, E; Parsons, S; Love, J B [Univ Edinburgh, EaStCHEM Sch Chem, Edinburgh EH9 3JJ, Midlothian (United Kingdom); Yahia, A; Maron, L [Univ Toulouse 3, LPCNO, UMR 5215, INSA, CNRS, F-31077 Toulouse 4 (France); Yahia, A; Maron, L [Univ Montpellier 2, ENSCM, CNRS, ICSM, UMR 5257, CEA, Ctr Marcoule, F-30207 Bagnols Sur Ceze (France)

    2010-07-01

    The oxo groups in the uranyl ion [UO{sub 2}]{sup 2+} - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

  20. Investigation of uranyl phosphite interaction with some amides

    International Nuclear Information System (INIS)

    Avduevskaya, K.A.; Ragulina, N.B.; Rozanov, I.A.; Mukhajlov, Yu.N.; Kanishcheva, A.S.; Grevtseva, T.G.

    1981-01-01

    Uranyl (amide) phosphitocomplexes of [UO 2 HPO 3 H 2 OAA]xH 2 O, [UO 2 HPO 3 (AA) 2 ], [UO 2 HPO 3 H 2 O DMC], [UO 2 HPO 3 H 2 ODMFA], [UO 2 HPO 3 DAMA] and UO 2 HPO 3 x2FAxH 2 O compositions, where AA-acetamide; DMC-N, N-dimetyl carbamide, DMFA-dimetyl formamide; DAMA-diamide of malonic acid; FA-formamide, are separated, identified and investigated. Derivatives of mono substituted uranyl phosphite of UO 2 (H 2 PO 3 ) 2 x2FA and [UO 2 (H 2 PO 3 ) 2 H 2 O]x2TMC composition (where TMC-tetramethyl carbamide), are synthesized. Structures of complexes with DAMA, TMC, DMFA and acid dimethyl-ammonium diphosphitouranylate-(CH 3 ] 2 NH 2 x[UO 2 (HPO 3 ) 3 (H 2 PO 3 )] are investigated [ru

  1. Investigation of uranyl nitrate complexes with trialkylphosphine oxides

    International Nuclear Information System (INIS)

    Kobets, L.V.; Kopashova, I.M.; Dik, T.A.; Volodin, I.A.; Kovalenko, M.A.; Semenij, V.Ya.

    1982-01-01

    Using the methods of vibrational spectroscopy and thermal analysis a number of uranyl complexes with trialkylphosphine oxides of the general formula UO 2 (NO 3 ) 2 x2R 3 PO, where R-C 2 H 5 -C 10 H 21 have been studied. Infrared and Raman spectra are interpreted according to vibration types. Comparison of vibrational spectra of the complexes in solid phase and solutions of organic solvents permitted to find the differences in position and amount of acids responsible for complexing. It is detected that in the series of complexes investigated the strength of uranyl bond with phosphoryl group oxygen practically remains stable, whereas degree of covalence of nitrate groups is observed. The pointed out peculiarities are interpreted proceeding from the presence of bridge nitrate groups in the structure of the complexes. Thermal stability of the complexes is studied, chemism of their decomposition being suggested

  2. Critical experiments on low enriched uranyl nitrate solution with STACY

    International Nuclear Information System (INIS)

    Miyoshi, Yoshinori

    1996-01-01

    As the STACY started steady operations, systematic criticality data on low enriched uranyl nitrate solution system could be accumulated. Main experimental parameters for the cylindrical tank of 60 cm in diameter were uranium concentration and the reflector condition. Basic data on a simple geometry will be helpful for the validation of the standard criticality safety codes, and for evaluating the safety margin included in the criticality designs. Experiments on the reactivity effects of structural materials such as borated concrete and polyethylene are on schedule next year as the second series of experiments using 10 wt% enriched uranyl solution. Furthermore, neutron interacting experiments with two slab tanks will be performed to investigate the fundamental properties of neutron interaction effects between core tanks. These data will be useful for making more reasonable calculation models and for evaluating the safety margin in the criticality designs for the multiple unit system. (J.P.N.)

  3. Transformation of zinc hydroxide chloride monohydrate to crystalline zinc oxide.

    Science.gov (United States)

    Moezzi, Amir; Cortie, Michael; McDonagh, Andrew

    2016-04-25

    Thermal decomposition of layered zinc hydroxide double salts provides an interesting alternative synthesis for particles of zinc oxide. Here, we examine the sequence of changes occurring as zinc hydroxide chloride monohydrate (Zn5(OH)8Cl2·H2O) is converted to crystalline ZnO by thermal decomposition. The specific surface area of the resultant ZnO measured by BET was 1.3 m(2) g(-1). A complicating and important factor in this process is that the thermal decomposition of zinc hydroxide chloride is also accompanied by the formation of volatile zinc-containing species under certain conditions. We show that this volatile compound is anhydrous ZnCl2 and its formation is moisture dependent. Therefore, control of atmospheric moisture is an important consideration that affects the overall efficiency of ZnO production by this process.

  4. Dehydration of aluminum chloride hexahydrate: a technical assessment

    International Nuclear Information System (INIS)

    Miller, R.L.

    1984-04-01

    Physical and chemical properties of aluminum chloride hexahydrate, ACH, and related compounds are noted as well as the relation of these properties to the problem of dehydration of ACH to form anhydrous aluminum chloride. Several approaches to the dehydration of ACH are discussed and a rationale or each approach is given: solvent extraction, ligand exchange, azeotropic distillation, chemical dehydration, and energy specific direct heating. While the thermodynamics of dehydration are frequently favorable, the rate of reaction and the mechanisms of reaction are more frequently unfavorable. However, each approach requires experimentation to test its effectiveness. The stability of the aluminum-oxygen bond in the hydrate is such that dehydration without decomposition to the oxide will be very difficult

  5. Uranyl(VI) luminescence spectroscopy at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Steudtner, Robin; Franzen, Carola; Brendler, Vinzenz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Surface Processes; Haubitz, Toni [Brandenburg Univ. of Technology, Cottbus-Senftenberg (Germany)

    2016-07-01

    We studied the influence of temperature and ionic strength on the luminescence characteristics (band position, decay time and intensity) of the free uranyl ion (UO{sub 2}{sup 2+}) in acidic aqueous solution. Under the chosen conditions an increasing temperature reduced both intensity and luminescence decay time of the UO{sub 2}{sup 2+} luminescence, but the individual U(VI) emission bands did not change.

  6. Tritium gettering from air with hydrogen uranyl phosphate

    International Nuclear Information System (INIS)

    Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, R.T.

    1985-01-01

    Hydrogen uranyl phosphate (HUP), a solid proton electrolyte, getters tritium gas and water vapor from air by DC electrical action. We have reduced the formation of residual tritiated water to less than 2%, and demonstrated that HUP can clean a 5.5 m 3 working glove box. Data are presented to illustrate the parameters of the gettering and a model is derived. Two other tritium gettering electrolytes have been discovered. 9 refs., 5 figs., 3 tabs

  7. Tritium gettering from air with hydrogen uranyl phosphate. Revision 1

    International Nuclear Information System (INIS)

    Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, R.T.

    1985-01-01

    Hydrogen uranyl phosphate (HUP), a solid proton electrolyte, getters tritium gas and water vapor from air by DC electrical action. We have reduced the formation of residual tritiated water to less than 2%, and demonstrated that HUP can clean a 5.5 m 3 working glove box. Data are presented to illustrate the parameters of the gettering and a model is derived. Two other tritium gettering electrolytes have been discovered. 9 refs., 5 figs., 3 tabs

  8. Structural determination of some uranyl compounds by vibrational spectroscopy

    International Nuclear Information System (INIS)

    Rodriguez S, A.; Martinez Q, E.

    1990-07-01

    The vibrational spectra of different uranyl compounds has been studied and of it spectral information has been used the fundamental asymmetric vibrational frequency, to determine the length and constant bond force U=O by means of the combination of the concept of absorbed energy and the mathematical expression of Badger modified by Jones. It is intended a factor that simplifies the mathematical treatment and the results are compared with the values obtained for other methods. (Author)

  9. Crystal structure of the uranyl-oxide mineral rameauite

    Czech Academy of Sciences Publication Activity Database

    Plášil, Jakub; Škoda, R.; Čejka, J.; Bourgoin, V.; Boulliard, J.C.

    2016-01-01

    Roč. 28, č. 5 (2016), s. 959-967 ISSN 0935-1221 R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : rameauite * uranyl-oxide hydroxy-hydrate * crystal structure * Raman spectrum Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.362, year: 2016

  10. Chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions

    International Nuclear Information System (INIS)

    Anon.

    1981-01-01

    The standard covers analytical procedures to determine compliance of nuclear-grade uranyl nitrate solution to specifications. The following methods are described in detail: uranium by ferrous sulfate reduction-potassium dichromate titrimetry and by ignition gravimetry; specific gravity by pycnometry; free acid by oxalate complexation; thorium by the Arsenazo(III) (photometric) method; chromium by the diphenylcarbazide (photometric) method; molybdenum by the thiocyanate (photometric) method; halogens separation by steam distillation; fluorine by specific ion electrode; halogen distillate analysis: chloride, bromide and iodide by amperometric microtitrimetry; bromine by the fluorescein (photometric) method; sulfate sulfur by (photometric) turbidimetry; phosphorus by the molybdenum blue (photometric) method; silicon by the molybdenum blue (photometric) method; carbon by persulfate oxidation-acid titrimetry; nonvolatile impurities by spectrography; volatile impurities by rotating-disk spark spectrography; boron by emission spectrography; impurity elements by spark source mass spectrography; isotopic composition by multiple filament surface-ionization mass spectrometry; uranium-232 by alpha spectrometry; total alpha activity by direct alpha counting; fission product activity by beta and gamma counting; entrained organic matter by infrared spectrophotometry

  11. Preparation and thermogravimetric study of some uranyl phosphates

    International Nuclear Information System (INIS)

    Schaekers, J.M.

    1970-10-01

    The preparation of uranyl ammonium phosphate trihydrate (UAP = UO 2 NH 4 PO 4 .3H 2 O), acid uranyl phosphate tetrahydrate(AUP = UO 2 HPO 4 .4H 2 O) and neutral uranyl phosphate tetrahydrate (NUPT = (UO 2 ) 3 (PO 4 ) 2 .4H 2 O) was investigated during the data from the literature. The thermal decomposition in different atmospheres, such as air, oxygen, nitrogen and argon, was studied in the temperature range 25-1000 0 C. It was found that the pyrophosphate U 2 O 3 P 2 O 7 is a stable decomposition product of UAP as well as of AUP. A mixture of U 3 O 8 and U 2 O 3 P 2 O 7 is obtained when the NUPT is decomposed in an oxygen-free atmosphere. NUPT however is stable in an oxidising atmosphere. Hydrogen and carbon reductions were also carried out, and UO 2 or (UO) 2 P 2 O 7 as well as mixtures of these two products can be obtained, depending on the starting material and the reduction temperature. The different reduction and decomposition reactions were studied by means of thermogravimetric analysis, and activation energies were calculated where possible. I.R. spectral analysis was also used to identify various products with the same composition [af

  12. Safe use and waste disposal of uranyl acetate

    International Nuclear Information System (INIS)

    Sanchez, A.; Calvo, S.; Caparros, G.; Gallego, E.; Rascon, J.; Valladares, M.C.

    2006-01-01

    Radioactive labelled molecules are widely used in Biological Research Centres. The most common radioisotopes are: 32 P, 33 P, 35 S, 3 H, 14 C, 125 I and 45 Ca.Due to the inherent risk in the manipulation of these radiation unsealed sources, in these radioactive installations there are established radiological protection programs to reduce this potential risk and the professional exposure in the manipulation and in the radioactive waste generated. In these Biological Research Centres we used techniques with other radioactive products less used, that we must to control. It is the case of the use of uranyl acetate. Uranyl acetate is a uranium salt used in the preparation of samples for analysis in the electron microscope. Although the amounts used are relatively small, both the chemical and radiological toxicities of these compounds are significant and require working whit that some cautions, with the main emphasis on avoiding the possibility of inhalation of fine particulates or vapours. Due to changes in the Spanish regulations for this product, it was necessary to establish a specific control program in its manipulation. The purpose of this work is the accomplishment of specific protocols for the acquisition, manipulation, contamination measurements, inspections of the work zone and waste management, in order to minimize the risks in the manipulation of uranyl acetate,as well as apply the knowledge and use of specific norms for working with this product. (authors)

  13. Safe use and waste disposal of uranyl acetate

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez, A.; Calvo, S.; Caparros, G.; Gallego, E.; Rascon, J.; Valladares, M.C. [Centro de Biologia Molecular, Madrid (Spain)

    2006-07-01

    Radioactive labelled molecules are widely used in Biological Research Centres. The most common radioisotopes are: {sup 32}P,{sup 33}P, {sup 35}S,{sup 3}H,{sup 14}C,{sup 125}I and {sup 45}Ca.Due to the inherent risk in the manipulation of these radiation unsealed sources, in these radioactive installations there are established radiological protection programs to reduce this potential risk and the professional exposure in the manipulation and in the radioactive waste generated. In these Biological Research Centres we used techniques with other radioactive products less used, that we must to control. It is the case of the use of uranyl acetate. Uranyl acetate is a uranium salt used in the preparation of samples for analysis in the electron microscope. Although the amounts used are relatively small, both the chemical and radiological toxicities of these compounds are significant and require working whit that some cautions, with the main emphasis on avoiding the possibility of inhalation of fine particulates or vapours. Due to changes in the Spanish regulations for this product, it was necessary to establish a specific control program in its manipulation. The purpose of this work is the accomplishment of specific protocols for the acquisition, manipulation, contamination measurements, inspections of the work zone and waste management, in order to minimize the risks in the manipulation of uranyl acetate,as well as apply the knowledge and use of specific norms for working with this product. (authors)

  14. Design of one evaporation system for uranyl nitrate solution

    International Nuclear Information System (INIS)

    Mancilla Romero, R.J.

    1975-01-01

    The authors propose an instant evaporation system with recirculation of the concentrated solution to raise the concentration from 50 to 1500 g of uranium per litre of solution. The capacity of the plant is to be 14.1 kg of uranium per hour. The main equipment used in the system is as follows: 1. Ring-type heat exchanger, for increasing the temperature of the mixture of fresh and recirculated solution from 80 to 115 0 C; 2. Separation tank, in which instant evaporation is carried out. The absolute pressure inside the tank will be 500 mmHg, with steam separation from a concentrated (78.5 wt.%) uranyl nitrate solution; 3. Desuperheater-condenser of horizontal tubular type for condensing water vapour and recovering any uranyl nitrate that may have been entrained; 4. Storage tank for the concentrate, with a capacity for one day's normal operation, and a heating coil to prevent crystallization of the concentrated solution; 5. Two storage tanks for feed and condensate with capacity for one day's normal operation; 6. Supporting structure for the above components. Virtually all equipment in contact with the uranyl nitrate solution will be made of 304 stainless steel. Saturated steam at 143.3 0 C will be required. The cost of the proposed system is $543 030.00. (author)

  15. Photochemistry and exciplex of the uranyl ion in aqueous solution

    International Nuclear Information System (INIS)

    Marcantonatos, M.D.

    1980-01-01

    The effects of acidity, temperature, self-quenching and H-donor concentration on the luminescent state of the aqua-uranyl(VI) ion have been studied in aqueous acidic nitrate and perchlorate solution. The detailed results cannot be explained by any single simple mechanism such as radiative, non-radiative or spontaneous collisional quenching, or irreversible hydrogen abstraction from water. Quantitative analysis of the results shows a far more complex mechanism, involving the adiabatic formation of the species *UO 2 H 2+ and *U 2 O 4 H 4+ , as already proposed by the author. This mechanism is supported by state and m.o. correlations. The abstraction of hydrogen from water is shown to take place by H atom transfer in a *uranyl-water complex intermediate, rather than by attack of H + on the fully occupied πsub(u) orbitals of uranium(V) in a well-defined uranyl water complex with strong charge transfer character. A qualitative description of the exciplex *U 2 O 4 H 4+ is shown to be possible in a v.b. formalism and the origin of its radiative properties is discussed on this basis. (author)

  16. Variable Denticity in Carboxylate Binding to the Uranyl Coordination Complexes

    International Nuclear Information System (INIS)

    Groenewold, G.S.; De Jong, Wibe A.; Oomens, Jos; Van Stipdonk, Michael J.

    2010-01-01

    Tris-carboxylate complexes of the uranyl (UO2)2+ cation with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transformion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetatouranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric -CO2 stretches of both the monodentate and bidentate acetate, CH3 bending and umbrella vibrations, and a uranyl O-U-O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate, and two bidentate benzoate ligands.

  17. Synthesis of fertilizers nitrogen and 15N-enriched. Pt. I. Production of enriched 15N-anhydrous ammonia

    International Nuclear Information System (INIS)

    Bendassolli, J.A.; Mortatti, J.; Trivelin, P.C.O.; Victoria, R.L.

    1988-01-01

    The results of 15 N-anhydrous ammonia production through reaction between 15 N-enriched ammonium sulphate and sodium hidroxide are reported. Influence of the reaction temperature, carrier gas flow, reaction time and mass of ammonium sulphate on the production of anhydrous ammonia were studied. Analyses for the cost of production of 5% atoms in 15 N-enriched anhydrous ammonia were made. (M.A.C.) [pt

  18. Chloride test - blood

    Science.gov (United States)

    Serum chloride test ... A greater-than-normal level of chloride is called hyperchloremia. It may be due to: Carbonic anhydrase inhibitors (used to treat glaucoma) Diarrhea Metabolic acidosis Respiratory alkalosis (compensated) Renal ...

  19. Chloride in diet

    Science.gov (United States)

    ... this page: //medlineplus.gov/ency/article/002417.htm Chloride in diet To use the sharing features on this page, please enable JavaScript. Chloride is found in many chemicals and other substances ...

  20. Mercuric chloride poisoning

    Science.gov (United States)

    ... page: //medlineplus.gov/ency/article/002474.htm Mercuric chloride poisoning To use the sharing features on this page, please enable JavaScript. Mercuric chloride is a very poisonous form of mercury. It ...

  1. Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

    International Nuclear Information System (INIS)

    Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

    2012-01-01

    Highlights: ► The stability of peroxide in uranyl peroxo carbonato complex solutions with different temperatures was characterized. ► The decomposition rate of uranyl peroxo carbonato complex ion to uranyl tris-carbonato complex ion was observed to increase with temperature ► The decomposition kinetics of uranyl peroxo carbonato complex ions was evaluated by absorption and Raman spectroscopies. ► A precipitate of uranyl peroxo carbonato complex solution was evaluated with XRD. - Abstract: This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144 × 10 3 J mol −1 . The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.

  2. Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kwang-Wook, E-mail: nkwkim@kaeri.re.kr [Korea Atomic Energy Research Institute, 1045 Daedeok daero, Yuseong, Daejeon 305-353 (Korea, Republic of); Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon [Korea Atomic Energy Research Institute, 1045 Daedeok daero, Yuseong, Daejeon 305-353 (Korea, Republic of); Shin, Dong-Woo [Gyeongsang National University, 900 Gajwa, Jinju 660-701 (Korea, Republic of)

    2012-09-30

    Highlights: Black-Right-Pointing-Pointer The stability of peroxide in uranyl peroxo carbonato complex solutions with different temperatures was characterized. Black-Right-Pointing-Pointer The decomposition rate of uranyl peroxo carbonato complex ion to uranyl tris-carbonato complex ion was observed to increase with temperature Black-Right-Pointing-Pointer The decomposition kinetics of uranyl peroxo carbonato complex ions was evaluated by absorption and Raman spectroscopies. Black-Right-Pointing-Pointer A precipitate of uranyl peroxo carbonato complex solution was evaluated with XRD. - Abstract: This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144 Multiplication-Sign 10{sup 3} J mol{sup -1}. The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.

  3. Energy transfer and quenching processes of excited uranyl ion and lanthanide ions in solutions

    International Nuclear Information System (INIS)

    Yamamura, Tomoo; Tomiyasu, Hiroshi

    1995-01-01

    Deactivation processes of photoexcited uranyl ion by various lanthanide ions in aqueous solution were studied. Each lanthanide ions show different interaction with excited uranyl ion depending on its lowest excited energy level, the number of 4f electrons and the acid concentration of the solution. (author)

  4. A surface structural model for ferrihydrite II: Adsorption of uranyl and carbonate

    NARCIS (Netherlands)

    Hiemstra, T.; Riemsdijk, van W.H.; Rossberg, A.; Ulrich, K.

    2009-01-01

    The adsorption of uranyl (UO22+) on ferrihydrite has been evaluated with the charge distribution (CD) model for systems covering a very large range of conditions, i.e. pH, ionic strength, CO2 pressure, U(VI) concentration, and loading. Modeling suggests that uranyl forms bidentate inner sphere

  5. A protein engineered to bind uranyl selectively and with femtomolar affinity

    Science.gov (United States)

    Zhou, Lu; Bosscher, Mike; Zhang, Changsheng; Özçubukçu, Salih; Zhang, Liang; Zhang, Wen; Li, Charles J.; Liu, Jianzhao; Jensen, Mark P.; Lai, Luhua; He, Chuan

    2014-03-01

    Uranyl (UO22+), the predominant aerobic form of uranium, is present in the ocean at a concentration of ~3.2 parts per 109 (13.7 nM) however, the successful enrichment of uranyl from this vast resource has been limited by the high concentrations of metal ions of similar size and charge, which makes it difficult to design a binding motif that is selective for uranyl. Here we report the design and rational development of a uranyl-binding protein using a computational screening process in the initial search for potential uranyl-binding sites. The engineered protein is thermally stable and offers very high affinity and selectivity for uranyl with a Kd of 7.4 femtomolar (fM) and >10,000-fold selectivity over other metal ions. We also demonstrated that the uranyl-binding protein can repeatedly sequester 30-60% of the uranyl in synthetic sea water. The chemical strategy employed here may be applied to engineer other selective metal-binding proteins for biotechnology and remediation applications.

  6. Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

    International Nuclear Information System (INIS)

    Maroun, E.B.; Hagege, A.; Asfari, Z.; Basset, CH.; Quemeneur, E.; Vidaud, C.

    2009-01-01

    With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

  7. Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

    Energy Technology Data Exchange (ETDEWEB)

    Maroun, E.B.; Hagege, A.; Asfari, Z. [Laboratoire de Chimie Analytique et Minerale, UMR 7178 ULP/CNRS/IN2P3 LC4, ECPM, Strasbourg Cedex (France); Basset, CH.; Quemeneur, E.; Vidaud, C. [CEA IBEB, SBTN, Centre de Marcoule, Bagnols-sur-Ceze (France)

    2009-07-01

    With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

  8. Synthesis, structural characterization, and dehydration analysis of uranyl zinc mellitate, (UO{sub 2})Zn(H{sub 2}O){sub 4}(H{sub 2}mel).2H{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Olchowka, Jakub; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS) - UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

    2013-04-15

    A new heterometallic uranyl zinc carboxylate, (UO{sub 2})Zn(H{sub 2}O){sub 4}(H{sub 2}mel).2H{sub 2}O, has been hydrothermally prepared (150 C, 24 h) by using 1,2,3,4,5,6-benzenehexacarboxylic acid (mellitic acid) as organic linker in order to form a three-dimensional network. Four of the six carboxylate groups of the mellitate ligand interact with mononuclear uranyl or zinc cations, which are eightfold (hexagonal bipyramid, UO{sub 8}) or sixfold [octahedron, ZnO{sub 2}(H{sub 2}O){sub 4}] coordinated, respectively. The remaining free carboxylate arms of the mellitate species preferentially interact through hydrogen bonds with water molecules trapped within the framework. Thermogravimetric and X-ray thermodiffraction (up to 800 C) analyses and in situ infrared spectroscopy (up to 210 C) indicated that both free and bound water species are evacuated from the structure in one step between 80 and 170 C, followed by its transformation into an unknown, anhydrous, poorly crystalline phase [UO{sub 2}Zn(mel)] up to 320 C. After the formation of an amorphous phase, the re-crystallization of oxides α-ZnU{sub 3}O{sub 10} and ZnO was observed from 460 C. The fluorescence spectrum of the as-synthesized uranyl zinc mellitate shows the six bands that are typical for vibronic couplings of the [O=U=O]{sup 2+} moiety. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Quantification of uranyl in presence of citric acid; Cuantificacion de uranilo en presencia de acido citrico

    Energy Technology Data Exchange (ETDEWEB)

    Garcia G, N.; Barrera D, C.E. [UAEM, Facultad de Quimica, 50000 Toluca, Estado de Mexico (Mexico); Ordonez R, E. [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)]. e-mail: nidgg@yahoo.com.mx

    2007-07-01

    To determine the influence that has the organic matter of the soil on the uranyl sorption on some solids is necessary to have a detection technique and quantification of uranyl that it is reliable and sufficiently quick in the obtaining of results. For that in this work, it intends to carry out the uranyl quantification in presence of citric acid modifying the Fluorescence induced by UV-Vis radiation technique. Since the uranyl ion is very sensitive to the medium that contains it, (speciation, pH, ionic forces, etc.) it was necessary to develop an analysis technique that stands out the fluorescence of uranyl ion avoiding the out one that produce the organic acids. (Author)

  10. Comparative study of uranyl(VI) and -(V) carbonato complexes in an aqueous solution.

    Science.gov (United States)

    Ikeda, Atsushi; Hennig, Christoph; Tsushima, Satoru; Takao, Koichiro; Ikeda, Yasuhisa; Scheinost, Andreas C; Bernhard, Gert

    2007-05-14

    Electrochemical, complexation, and electronic properties of uranyl(VI) and -(V) carbonato complexes in an aqueous Na2CO3 solution have been investigated to define the appropriate conditions for preparing pure uranyl(V) samples and to understand the difference in coordination character between UO22+ and UO2+. Cyclic voltammetry using three different working electrodes of platinum, gold, and glassy carbon has suggested that the electrochemical reaction of uranyl(VI) carbonate species proceeds quasi-reversibly. Electrolysis of UO22+ has been performed in Na2CO3 solutions of more than 0.8 M with a limited pH range of 11.7 < pH < 12.0 using a platinum mesh electrode. It produces a high purity of the uranyl(V) carbonate solution, which has been confirmed to be stable for at least 2 weeks in a sealed glass cuvette. Extended X-ray absorption fine structure (EXAFS) measurements revealed the structural arrangement of uranyl(VI) and -(V) tricarbonato complexes, [UO2(CO3)3]n- [n = 4 for uranyl(VI), 5 for uranyl(V)]. The bond distances of U-Oax, U-Oeq, U-C, and U-Odist are determined to be 1.81, 2.44, 2.92, and 4.17 A for the uranyl(VI) complex and 1.91, 2.50, 2.93, and 4.23 A for the uranyl(V) complex, respectively. The validity of the structural parameters obtained from EXAFS has been supported by quantum chemical calculations for the uranyl(VI) complex. The uranium LI- and LIII-edge X-ray absorption near-edge structure spectra have been interpreted in terms of electron transitions and multiple-scattering features.

  11. Comparing uranyl sorption complexes on soil and reference clays

    International Nuclear Information System (INIS)

    Chisholm-Brause, C.J.; Berg, J.M.; Conradson, S.D.; Morris, D.E.; McKinley, J.P.; Zachara, J.M.

    1993-01-01

    Clay minerals and other components in natural soils may play a key role in limiting the mobility of uranium in the environment through the formation of sorption complexes. Reference clays are frequently used as models to study sorption processes because they have well-known chemical and physical properties, but they may differ chemically and morphologically from clays derived from natural soils. Therefore, inferences based on reference clay data have been questioned. The authors have used luminescence and x-ray absorption spectroscopies to characterize the sorption complexes of aqueous uranyl (UO 2 2+ ) species on two soil smectites from the Kenoma and Ringold formations, and compared these results to those obtained on reference smectite clays. The pH dependence of uptake suggests that the ratio of sorption on amphoteric edge sites is greater for the soil smectites than for reference clays such as Wyoming montmorillonite (SWy-1). The luminescence spectra for uranyl sorbed to the soil clays are very similar to those for uranyl sorbed principally to the edge sites of SWy-1. This observation supports the solution data suggesting that adsorption to amphoteric sites is a more important mechanism for soil clays. However, the spectral data indicate that the sorption complexes on natural and reference clays are quite similar. Furthermore, as with the reference clays, the authors have found that the chemistry of the solution plays a greater role in defining the sorption complex than does the clay matrix. Thus, if differences in surface properties are adequately taken into account, the reference clays may serve as useful analogs for soil clays in investigations of metal-ion sorption

  12. Determination of free nitric acid in uranyl nitrate solution

    International Nuclear Information System (INIS)

    Mayankutty, P.C.; Ravi, S.; Nadkarni, M.N.

    1981-01-01

    Potentiometric titration of uranyl nitrate solution with sodium hydroxide exhibits two peaks. The first peak characterises the following reaction, UO 2 (C 2 O 4 )+NaOH Na[UO 2 (C 2 O 4 )(OH)]. This reaction, indicating the partial hydrolysis of uranyl oxalate complex, appears to be complete at pH9. If the titration is carried out to this end-point pH, the total alkali consumed can be equated to the sum of uranium content and the free acidity present in the sample volume. Based on this, a method was standardised to determine the free acidity in uranyl nitrate solution. The sample, taken in a solution of potassium oxalate previously adjusted to pH9, is titrated to this pH with standard sodium hydroxide. The free acidity in the sample can be computed by subtracting the alkali reacted with uranium from the total alkali consumed. Analyses of several synthetic samples containing uranium and nitric acid in a wide range of combinations indicate that the free acidity can be accurately determined by this method, if uranium concentration in the sample is known. The results are compared to those obtained by two other widely used methods, viz., (i) titration of pH7 in the presence of neutral potassium oxalate to suppress hydrolysis and (ii) separation of hydrolyzable ions on a cationic resin and alkali titration of the free acid released. The advantages of and the precision obtained with the present method over the above two methods are discussed. (author)

  13. Formation of a new crystalline form of anhydrous β-maltose by ethanol-mediated crystal transformation.

    Science.gov (United States)

    Verhoeven, Nicolas; Neoh, Tze Loon; Ohashi, Tetsuya; Furuta, Takeshi; Kurozumi, Sayaka; Yoshii, Hidefumi

    2012-04-01

    β-Maltose monohydrate was transformed into an anhydrous form by ethanol-mediated method under several temperatures with agitation. A new stable anhydrous form of β-maltose (Mβ(s)) was obtained, as substantiated by the X-ray diffraction patterns. Mβ(s) obtained by this method presented a fine porous structure, resulting in greater specific surface area compared to those of β-maltose monohydrate and anhydrous β-maltose obtained by vacuum drying (Mβ(h)). The crystal transformation presumably consisted of two steps: dehydration reaction from the hydrous to amorphous forms and crystal formation from the amorphous forms to the noble anhydrous form. The kinetics of these reactions were determined by thermal analysis using Jander's equation and Arrhenius plots. The overall activation energies of the dehydration reaction and the formation of anhydrous maltose were evaluated to be 100 and 90 kJ/mol, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Study of diamagnetism in uranyl complexes of some Schiff bases

    International Nuclear Information System (INIS)

    Dodwad, S.S.; Sawant, A.S.

    1992-01-01

    Uranyl complexes of Schiff bases obtained by condensing salicylaldehyde with aromatic amines have been isolated and characterised. The complexes have the formula M (LH) 2 (NO 3 ) 2 where M = UO 2 and LH = Schiff base. The magnetic susceptibilities of these complexes have been measured on a Gouy balance. These values have been compared with the computed ones. The percentage deviation between the observed and computed values of molar magnetic susceptibilities clearly show that they are outside experimental error and therefore significant. These deviations have been discussed in the light of VanVleck's, equation for molar susceptibility of polyatomic molecule. (author). 3 refs., 1 tab

  15. Acute toxicity of uranium hexafluoride, uranyl fluoride and hydrogen fluoride

    International Nuclear Information System (INIS)

    Just, R.A.

    1988-01-01

    Uranium hexafluoride (UF 6 ) released into the atmosphere will react rapidly with moisture in the air to form the hydrolysis products uranyl fluoride (UO 2 F 2 ) and hydrogen fluoride (HF). Uranium compounds such as UF 6 and UO 2 F 2 exhibit both chemical toxicity and radiological effects, while HF exhibits only chemical toxicity. This paper describes the development of a methodology for assessing the human health consequences of a known acute exposure to a mixture of UF 6 , UO 2 F 2 , and HF. 4 refs., 2 figs., 5 tabs

  16. Biosolubilization of uranyl ions in uranium ores by hydrophyte plants

    International Nuclear Information System (INIS)

    Cecal, Alexandru; Calmoi, Rodica; Melniciuc-Puica, Nicoleta

    2006-01-01

    This paper investigated the bioleaching of uranyl ions from uranium ores, in aqueous medium by hydrophyte plants: Lemna minor, Azolla caroliniana and Elodea canadensis under different experimental conditions. The oxidation of U(IV) to U(VI) species was done by the atomic oxygen generated in the photosynthesis process by the aquatic plants in the solution above uranium ores. Under identical experimental conditions, the capacity of bioleaching of uranium ores decreases according to the following series: Lemna minor > Elodea canadensis > Azolla caroliniana. The results of IR spectra suggest the possible use of Lemna minor and Elodea canadensis as a biological decontaminant of uranium containing wastewaters. (author)

  17. Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O and anhydrous Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Na; Klepov, Vladislav V. [Forschungszentrum Jülich GmbH, Institute for Energy and Climate Research (IEK-6), 52428 Jülich (Germany); Villa, Eric M. [Department of Chemistry, Creighton University, 2500 California Plaza, Omaha NE 68178 (United States); Bosbach, Dirk [Forschungszentrum Jülich GmbH, Institute for Energy and Climate Research (IEK-6), 52428 Jülich (Germany); Suleimanov, Evgeny V. [Department of Chemistry, Lobachevsky State University of Nizhny Novgorod, 603950 Nizhny Novgorod (Russian Federation); Depmeier, Wulf [Institut für Geowissenschaften, Universität zu Kiel, 24118 Kiel (Germany); Albrecht-Schmitt, Thomas E., E-mail: albrecht-schmitt@chem.fsu.edu [Department of Chemistry and Biochemistry, Florida State University, 102 Varsity Way, Tallahassee, FL 32306-4390 (United States); Alekseev, Evgeny V., E-mail: e.alekseev@fz-juelich.de [Forschungszentrum Jülich GmbH, Institute for Energy and Climate Research (IEK-6), 52428 Jülich (Germany); Institut für Kristallographie, RWTH Aachen University, 52066 Aachen (Germany)

    2014-07-01

    The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O (α-, β-RbUAs) and the anhydrous phase Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions. - Graphical abstract: Three different layer geometries observed in the structures of Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] and α- and β- Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O. Two different coordination environments of uranium polyhedra (types I and II) are shown schematically on the top of the figure. - Highlights: • Three new uranyl arsenates were synthesized from the hydrothermal reactions. • The phases consist of the topologically identical but geometrically different layers. • Topotactic transitions were observed in the processes of mono-hyrates dehydration.

  18. Outcomes of curettage and anhydrous alcohol adjuvant for low-grade chondrosarcoma of long bone.

    Science.gov (United States)

    Kim, Wanlim; Han, Ilkyu; Kim, Eo Jin; Kang, Seungcheol; Kim, Han-Soo

    2015-06-01

    Low-grade chondrosarcoma of long bones can be treated successfully with extended intralesional curettage using adjuvants. However, there is no study reporting the use of anhydrous alcohol as an adjuvant in the treatment of low-grade chondrosarcoma. We asked (1) whether intralesional curettage and anhydrous alcohol adjuvant for low-grade chondrosarcoma is associated with good oncologic outcomes; and we report (2) the complications of the procedure. Thirty-six patients (13 men, 23 women) with a mean age of 46 years (range, 18-67 years) were treated for low-grade chondrosarcoma and followed up for a median of 62 months (range, 24-169 months). After intralesional curettage, and additional burring, anhydrous alcohol was used as an adjuvant therapy. At the time of last follow-up, there were no local recurrences or distant metastases. Six patients developed complications: 4 postoperative fractures (11%), 1 intra-articular loose body (3%) and 1 postoperative joint stiffness (3%). Anhydrous alcohol is a reasonable adjuvant for the curettage of low-grade chondrosarcoma of long bones. A long-term follow-up study is necessary, considering the slow biological progression of low-grade chondrosarcoma. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. 7 CFR 58.715 - Cream, plastic cream and anhydrous milkfat.

    Science.gov (United States)

    2010-01-01

    ... Service 1 Quality Specifications for Raw Material § 58.715 Cream, plastic cream and anhydrous milkfat. These food products shall be pasteurized, sweet, have a pleasing and desirable flavor and be free from objectionable flavors, and shall be obtained from milk which complies with the quality requirements as specified...

  20. Structural observations of heterometallic uranyl copper(II) carboxylates and their solid-state topotactic transformation upon dehydration.

    Science.gov (United States)

    Olchowka, Jakub; Falaise, Clément; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

    2013-02-04

    The hydrothermal reactions of uranyl nitrate and metallic copper with aromatic polycarboxylic acids gave rise to the formation of five heterometallic UO(2)(2+)-Cu(2+) coordination polymers: (UO(2))Cu(H(2)O)(2)(1,2-bdc)(2) (1; 1,2-bdc = phthalate), (UO(2))Cu(H(2)O)(2)(btec)⋅4 H(2)O (2) and (UO(2))Cu(btec) (2'; btec = pyromellitate), (UO(2))(2)Cu(H(2)O)(4)(mel) (3; mel = mellitate), and (UO(2))(2)O(OH)(2)Cu(H(2)O)(2)(1,3-bdc)⋅H(2)O (4; 1,3-bdc = isophthlalate). Single-crystal X-ray diffraction (XRD) analysis of compound 1 revealed 2D layers of chains of UO(8) and CuO(4)(H(2)O)(2) units that were connected through the phthalate ligands. In compound 2, these sheets were connected to each other through the two additional carboxylate arms of the pyromellitate, thus resulting in a 3D open-framework with 1D channels that trapped water molecules. Upon heating, free and bonded water species (from Cu-OH(2)) were evacuated from the structure. This thermal transition was followed by in situ XRD and IR spectroscopy. Heating induced a solid-state topotactic transformation with the formation of a new set of Cu-O interactions in the crystalline anhydrous structure (2'), in order to keep the square-planar environment around the copper centers. The structure of compound 3 was built up from trinuclear motifs, in which one copper center, CuO(4)(OH(2))(2), was linked to two uranium units, UO(5)(H(2)O)(2). The assembly of this trimer, "U(2)Cu", with the mellitate generated a 3D network. Complex 4 contained a tetranuclear uranyl core of UO(5)(OH)(2) and UO(6)(OH) units that were linked to two copper centers, CuO(OH)(2)(H(2)O)(2), which were then connected to each other through isophthalate ligands and U=O-Cu interactions to create a 3D structure. The common structural feature of these different compounds is a bridging oxo group of U=O-Cu type, which is reflected by apical Cu-O distances in the range 2.350(3)-2.745(5) Å. In the case of a shorter Cu-O distance, a slight lengthening

  1. Structural observations of heterometallic uranyl copper(II) carboxylates and their solid-state topotactic transformation upon dehydration

    International Nuclear Information System (INIS)

    Olchowka, Jakub; Falaise, Clement; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

    2013-01-01

    The hydrothermal reactions of uranyl nitrate and metallic copper with aromatic polycarboxylic acids gave rise to the formation of five heterometallic UO 2 2+ -Cu 2+ coordination polymers: (UO 2 )Cu(H 2 O) 2 (1,2-bdc) 2 (1; 1,2-bdc=phthalate), (UO 2 )Cu(H 2 O) 2 (btec).4 H 2 O (2) and (UO 2 )Cu(btec) (2'; btec=pyromellitate), (UO 2 ) 2 Cu(H 2 O) 4 (mel) (3; mel=mellitate), and (UO 2 ) 2 O(OH) 2 Cu(H 2 O) 2 (1,3-bdc).H 2 O (4; 1,3-bdc=isophthlalate). Single-crystal X-ray diffraction (XRD) analysis of compound 1 revealed 2D layers of chains of UO 8 and CuO 4 (H 2 O) 2 units that were connected through the phthalate ligands. In compound 2, these sheets were connected to each other through the two additional carboxylate arms of the pyromellitate, thus resulting in a 3D open-framework with 1D channels that trapped water molecules. Upon heating, free and bonded water species (from Cu-OH 2 ) were evacuated from the structure. This thermal transition was followed by in situ XRD and IR spectroscopy. Heating induced a solid-state topotactic transformation with the formation of a new set of Cu-O interactions in the crystalline anhydrous structure (2'), in order to keep the square-planar environment around the copper centers. The structure of compound 3 was built up from trinuclear motifs, in which one copper center, CuO 4 (OH 2 ) 2 , was linked to two uranium units, UO 5 (H 2 O) 2 . The assembly of this trimer, ''U 2 Cu'', with the mellitate generated a 3D network. Complex 4 contained a tetranuclear uranyl core of UO 5 (OH) 2 and UO 6 (OH) units that were linked to two copper centers, CuO(OH) 2 (H 2 O) 2 , which were then connected to each other through isophthalate ligands and U=O-Cu interactions to create a 3D structure. The common structural feature of these different compounds is a bridging oxo group of U=O-Cu type, which is reflected by apical Cu-O distances in the range 2.350(3)-2.745(5) Aa. In the case of a shorter Cu-O distance, a slight

  2. Structural observations of heterometallic uranyl copper(II) carboxylates and their solid-state topotactic transformation upon dehydration

    Energy Technology Data Exchange (ETDEWEB)

    Olchowka, Jakub; Falaise, Clement; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS), UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

    2013-02-04

    The hydrothermal reactions of uranyl nitrate and metallic copper with aromatic polycarboxylic acids gave rise to the formation of five heterometallic UO{sub 2}{sup 2+}-Cu{sup 2+} coordination polymers: (UO{sub 2})Cu(H{sub 2}O){sub 2}(1,2-bdc){sub 2} (1; 1,2-bdc=phthalate), (UO{sub 2})Cu(H{sub 2}O){sub 2}(btec).4 H{sub 2}O (2) and (UO{sub 2})Cu(btec) (2'; btec=pyromellitate), (UO{sub 2}){sub 2}Cu(H{sub 2}O){sub 4}(mel) (3; mel=mellitate), and (UO{sub 2}){sub 2}O(OH){sub 2}Cu(H{sub 2}O){sub 2}(1,3-bdc).H{sub 2}O (4; 1,3-bdc=isophthlalate). Single-crystal X-ray diffraction (XRD) analysis of compound 1 revealed 2D layers of chains of UO{sub 8} and CuO{sub 4}(H{sub 2}O){sub 2} units that were connected through the phthalate ligands. In compound 2, these sheets were connected to each other through the two additional carboxylate arms of the pyromellitate, thus resulting in a 3D open-framework with 1D channels that trapped water molecules. Upon heating, free and bonded water species (from Cu-OH{sub 2}) were evacuated from the structure. This thermal transition was followed by in situ XRD and IR spectroscopy. Heating induced a solid-state topotactic transformation with the formation of a new set of Cu-O interactions in the crystalline anhydrous structure (2'), in order to keep the square-planar environment around the copper centers. The structure of compound 3 was built up from trinuclear motifs, in which one copper center, CuO{sub 4}(OH{sub 2}){sub 2}, was linked to two uranium units, UO{sub 5}(H{sub 2}O){sub 2}. The assembly of this trimer, ''U{sub 2}Cu'', with the mellitate generated a 3D network. Complex 4 contained a tetranuclear uranyl core of UO{sub 5}(OH){sub 2} and UO{sub 6}(OH) units that were linked to two copper centers, CuO(OH){sub 2}(H{sub 2}O){sub 2}, which were then connected to each other through isophthalate ligands and U=O-Cu interactions to create a 3D structure. The common structural feature of these different compounds is

  3. Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures.

    Science.gov (United States)

    Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

    2012-09-30

    This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144×10(3) J mol(-1). The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature. Copyright © 2012 Elsevier B.V. All rights reserved.

  4. Lean hydrous and anhydrous bioethanol combustion in spark ignition engine at idle

    International Nuclear Information System (INIS)

    Chuepeng, Sathaporn; Srisuwan, Sudecha; Tongroon, Manida

    2016-01-01

    Highlights: • Anhydrous ethanol burns fastest in uncalibrated engine at equal equivalence ratio. • The leaner hydrous ethanol combustion tends to elevate the COV in imep. • Hydrous ethanol consumption was 10% greater than anhydrous ethanol at ϕ = 0.67 limit. • Optimizing alternative fuel engine at idle for stability and emission is suggested. - Abstract: The applications of anhydrous bioethanol to substitute or replace gasoline fuel have shown to attain benefits in terms of engine thermal efficiency, power output and exhaust emissions from spark ignition engines. A hydrous bioethanol has also been gained more attention due to its energy and cost effectiveness. The main aim of this work is to minimize fuel quantity injected to the intake ports of a four-cylinder engine under idle condition. The engine running with hydrous ethanol undergoes within lean-burn condition as its combustion stability is analyzed using an engine indicating system. Coefficient of variation in indicated mean effective pressure is an indicator for combustion stability with hydrocarbon and carbon monoxide emission monitoring as a supplement. Anhydrous ethanol burns faster than hydrous ethanol and gasoline in the uncalibrated engine at the same fuel-to-air equivalence ratio under idle condition. The leaner hydrous ethanol combustion tends to elevate the coefficient of variation in indicated mean effective pressure. The experimental results have found that the engine consumes greater hydrous ethanol by 10% on mass basis compared with those of anhydrous ethanol at the lean limit of fuel-to-air equivalence ratio of 0.67. The results of exhaust gas analysis were compared with those predicted by chemical equilibrium analysis of the fuel-air combustion; the resemble trends were found. Calibrating the alternative fueled engine for fuel injection quantity should be accomplished at idle with combustion stability and emissions optimization.

  5. Influence of uranyl dibutylphosphate on the UV/VIS spectrophotometric online monitoring of uranium in tributylphosphate/hydrocarbon solvent

    International Nuclear Information System (INIS)

    Creech, E.T.; Rutenberg, A.C.; Smithwick, R.W.; Seals, R.D.

    1984-01-01

    In the uranium recovery process at the Y-12 Plant uranium is recovered from aqueous uranyl solutions by extraction into a solvent consisting of 30% tributylphosphate (TBP) and 70% hydrocarbon solvent. Within this process the uranium is continuously monitored by a UV/VIS absorbance measurement of the uranyl/tributylphosphate complex in the organic phase. The uranium is then further extracted from the organic phase to a final water phase. Dibutylphosphate (DBP), which is a decomposition product of TBP, builds up in the organic solvent. A very strong complex of uranyl/dibutylphosphate is formed which cannot be extracted into the aqueous phase. Prior to this work the uranyl/dibutylphosphate complex absorbance was assumed to be the same as the uranyl tributylphosphate complex. To determine the effect of the presence of uranyl/dibutylphosphate on the continuous UV/VIS monitor required (a) the purification of commercial dibutylphosphate, (b) the synthesis, and (c) the characterization of uranyl/dibutylphosphate

  6. Microporous uranyl chromates successively formed by evaporation from acidic solution

    Energy Technology Data Exchange (ETDEWEB)

    Siidra, Oleg I.; Nazarchuk, Evgeny V.; Bocharov, Sergey N.; Kayukov, Roman A. [St. Petersburg State Univ. (Russian Federation). Dept. of Crystallography; Depmeier, Wulf [Kiel Univ. (Germany). Inst. fuer Geowissenschaften

    2018-04-01

    The first microporous framework structures containing uranium and chromium have been synthesized and characterized. Rb{sub 2}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 3}(H{sub 2}O){sub 2}](H{sub 2}O){sub 3} (1) was crystallized from uranyl chromate solution by evaporation. Further evaporation led to increased viscosity of the solution and overgrowing of Rb{sub 2}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 3}(H{sub 2}O)](H{sub 2}O) (2) on the crystals of 1. With respect to 1, the framework of 2 is partially dehydrated. Both frameworks differ compositionally by only one water molecule, but this seemingly small difference affects significantly the pore size and overall structural topology of the frameworks, which present very different flexibility of the U-O-Cr links. These are rigid in the pillared framework of 1, in contrast to 2 where the U-O-Cr angles range from 126.3 to 168.2 , reflecting the substantial flexibility of Cr-O-U connections which make them comparable to the corresponding Mo-O-U links in uranyl molybdates.

  7. SEPARATION OF BARIUM VALUES FROM URANYL NITRATE SOLUTIONS

    Science.gov (United States)

    Tompkins, E.R.

    1959-02-24

    The separation of radioactive barium values from a uranyl nitrate solution of neutron-irradiated uranium is described. The 10 to 20% uranyl nitrate solution is passed through a flrst column of a cation exchange resin under conditions favoring the adsorption of barium and certain other cations. The loaded resin is first washed with dilute sulfuric acid to remove a portion of the other cations, and then wash with a citric acid solution at pH of 5 to 7 to recover the barium along with a lesser amount of the other cations. The PH of the resulting eluate is adjusted to about 2.3 to 3.5 and diluted prior to passing through a smaller second column of exchange resin. The loaded resin is first washed with a citric acid solution at a pH of 3 to elute undesired cations and then with citric acid solution at a pH of 6 to eluts the barium, which is substantially free of undesired cations.

  8. Preparation and physicochemical characterization of anionic uranyl. beta. -ketoenolates

    Energy Technology Data Exchange (ETDEWEB)

    Marangoni, G; Paolucci, G [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Graziani, R; Celon, E

    1978-01-01

    New classes of anionic uranyl ..beta..-ketoenolates of formula (UO/sub 2/L/sub 2/X)/sup -/ (where L = 1,3-diphenylpropane-1,3-dionate (dppd), 4,4,4-trifluoro-1-phenylbutane-1,3-dionate (tfpbd), or 1-phenylbutane-1,3-dionate (pbd); X = Cl/sup -/, Br/sup -/, I/sup -/, (NO/sub 3/)/sup -/, (O/sub 2/CMe)/sup -/, or (NCS)/sup -/) and (L/sub 2/O/sub 2/U(..mu..-X) UO/sub 2/L/sub 2/)/sup -/ (where X = F/sup -/, and also Cl/sup -/ only in the case of L = dppd) have been synthesized and characterized by a number of physical measurements. The different ability of the various anionic ligands to enter into the co-ordination sphere of the uranyl ion, their potentially different bonding modes, and the possible correlations between physical parameters and the nature of either the chelate substituents or the anionic ligand are discussed.

  9. Bases for DOT exemption uranyl nitrate solution shipments

    International Nuclear Information System (INIS)

    Moyer, R.A.

    1982-07-01

    Uranyl nitrate solutions from a Savannah River Plant reprocessing facility have been transported in cargo tank trailers for more than 20 years without incident during transit. The solution is shipped to Oak Ridge for further processing and returned to SRP in a solid metal form for recycle. This solution, called uranyl nitrate hexahydrate (UNH) solution in Department of Transportation (DOT) regulations, is currently diluted about 2-fold to comply with DOT concentration limits (10% of low specific activity levels) specified for bulk low specific activity (LSA) liquid shipments. Dilution of the process solution increases the number of shipments, the cost of transportation, the cost of shipper preparations, the cost of further reprocessing in the receiving facility to first evaporate the added water, and the total risk to the population along the route of travel. However, the radiological risk remains about the same. Therefore, obtaining an exemption from DOT regulations to permit shipment of undiluted UNH solution, which is normally about two times the present limit, is prudent and more economical. The radiological and nonradiological risks from shipping a unit load of undiluted solution are summarized for the probable route. Data and calculations are presented on a per load or per shipment basis throughout this memorandum to keep it unclassified

  10. Modulation of the unpaired spin localization in Pentavalent Uranyl Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Vetere, V.; Maldivi, P.; Mazzanti, M. [CEA Grenoble, INAC, SCIB, laboratoire de reconnaissance ionique et chimie de coordination, 38 (France); Vetere, V. [UMR5626, laboratoire de chimie et physique quantique, universite de Toulouse, 31 - Toulouse (France)

    2010-06-15

    The electronic structure of various complexes of pentavalent uranyl species, namely UO{sub 2}{sup +}, is described, using DFT methods, with the aim of understanding how the structure of the ligands may influence the localisation of the unpaired 5f electron of uranium (V) and, finally, the stability of such complexes towards oxidation. Six complexes have been inspected: [UO{sub 2}py{sub 5}]{sup +} (1), [(UO{sub 2}py{sub 5})KI{sub 2}] (2), [UO{sub 2}(salan-{sup t}Bu{sub 2})(py)K] (3), [UO{sub 2}(salophen-{sup t}Bu{sub 2})(thf)K] (4), [UO{sub 2}(salen-{sup t}Bu{sub 2})(py)K] (5), [and UO{sub 2}-cyclo[6]pyrrole]{sup 1-} (6), chosen to explore various ligands. In the five first complexes, the UO{sub 2}{sup +} species is well identified with the unpaired electron localized on the 5f uranium orbital. Additionally, for the salan, salen and salophen ligands, some covalent interactions have been observed, resulting from the presence of both donor and acceptor binding sites. In contrast, the last complex is best described by a UO{sub 2}{sup 2+} uranyl (VI) coordinated by the anionic radical cyclo-pyrrole, the highly delocalized p orbitals set stabilizing the radical behaviour of this ligand. (authors)

  11. Photophysics of the excited uranyl ion in aqueous solutions

    International Nuclear Information System (INIS)

    Formosinho, S.J.; Miguel, M. da G.M.

    1985-01-01

    The effect of the micelles of Triton X-100 on the biexponential decay of (UO 2 2+ )* has been investigated. Data are analysed in terms of a reversible crossing mechanism for the decay. Azulene fluorescence quenching and 13 C n.m.r. studies strongly suggest that uranyl ions are able to penetrate deep inside the micelle core. Micelle quenching for the reversible decay of (UO 2 2+ )* occurs in the interior (ksub(q) = 3 x 10 10 dm 3 mol -1 s -1 ) and at the surface (Ksub(q) = 1.5 x 10 9 mol -1 dm 3 s -1 ) of the micelles. The latter process has a rate virtually identical to that for the free surfactant molecules. Penetration of (UO 2 2+ )* inside the non-polar regions of the micelle core increases solvent exchange rates by ca. two orders of magnitude. Uranyl-ion excimers are formed in occupied micelles. The quenching processes decrease strongly for these species because excimers do not penetrate the micelles. (author)

  12. Enhanced Adsorption and Recovery of Uranyl Ions by NikR Mutant-Displaying Yeast

    Directory of Open Access Journals (Sweden)

    Kouichi Kuroda

    2014-04-01

    Full Text Available Uranium is one of the most important metal resources, and the technology for the recovery of uranyl ions (UO22+ from aqueous solutions is required to ensure a semi-permanent supply of uranium. The NikR protein is a Ni2+-dependent transcriptional repressor of the nickel-ion uptake system in Escherichia coli, but its mutant protein (NikRm is able to selectively bind uranyl ions in the interface of the two monomers. In this study, NikRm protein with ability to adsorb uranyl ions was displayed on the cell surface of Saccharomyces cerevisiae. To perform the binding of metal ions in the interface of the two monomers, two metal-binding domains (MBDs of NikRm were tandemly fused via linker peptides and displayed on the yeast cell surface by fusion with the cell wall-anchoring domain of yeast α-agglutinin. The NikRm-MBD-displaying yeast cells with particular linker lengths showed the enhanced adsorption of uranyl ions in comparison to the control strain. By treating cells with citrate buffer (pH 4.3, the uranyl ions adsorbed on the cell surface were recovered. Our results indicate that the adsorption system by yeast cells displaying tandemly fused MBDs of NikRm is effective for simple and concentrated recovery of uranyl ions, as well as adsorption of uranyl ions.

  13. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sang-Won; Leckie, J.O. [Stanford Univ., CA (United States); Siegel, M.D. [Sandia National Labs., Albuquerque, NM (United States)

    1995-09-01

    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption.

  14. Influence of Acidity on Uranyl Nitrate Association in Aqueous Solutions: A Molecular Dynamics Simulation Study

    International Nuclear Information System (INIS)

    de Almeida, Valmor F.; Cui, Shengting; Khomami, Bamin; Ye, Xianggui; Smith, Rodney Bryan

    2010-01-01

    Uranyl ion complexation with water and nitrate is a key aspect of the uranium/plutonium extraction process. We have carried out a molecular dynamics simulation study to investigate this complexation process, including the molecular composition of the various complex species, the corresponding structure, and the equilibrium distribution of the complexes. The observed structures of the complexes suggest that in aqueous solution, uranyls are generally hydrated by 5 water molecules in the equatorial plane. When associating with nitrate ions, a water molecule is replaced by a nitrate ion, preserving the five-fold coordination and planar symmetry. Analysis of the pair correlation function between uranyl and nitrate suggests that nitrates bind to uranyl in aqueous solution mainly in a monodentate mode, although a small portion of bidentates occur. Dynamic association and dissociation between uranyls and nitrates take place in aqueous solution with a substantial amount of fluctuation in the number of various uranyl nitrate species. The average number of the uranyl mononitrate complexes shows a dependence on acid concentration consistent with equilibrium-constant analysis, namely, the concentration of [UO2NO3]+ increases with nitric acid concentration.

  15. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    International Nuclear Information System (INIS)

    Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

    1995-09-01

    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption

  16. Use of uranyl nitrate as a shift reagent in polar and inert solvents

    International Nuclear Information System (INIS)

    Nosov, B.P.

    1988-01-01

    This work examines the effect of uranyl nitrate as a shift reagent on the PMR spectra of different organic molecules in polar and inert solvents. In order to identify the coordination site of the uranyl ion, its effect on the spectra of amino acids and acetic or propionic acids in water was compared. It was found that the induced shifts of the protons in the corresponding positions of the different acids after addition of uranyl nitrate agreed to within ±0.01 ppm. When nitrogenous bases such as diethylamine and pyridine were added to solutions of the carboxylic acids with uranyl nitrate, an increase in the induced chemical shift of the resonance signals occurred. These facts suggest the coordination of the uranyl ion with the carboxyl oxygen both for acetic and propionic acids and for amino acids. The authors established that the addition of uranyl nitrate to solutions of organic compounds caused different downfield shifts of the resonance signals from the protons. In polar solvents shifts induced by uranyl nitrate in the PMR spectra of carboxylic acids occur only when nitrogenous bases are added

  17. Chloride ingress prediction

    DEFF Research Database (Denmark)

    Frederiksen, Jens Mejer; Geiker, Mette Rica

    2008-01-01

    Prediction of chloride ingress into concrete is an important part of durability design of reinforced concrete structures exposed to chloride containing environment. This paper presents experimentally based design parameters for Portland cement concretes with and without silica fume and fly ash...... in marine atmospheric and submersed South Scandinavian environment. The design parameters are based on sequential measurements of 86 chloride profiles taken over ten years from 13 different types of concrete. The design parameters provide the input for an analytical model for chloride profiles as function...... of depth and time, when both the surface chloride concentration and the diffusion coefficient are allowed to vary in time. The model is presented in a companion paper....

  18. Spectroscopic studies of 2-thenoyltrifluoro acetonate of uranyl salts doped with europium

    International Nuclear Information System (INIS)

    Nakagawa, F.T.; Luiz, J.E.M. de Sa; Felinto, M.C.F.C.; Brito, H.F.; Teotonio, E.E.S.

    2006-01-01

    Uranyl compounds present a great potential as luminescence materials. Some examples of applications are: in laser technology, cathode ray tube, X-rays diagnostic. In this work it was studied the synthesis, characterization and spectroscopic properties study of uranyl 2-thenoyl trifluoroacetonate and uranyl 2- thenoyl trifluoroacetonate doped with europium. The compounds were synthesized and characterized by infrared absorption spectroscopy, thermal analysis, scanning electronic microscopy, and electronic spectroscopy of emission and excitation. The Eu 3+ ion acted as an effective luminescent probe, however the process of energy transfer from UO 2 2+ to Eu 3+ ion has not been efficient. (author)

  19. Unusual case of a polar copper(II) uranyl phosphonate that fluoresces

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A.G.D.; Albrecht-Schmitt, Th.E. [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, Indiana (United States)

    2010-06-15

    A polar Cu(II) uranyl diphosphonate, Cu(H{sub 2}O){sub 4}(UO{sub 2}){sub 3}(H{sub 2}O){sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{sub 2}.5H{sub 2}O, has been prepared under mild hydrothermal conditions. This compound has direct linkages between the oxo atoms of the uranyl moieties and the Cu(II) centers. Despite the presence of Cu(II) in the structure, vibronically-coupled emission is still observed, most likely because there are two crystallographically unique uranyl moieties, only one of which bonds to Cu(II). (authors)

  20. Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives

    International Nuclear Information System (INIS)

    Schoendorff, George E.; Windus, Theresa L.; De Jong, Wibe A.

    2009-01-01

    The coordination of nitrile (acetonitrile, propionitrile, and benzonitrile) and carbonyl (formaldehyde, ethanal, and acetone) ligands to the uranyl dication (UO22+) has been examined using density functional theory (DFT) utilizing relativistic effective core potentials (RECPs). Complexes containing up to six ligands have been modeled for all ligands except formaldehyde, for which no minimum could be found. A comparison of relative binding energies indicates that five coordinate complexes are predominant while a six coordinate complex involving propionitrile ligands might be possible. Additionally, the relative binding energy and the weakening of the uranyl bond is related to the size of the ligand and, in general, nitriles bind more strongly to uranyl than carbonyls.

  1. Removal of uranyl ions from residual waters using some algae types

    International Nuclear Information System (INIS)

    Cecal, A.; Palamaru, I.; Humelnicu, D.; Popa, K.; Salaru, V.V.; Rudic, V.; Gulea, A.

    1999-01-01

    This paper deals with a study on the bioaccumulation of uranyl ions resulted from residual effluents by means of some microbiological collectors: Scenedesmus quadricauda, Anabaena karakumica, Calothrix brevissima, Penicillinium sp, as well as the Glucid extract of Porphyridium cruentum, under various experimental conditions. The retaining degree of the bioaccumulated uranyl ions, as well as the leaching degree, in HCl and H 2 O media, of the same ions previously retained on algae were established. The retaining degree decreases in the series: Scenedesmus quadricauda > Anabaena karakumica > Penicillinium sp > Calothrix brevissima. The leaching effect of bioaccumulated uranyl ions is higher in hydrochloric acid than in water. (author)

  2. Mass-spectrometric study of volatile uranyl β-diketonates and their adducts

    International Nuclear Information System (INIS)

    Adamov, V.M.; Belyaev, B.N.; Berezinskij, S.O.; Sidorenko, G.V.; Suglobov, D.N.

    1985-01-01

    The mass spectra of a number of uranyl β-diketonates containing methyl, trifluoromethyl and tert-butyl substituents in β-diketonate anion, and their adducts are measured. The form of the unsolvated β-diketonates and their adducts in gas phase is studied. The ways of fragmentation of uranyl β-diketonates and their adducts are investigated. The data concerning the thermal and chemical side reactions proceeding with uranyl β-diketonates and their addicts in an ion source are obtained. The mass spectra of the samples of neptunyl and plutonyl β-diketonate adducts synthesized for the first time are measured

  3. Removal of uranyl ions from residual waters using some algae types

    International Nuclear Information System (INIS)

    Cecal, Al.; Rudic, V.; Gulea, A.; Palamaru, I.; Humelnicu, D.; Salaru, V.V.; Popa, K.

    1997-01-01

    This paper deals with a study on the bioaccumulation of uranyl ions resulted from residual effluents, by means of some microbiological collectors: Scenedesmus quadricauda, Anabaena karakumica, Calothrix brevissima, Penicillium sp, as well as the Glucide extract of Porphyridium cruentum, in several experimental conditions. The retaining degree of the bioaccumulated uranyl ions, as well as the leaching degree, in HCl and H 2 O media, of the same ions previously retained on algae, were karakumica >Penicillium sp> Calothrix brevissima. The leaching effect of bioaccumulated uranyl ions is higher in hydrochloric acid then in water. (authors)

  4. Charge-density matching in organic-inorganic uranyl compounds

    International Nuclear Information System (INIS)

    Krivovichev, S.V.; Krivovichev, S.V.; Tananaev, I.G.; Myasoedov, B.F.

    2007-01-01

    Single crystals of [C 10 H 26 N 2 ][(UO 2 )(SeO 4 ) 2 (H 2 O)](H 2 SeO 4 ) 0.85 (H 2 O) 2 (1), [C 10 H 26 N 2 ][(UO 2 )(SeO 4 ) 2 ] (H 2 SeO 4 ) 0.50 (H 2 O) (2), and [C 8 H 20 N] 2 [(UO 2 )(SeO 4 ) 2 (H 2 O)] (H 2 O) (3) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amines. The structures of the compounds have been solved by direct methods and structural models have been obtained. The structures of the compounds 1, 2, and 3 contain U and Se atoms in pentagonal bipyramidal and tetrahedral coordinations, respectively. The UO 7 and SeO 4 polyhedra polymerize by sharing common O atoms to form chains (compound 1) or sheets (compounds 2 and 3). In the structure of 1, the layers consisting of hydrogen-bonded [UO 2 (SeO 4 ) 2 (H 2 O)] 2- chains are separated by mixed organic-inorganic layers comprising from [NH 3 (CH 2 ) 10 NH 3 ] 2+ molecules, H 2 O molecules, and disordered electroneutral (H 2 SeO 4 ) groups. The structure of 2 has a similar architecture but a purely inorganic layer is represented by a fully connected [UO 2 (SeO 4 ) 2 ] 2- sheet. The structure of 3 does not contain disordered (H 2 SeO 4 ) groups but is based upon alternating [UO 2 (SeO 4 ) 2 (H 2 O)] 2- sheets and 1.5-nm-thick organic blocks consisting of positively charged protonated octylamine molecules, [NH 3 (CH 2 ) 7 CH 3 ] + . The structures may be considered as composed of anionic inorganic sheets (2D blocks) and cationic organic blocks self-organized according to competing hydrophilic-hydrophobic interactions. Analysis of the structures allows us to conclude that the charge-density matching principle is observed in uranyl compounds. In order to satisfy some basic peculiarities of uranyl (in general, actinyl) chemistry, it requires specific additional mechanisms: (a) in long-chain-amine-templated compounds, protonated amine molecules inter-digitate; (b) in long-chain-diamine-templated compounds, incorporation of acid-water interlayers into

  5. Chloride flux in phagocytes.

    Science.gov (United States)

    Wang, Guoshun

    2016-09-01

    Phagocytes, such as neutrophils and macrophages, engulf microbes into phagosomes and launch chemical attacks to kill and degrade them. Such a critical innate immune function necessitates ion participation. Chloride, the most abundant anion in the human body, is an indispensable constituent of the myeloperoxidase (MPO)-H2 O2 -halide system that produces the potent microbicide hypochlorous acid (HOCl). It also serves as a balancing ion to set membrane potentials, optimize cytosolic and phagosomal pH, and regulate phagosomal enzymatic activities. Deficient supply of this anion to or defective attainment of this anion by phagocytes is linked to innate immune defects. However, how phagocytes acquire chloride from their residing environment especially when they are deployed to epithelium-lined lumens, and how chloride is intracellularly transported to phagosomes remain largely unknown. This review article will provide an overview of chloride protein carriers, potential mechanisms for phagocytic chloride preservation and acquisition, intracellular chloride supply to phagosomes for oxidant production, and methods to measure chloride levels in phagocytes and their phagosomes. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  6. Electroenzymatic Reactions With Oxygen on Laccase-Modified Electrodes in Anhydrous (Pure) Organic Solvent

    DEFF Research Database (Denmark)

    Yarapolov, A.; Shleev, S.; Zaitseva, E.

    2007-01-01

    in two different ways: (i) by studying the electroreduction of oxygen in anhydrous DMSO via a direct electron transfer mechanism without proton donors and (ii) by doing the same experiments in the presence of laccase substrates, which display in pure organic solvents both the properties of electron......The electroenzymatic reactions of Trametes hirsuta laccase in the pure organic solvent dimethyl sulfoxide (DMSO) have been investigated within the framework for potential use as a catalytic reaction scheme for oxygen reduction. The bioelectrochemical characteristics of laccase were investigated...... donors as well as the properties of weak acids. The results obtained with laccase in anhydrous DMSO were compared with those obtained previously in aqueous buffer. It was shown that in the absence of proton donors under oxygenated conditions, formation of superoxide anion radicals is prevented at bare...

  7. Anhydrous proton conducting composite membranes containing Nafion and triazole modified POSS

    International Nuclear Information System (INIS)

    Lei, M.; Wang, Y.G.; Zhang, F.F.; Huang, C.; Xu, X.; Zhang, R.; Fan, D.Y.

    2014-01-01

    Development of membrane electrolytes having reasonable proton conductivity and mechanical strength under anhydrous conditions is of great importance for proton exchange membrane fuel cells operated at elevated temperature. With the introduction of triazole modified polyhedral oligomeric silsesquioxanes (Tz-POSS) into Nafion membrane, the formed composite electrolytes exhibit improved mechanical properties compared to pristine Nafion membrane due to the well distribution of Tz-POSS inside the membrane. The anhydrous proton conductivity of the formed composite membranes increases initially with the increase in temperature, reaching about 0.02 Scm −1 at 140 °C. With further increase in temperature to about 150 °C, the composite membrane reaches its glass transition point above which the proton conductivity decreases dramatically. The performance of assembled single cell from composite membrane is slightly dependent on humidification conditions at 95 °C, reaching 0.45 V at 600 mAcm −2 using hydrogen and oxygen as reaction gases

  8. Method for application of nitrogen-15-labeled anhydrous ammonia to small plots

    International Nuclear Information System (INIS)

    Sanchez, C.A.; Blackmer, A.M.

    1987-01-01

    A method is described that permits precise application of anhydrous ammonia in bands to plots of the size often used in 15 N-tracer studies. This method involves placing a stainless-steel capillary tube in the soil where the ammonia is to be banded, attaching this tube to a cylinder of ammonia, and then pulling the tube through the soil with deposition of ammonia as an even band. The procedure has marked advantages over previously described methods because it can be used with mixtures of anhydrous ammonia and nitrification inhibitors and because the soil environment at the point of application is representative of the soil environment found when a conventional applicator is used

  9. Ab initio and DFT studies of the structure and vibrational spectra of anhydrous caffeine

    Science.gov (United States)

    Srivastava, Santosh K.; Singh, Vipin B.

    2013-11-01

    Vibrational spectra and molecular structure of anhydrous caffeine have been systematically investigated by second order Moller-Plesset (MP2) perturbation theory and density functional theory (DFT) calculations. Vibrational assignments have been made and many previous ambiguous assignments in IR and Raman spectra are amended. The calculated DFT frequencies and intensities at B3LYP/6-311++G(2d,2p) level, were found to be in better agreement with the experimental values. It was found that DFT with B3LYP functional predicts harmonic vibrational wave numbers more close to experimentally observed value when it was performed on MP2 optimized geometry rather than DFT geometry. The calculated TD-DFT vertical excitation electronic energies of the valence excited states of anhydrous caffeine are found to be in consonance to the experimental absorption peaks.

  10. Synthesis of anhydrous K2TiOF4 via a mild hydrothermal method

    Science.gov (United States)

    Felder, Justin B.; Yeon, Jeongho; zur Loye, Hans-Conrad

    2015-10-01

    The synthesis of anhydrous K2TiOF4 has been previously attempted by transforming precursor compounds, such as the peroxide (K2Ti(O2)F4), hydrate (K2TiOF4·H2O) and fluoride (K2TiF6). Due to the large structural differences between these precursors and the anhydrous oxyfluorides, however, these preparations have been unsuccessful. Therefore, a direct method of synthesis has been employed to grow single crystals of K2TiOF4 that were characterized by single crystal x-ray diffraction. K2TiOF4 was found to be isostructural with the previously known K2VOF4.

  11. The application of time-resolved luminescence spectroscopy to a remote uranyl sensor

    International Nuclear Information System (INIS)

    Varineau, P.T.; Duesing, R.; Wangen, L.E.

    1991-01-01

    Time resolved luminescence spectroscopy is an effective method for the determination of a wide range of uranyl concentrations in aqueous samples. We have applied this technique to the development of a remote sensing device using fiber optic cables coupled with a micro flow cell in order to probe for uranyl in aqueous samples. This sensor incorporates a Nafion membrane through which UO 2 2+ can diffuse in to a reaction/analysis chamber which holds phosphoric acid, a reagent which enhances the uranyl luminescence intensity and lifetime. With this device, anionic and fluorescing organic interferences could be eliminated, allowing for the determination of uranyl over a concentration range of 10 4 to 10 -9 M. 17 refs., 5 figs

  12. Aggregation-induced emission active tetraphenylethene-based sensor for uranyl ion detection.

    Science.gov (United States)

    Wen, Jun; Huang, Zeng; Hu, Sheng; Li, Shuo; Li, Weiyi; Wang, Xiaolin

    2016-11-15

    A novel tetraphenylethene-based fluorescent sensor, TPE-T, was developed for the detection of uranyl ions. The selective binding of TPE-T to uranyl ions resulted in a detectable signal owing to the quenching of its aggregation-induced emission. The developed sensor could be used to visually distinguish UO2(2+) from lanthanides, transition metals, and alkali metals under UV light; the presence of other metal ions did not interfere with the detection of uranyl ions. In addition, TPE-T was successfully used for the detection of uranyl ions in river water, illustrating its potential applications in environmental systems. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Uranyl determination using pyridylazoresorcinol as complexing active by adsorb voltametry technique with cathodic redissolution

    International Nuclear Information System (INIS)

    Ohara, A.K.; Farias, P.A.M.

    1990-01-01

    The development method for uranyl ion determination by the optimization of chemical reaction and instrumental parameters is shown. This method is based on preconcentration stage, where in adsorptive accumulation of metallic complex in a static electrode is presented. (author)

  14. The uranyl influence on a mutation process in germ and somatic cells of mice

    International Nuclear Information System (INIS)

    Kostrova, L.N.; Mosseh, I.B.; Molofej, V.P.

    2008-01-01

    The mutagenic effect of uranyl was revealed by the chromosome rearrangement test in germ and somatic cells of mice. The effect value depended on duration of substance administration into organism. (authors)

  15. Sorption rate of uranyl ions by hyphan cellulose exchangers and by hydrated titanium dioxide

    International Nuclear Information System (INIS)

    Ambe, F.; Burba, P.; Lieser, K.H.

    1979-01-01

    Sorption of uranyl ions by the cellulose exchanger Hyphan proceeds rather fast. Two steps are observed with half-times of the order of 10 s and 2 min. The majority of the uranyl ions is bound in 1 min. Sorption of uranyl ions by titanium dioxide is a very slow process. For particle sizes between 0,1 and 0,5 mm the half-time is about 3 h and equilibrium is attained in about 1 day. The effect of stirring suspensions of inorganic sorbents like titanium dioxide in solution is investigated in detail. Sorption of uranyl ions by titanium dioxide and change in pH in solution are measured simultaneously as a function of time. (orig.) [de

  16. Giant regular polyhedra from calixarene carboxylates and uranyl

    Science.gov (United States)

    Pasquale, Sara; Sattin, Sara; Escudero-Adán, Eduardo C.; Martínez-Belmonte, Marta; de Mendoza, Javier

    2012-01-01

    Self-assembly of large multi-component systems is a common strategy for the bottom-up construction of discrete, well-defined, nanoscopic-sized cages. Icosahedral or pseudospherical viral capsids, built up from hundreds of identical proteins, constitute typical examples of the complexity attained by biological self-assembly. Chemical versions of the so-called 5 Platonic regular or 13 Archimedean semi-regular polyhedra are usually assembled combining molecular platforms with metals with commensurate coordination spheres. Here we report novel, self-assembled cages, using the conical-shaped carboxylic acid derivatives of calix[4]arene and calix[5]arene as ligands, and the uranyl cation UO22+ as a metallic counterpart, which coordinates with three carboxylates at the equatorial plane, giving rise to hexagonal bipyramidal architectures. As a result, octahedral and icosahedral anionic metallocages of nanoscopic dimensions are formed with an unusually small number of components. PMID:22510690

  17. Effect of temperature on internal structure of uranyl gels

    International Nuclear Information System (INIS)

    Landspersky, H.; Urbanek, V.

    1983-01-01

    Tempering freshly prepared uranyl gel serves the homogenization of the volume of the individual spheres and the whole volume of the processed material. Tempering is carried out at a temperature of 90 degC in a special countercurrent through-flow column. The tempered gel particles were analyzed for specific surface and porosity using different methods, subjected to phase analysis, and the crystallite mean size was determined. It was found that the quality of the final gel depends on the residence time in the tempering column. Gel recrystallization probably takes place during tempering leading to stress and cracks which in the final stage lead to the disintegration of the xerogel. Maximum permissible gel residence time in the tempering column is 15 mins. (M.D.)

  18. Process control for a continuous uranyl nitrate evaporator

    International Nuclear Information System (INIS)

    Peterson, S.F.; MacIntyre, L.P.

    1984-07-01

    A continuous uranyl nitrate evaporator at the Savannah River Plant (SRP) in Aiken, South Carolina ws the subject of this work. A rigorous mathematical model of the evaporator was developed. A difference equation form of the model was then constructed and used for control studies. Relative gain analysis was done on the system in order to identify any promising multivariable control schemes. Several alternate control schemes were modeled, tuned, and compared against the scheme presently in use at SRP. As the pneumatic specific gravity instrumentation at SRP is very noisy, the noise was simulated and used in the second phase of the control study. In this phase, alternate tuning methods and filters were invesigated and compared. The control studies showed that the control algorithm now in use at SRP is the simplest and best available. 10 references, 53 figures, 22 tables

  19. Pilot scale for preparation of ammonium uranyl carbonate

    International Nuclear Information System (INIS)

    Santos, L.R. dos.

    1989-01-01

    The procedure adopted for obtaining Ammonium Uranyl Carbonate (AUC) from uranium hexafluoride (UF sub(6)) or aqueous solutions of uranylnitrate (UO sub(2)(NO sub(3)) sub(2)) is described in the present work. This procedure involves the precipitation of AUC in a chemical reactor by the addition of gaseous UF sub(6) or solutions of uranylnitrate to NH sub(3) and CO sub(2) gases in a solution containing ammonium bicarbonate, where pH and temperature are controlled. Details regarding the characterization and quality control methods in the preparation of AUC are presented along with their physical and chemical properties. Some informations about effluents generated during the process are presented too. An attempt is made to correlate the parameters involved in the precipitation process of AUC and their characteristics. (author)

  20. Cutaneous contamination after a uranyl nitrate skin burn: incident report

    International Nuclear Information System (INIS)

    Berard, P.; Chalabreysse, J.; Quesne, B.; Auriol, B.

    1994-01-01

    The authors review the circumstances of a handburn incident by a mixture of dilute nitric acid and uranyl nitrate. The burn was localised on the thumb and three fingers of the left hand. After abundant washing, external direct measurements revealed the presence of uranium on the fingers. The injured employee was maintained under observation for ten days, and therapy was performed until all the activity disappeared. External monitoring with various detectors, and measurements of the bandages and skin showed a rapid decrease of uranium fixation. All urine was collected throughout the duration of the treatment. The study shows that all the activity was retained on the burnt skin, with very little systemic uptake. Rapid peeling eliminated the cutaneous retention. Internal and external dose assessments were calculated and the committed effective dose equivalent and the committed dose equivalent for the skin and bone surfaces were low. (author)

  1. Complex formation between uranyl and various thiosemicarbazide derivatives

    International Nuclear Information System (INIS)

    Chuguryan, D.G.; Dzyubenko, V.I.

    1987-01-01

    Complex formation between hexavalent uranium and salicylaldehyde thiosemicarbazone (H 2 L), salicylaldehyde S-methyl-isothiosemicarbazone (H 2 Q), S-methyl-N 1 ,N 4 -bis(salicylidene)isothiosemicarbazide(H 2 Z), and thiosemicarbazidodiacetic acid (H 2 R) has been studied spectrophotometrically in solution. Stability constants for complexes having the composition UO 2 A have been calculated. Solid uranyl derivatives having the composition UO 2 L x 2H 2 O, UO 2 Q x 2H 2 O, UO 2 Z x 2H 2 O, and UO 2 R x 2H 2 O have been obtained. These derivatives were isolated and their IR spectroscopic behavior and thermal properties were investigated

  2. Hydrothermal syntheses and characterization of uranyl tungstates with electro-neutral structural units

    Energy Technology Data Exchange (ETDEWEB)

    Balboni, Enrica; Burns, Peter C. [Univ. of Notre Dame, IN (United States). Dept. of Civil and Enviromental Engineering and Earth Sciences; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry

    2015-11-01

    Two uranyl tungstates, (UO{sub 2})(W{sub 2}O{sub 7})(H{sub 2}O){sub 3} (1) and (UO{sub 2}){sub 3}(W{sub 2}O{sub 8})F{sub 2}(H{sub 2}O){sub 3} (2), were synthesized under hydrothermal conditions at 220 C and were structurally, chemically, and spectroscopically characterized. 1 Crystallizes in space group Pbcm, a = 6.673(5) Aa, b = 12.601(11) Aa, c = 11.552 Aa; 2 is in C2/m, a = 13.648(1) Aa, b = 16.852(1) Aa, c = 9.832(1) Aa, β = 125.980(1) {sup circle}. In 1 the U(VI) cations are present as (UO{sub 2}){sup 2+} uranyl ions that are coordinated by five oxygen atoms to give pentagonal bipyramids. These share two edges with two tungstate octahedra and single vertices with four additional octahedra, resulting in a sheet with the iriginite-type anion topology. Only water molecules are located in the interlayer. The structural units of 2 consist of (UO{sub 2}){sup 2+} uranyl oxy-fluoride pentagonal bipyramids present as either [UO{sub 2}F{sub 2}O{sub 3}]{sup -6} or [UO{sub 2}FO{sub 4}]{sup -5}, and strongly distorted tungstate octahedra. The linkage of uranyl pentagonal bipyramids and tungstate octahedra gives a unique sheet anion topology consisting of pentagons, squares and triangles. In 2, the uranyl tungstates sheets are connected into a novel electro-neutral three-dimensional framework through dimers of uranyl pentagonal bipyramids. These dimers connecting the sheets share an edge defined by F anions. 2 is the first example of a uranyl tungstate oxy-fluoride, and 1 and 2 are rare examples of uranyl compounds containing electro-neutral structural units.

  3. Ligand exchange in uranyl complexes in non-aqueous solutions: equilibrium properties

    International Nuclear Information System (INIS)

    Egozy, Y.; Weiss, S.

    1976-01-01

    The systems uranyl nitrate, tributylphosphate and 8-hydroxyquinoline or diphenylcarbazone were studied in chloroform, carbon tetrachloride and 1,2-dichloroethane at a number of temperatures. The nature of the complexes formed was determined and the equilibrium constants and several thermodynamic functions were measured. 8-hydroxyquinoline and diphenylcarbazone will be valuable as indicators for uranyl in kinetic studies. They are also interesting since they participate, along with tributylphosphate, in formation of synergistic complexes. (author)

  4. Investigation of uranyl sorbed to Wyoming montmorillonite at amphoteric and exchange sites by optical spectroscopy

    International Nuclear Information System (INIS)

    Morris, D.E.; Chisholm-Brause, C.J.; Berg, J.M.; McKinley, J.P.; Zachara, J.M.; Smith, S.C.

    1993-01-01

    Using optical spectroscopy, the authors have characterized aqueous uranyl (UO 2 2+ ) sorption complexes on a sodium-saturated Wyoming montmorillonite (SWy-1) at low and high ionic strength (IS, as NaClO 4 . McKinley et al. (1193), ACS Spring Meeting) have shown that uranyl uptake is suppressed at high IS at these pH values, reflecting increased cation competition for exchange sites, and an increase in the ratio of uranyl species sorbed on amphoteric edge sites to those in exchange sites. At higher pH, sorption is less dependent on IS, with complexation by amphoteric edge sites becoming dominant as pH increases. At low pH, emission spectra for uranyl sorbed to SWy-1 from solutions with high IS ([Na]/[U] > 1000) are distinct from those at low IS ([Na]/[U] < 10). The low IS spectra are dominanted by a short lifetime component (τ∼0.5μs), and have low integrated intensities (normalized for uranium concentration). However, gated detection clearly resolves an additional, longer-loved component. The high IS spectra have significant contributions form 2-3 longer-lived components (5<τ120μs), and have much stronger intensities. Based on comparison to solution data, these results suggest that the uranyl moiety in the exchange sites is strikingly similar to the fully aquated uranyl monomer in solution, whereas the uranyl species occupying the edge sites are structurally more similar to hydrolyzed uranyl species in solution. At higher pH values, the emission spectra represent composites of at least the two distinct spectra identified at lower pH. However, the ratios of the different components and thus the overall emission spectra vary as a function of ionic strength. These results demonstrate that several spectroscopically (and therefore structurally) distinct sorption complexes exist in exchange and edges of SWy-1

  5. High-affinity uranyl-specific antibodies suitable for cellular imaging

    Energy Technology Data Exchange (ETDEWEB)

    Reisser-Rubrecht, L.; Torne-Celer, C.; Renier, W.; Averseng, O.; Plantevin, S.; Quemeneur, E.; Bellanger, L.; Vidaud, C. [CEA Valrho, DSV, IBEB, Serv Biochim et Toxicol Nucl, F-30207 Bagnols Sur Ceze (France)

    2008-07-01

    Monoclonal antibodies (mAbs) have proved to be valuable models for the study of protein-metal interactions, and previous reports have described very specific antibodies to chelated metal ions, including uranyl. We raised specific mAbs against UO{sub 2}{sup 2+}-DCP-BSA (DCP, 1, 10-phenanthroline-2,9-dicarboxylic acid) to generate new sets of antibodies that might cross-react with various complexed forms of uranyl in different environments for further application in the field of toxicology. Using counter-screening with UO{sub 2}{sup 2+}-DCP-casein, we selected two highly specific mAbs against uranyl-DCP (K{sub D} = 10-100 pM): U04S and U08S. Competitive assays in the presence of different metal ions (UO{sub 2}{sup 2+}, Fe{sup 3+}, Zn{sup 2+}, Cu{sup 2+}, and Ca{sup 2+}) showed that uranyl in solution can act as a good competitor, suggesting some antibody ability to cross-react with chelating groups other than DCP in the UO{sub 2}{sup 2+} equatorial coordination plane. Interestingly, one of the antibodies could be used for revealing uranyl cations in cell samples. Fluorescence activated cell sorting analyses after immuno-labeling revealed the interaction of uranyl with human kidney cells HK2. The intracellular accumulation of uranyl could be directly visualized by metal-immunostaining using fluorescent-labeled mAb. Our results suggest that U04S mAb epitopes mostly include the uranyl fraction and its para-topes can accommodate a wide variety of chelating groups. (authors)

  6. Nephrotoxicity of uranyl acetate: effect on rat kidney brush border membrane vesicles

    International Nuclear Information System (INIS)

    Goldman, M.; Yaari, A.; Moran, A.; Doshnitzki, Z.; Cohen-Luria, R.

    2006-01-01

    Since the Gulf war exposure to depleted uranium, a known nephrotoxic agent, there is a renewed interest in the toxic effects of uranium in general and its mechanism of nephrotoxicity which is still largely unknown in particular. In order to investigate the mechanism responsible for uranium nephrotoxicity and the therapeutic effect of urine alkalization, we utilized rat renal brush border membrane vesicles (BBMV). Uranyl acetate (UA) caused a decrease in glucose transport in BBMV. The apparent K i of uranyl was 139±30 μg uranyl/mg protein of BBMV. Uranyl at 140 μg/mg protein of BBMV reduced the maximal capacity of the system to transport glucose [V max 2.2±0.2 and 0.96±0.16 nmol/mg protein for control and uranyl treated BBMV (P m (1.54±0.33 and 1.54±0.51 mM for control, and uranyl treated BBMV, respectively). This reduction in V max is at least partially due to a decrease in the number of sodium-coupled glucose transporters as apparent from the reduction in phlorizin binding to the uranyl treated membranes, V max was reduced from 247±13 pmol/mg protein in control BBMV to 119±3 pmol/mg protein in treated vesicles (P<0.001). The pH of the medium has a profound effect on the toxicity of UA on sodium-coupled glucose transport in BBMV: higher toxicity at neutral pH (around pH 7.0), and practically no toxicity at alkaline pH (7.6). This is the first report showing a direct inhibitory dose and pH dependent effect of uranyl on the glucose transport system in isolated apical membrane from kidney cortex. (orig.)

  7. High-affinity uranyl-specific antibodies suitable for cellular imaging

    International Nuclear Information System (INIS)

    Reisser-Rubrecht, L.; Torne-Celer, C.; Renier, W.; Averseng, O.; Plantevin, S.; Quemeneur, E.; Bellanger, L.; Vidaud, C.

    2008-01-01

    Monoclonal antibodies (mAbs) have proved to be valuable models for the study of protein-metal interactions, and previous reports have described very specific antibodies to chelated metal ions, including uranyl. We raised specific mAbs against UO 2 2+ -DCP-BSA (DCP, 1, 10-phenanthroline-2,9-dicarboxylic acid) to generate new sets of antibodies that might cross-react with various complexed forms of uranyl in different environments for further application in the field of toxicology. Using counter-screening with UO 2 2+ -DCP-casein, we selected two highly specific mAbs against uranyl-DCP (K D = 10-100 pM): U04S and U08S. Competitive assays in the presence of different metal ions (UO 2 2+ , Fe 3+ , Zn 2+ , Cu 2+ , and Ca 2+ ) showed that uranyl in solution can act as a good competitor, suggesting some antibody ability to cross-react with chelating groups other than DCP in the UO 2 2+ equatorial coordination plane. Interestingly, one of the antibodies could be used for revealing uranyl cations in cell samples. Fluorescence activated cell sorting analyses after immuno-labeling revealed the interaction of uranyl with human kidney cells HK2. The intracellular accumulation of uranyl could be directly visualized by metal-immunostaining using fluorescent-labeled mAb. Our results suggest that U04S mAb epitopes mostly include the uranyl fraction and its para-topes can accommodate a wide variety of chelating groups. (authors)

  8. A study of precipitation from pure solutions of uranyl nitrate; Etude de la precipitaion de solutions pures de nitrate d'uranyle

    Energy Technology Data Exchange (ETDEWEB)

    Decrop, J; Holder, J; Sauteron, J [Commissariat a l' Energie Atomique, Usine du Bouchet, Service des Lab. de Recherches et de Controle, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    After its purification by extraction of the uranyl nitrate from the organic solvent, uranium has to be converted into solid form again: uranium trioxide (UO{sub 3}). It can be done either by thermal decomposition of uranyl nitrate or by precipitation of uranium, followed by filtration and calcination. Only the second method has been studied for now at the Bouchet plant. This paper reports the bench-scale and pilot-scale experiments of the studies of the precipitation of pure solutions of uranyl nitrate using ammonia (gaseous or in solution) or ammonium carbonate. These have been carried out at the Bouchet plant. It investigates the chemical aspect (pH, precipitates chemical composition) and the technical aspect of the different ways of precipitation (conditions of precipitation, decantation and filtration of precipitates). (M.P.)

  9. Temperature and pH driven association in uranyl aqueous solutions

    Directory of Open Access Journals (Sweden)

    M. Druchok

    2012-12-01

    Full Text Available An association behavior of uranyl ions in aqueous solutions is explored. For this purpose a set of all-atom molecular dynamics simulations is performed. During the simulation, the fractions of uranyl ions involved in dimer and trimer formations were monitored. To accompany the fraction statistics one also collected distributions characterizing average times of the dimer and trimer associates. Two factors effecting the uranyl association were considered: temperature and pH. As one can expect, an increase of the temperature decreases an uranyl capability of forming the associates, thus lowering bound fractions/times and vice versa. The effect of pH was modeled by adding H+ or OH- ions to a "neutral" solution. The addition of hydroxide ions OH- favors the formation of the associates, thus increasing bound times and fractions. The extra H+ ions in a solution produce an opposite effect, thus lowering the uranyl association capability. We also made a structural analysis for all the observed associates to reveal the mutual orientation of the uranyl ions.

  10. Aggregation-induced emission active tetraphenylethene-based sensor for uranyl ion detection

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Jun; Huang, Zeng; Hu, Sheng [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, 621900, Sichuan Province (China); Li, Shuo, E-mail: lishuo@cqut.edu.cn [School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054 (China); Li, Weiyi, E-mail: weiyili@mail.xhu.edu.cn [School of Science, Xihua University, Chengdu, Sichuan, 610065 (China); Wang, Xiaolin, E-mail: xlwang@caep.cn [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, 621900, Sichuan Province (China)

    2016-11-15

    Highlights: • A novel AIE fluorescent sensor for the detection of uranyl has been developed. • TPE-T is capable of visually distinguish UO{sub 2}{sup 2+} among many metals owing to the AIE phenomenon. • TPE-T showed a wide effective pH range, high selectivity and good anti-interference qualities. • TPE-T showed good accuracy in the determination of uranyl in river water. - Abstract: A novel tetraphenylethene-based fluorescent sensor, TPE-T, was developed for the detection of uranyl ions. The selective binding of TPE-T to uranyl ions resulted in a detectable signal owing to the quenching of its aggregation-induced emission. The developed sensor could be used to visually distinguish UO{sub 2}{sup 2+} from lanthanides, transition metals, and alkali metals under UV light; the presence of other metal ions did not interfere with the detection of uranyl ions. In addition, TPE-T was successfully used for the detection of uranyl ions in river water, illustrating its potential applications in environmental systems.

  11. Theoretical insights into the uranyl adsorption behavior on vanadium carbide MXene

    Science.gov (United States)

    Zhang, Yu-Juan; Zhou, Zhang-Jian; Lan, Jian-Hui; Ge, Chang-Chun; Chai, Zhi-Fang; Zhang, Peihong; Shi, Wei-Qun

    2017-12-01

    Remediation of the contamination by long-lived actinide wastes is extremely important but also challenging. Adsorption based techniques have attracted much research attention for their potential as low-cost and effective methods to reduce the radioactive waste from solution. In this work, we have investigated the adsorption behavior of uranyl species [with the general form UO2(L1)x(L2)y(L3)z, where L1, L2 and L3 stand for ligands H2O, OH and CO3, respectively] on hydroxylated vanadium carbide V2C(OH)2 MXene nanosheets using density functional theory based simulation methods We find that all studied uranyl species can stably bond to hydroxylated MXene with binding energies ranging from -3.3 to -4.6 eV, suggesting that MXenes could be effective adsorbers for uranyl ions. The strong adsorption is achieved by forming two Usbnd O bonds with the hydroxylated Mxene. In addition, the axial oxygen atoms from the uranyl ions form hydrogen bonds with the hydroxylated V2C, further strengthening the adsorption. We have also investigated the effects of F termination on the uranyl adsorption properties of V2C nanosheets. Usbnd F bonds are in general weaker than Usbnd O bonds on the adsorption site, suggesting that F terminated Mexne is less favorable for uranyl adsorption applications.

  12. 78 FR 78393 - Standard on the Storage and Handling of Anhydrous Ammonia; Extension of the Office of Management...

    Science.gov (United States)

    2013-12-26

    ...OSHA solicits public comments concerning its proposal to extend OMB approval of the information collection requirements specified in the Storage and Handling of Anhydrous Ammonia Standard (29 CFR 1910.111). Paragraphs (b)(3) and (b)(4) of the Standard have paperwork requirements that apply to non-refrigerated containers and systems and refrigerated containers, respectively; employers use these containers and systems to store and transfer anhydrous ammonia in the workplace.

  13. Raman spectral titration method: an informative technique for studying the complexation of uranyl with uranyl(vi)-DPA/oxalate systems as examples.

    Science.gov (United States)

    Liu, Qian; Zhang, Qianci; Yang, Suliang; Zhu, Haiqiao; Liu, Quanwei; Tian, Guoxin

    2017-10-10

    The Raman band at about 870 cm -1 originating from the symmetric stretch vibration (ν 1 ) of uranyl, UO 2 2+ , has proven to be very informative for investigating the complexation of uranyl using perchlorate or nitrate of known concentration as internal standards. The concentration of uranyl can be conveniently calculated by using the ratio of the directly read band intensities of uranyl and the added reference, ClO 4 - , with a factor of 1.72. While with NO 3 - of concentration lower than 1.8 M as the reference, a factor of 0.85 should be used. Furthermore, with added internal standards, the linear relationship between the Raman intensity and the concentration of the corresponding species is illustrated by the spectral titration of U(vi) with a very strong ligand, dipicolinic acid (DPA); and the application of a spectral titration method with Raman spectroscopy in studying the complexation of uranyl is demonstrated by the titration of U(vi) with oxalate. The stepwise changes in the Raman shift of 18, 17, and 6 cm -1 , corresponding to the three oxalate anions successively bonding to UO 2 2+ , imply that the coordination modes are different. In the 1 : 1 and 1 : 2 ratios of metal to ligand complexes, the oxalate anions bond to the uranyl ion in side-on bidentate mode, but in the 1 : 3 complex the third oxalate bonds in head-on mode, which is much weaker than the first two.

  14. The electrochemical behaviour study of La3+ ion in fused chlorides bath. The LaNi5 formation

    International Nuclear Information System (INIS)

    Dias, Cristiane

    2002-01-01

    The electrochemical behaviour of La 3+ ion was studied in fused chlorides bath, with purpose to obtain LaNi 5 formation parameters. The lanthanum reduction/reoxidation mechanism and intermetallic compound formation were investigated by cyclic voltammetry, chronopotentiommetry and galvanostatic electrodeposition. The electrolyte employed was eutectic mixture NaCl-KCl (1:1) with anhydrous LaCl 3 as solute, since 0,25 mol. L -1 up to 2 mol. L -1 , between 700 deg C and 800 deg C. The anhydrous LaCl 3 was prepared by lanthanum chloride slow dehydration with HCl flow and heating until 300 deg C. Over molybdenum, results depicted that lanthanum electrochemical behaviour was quasi-reversible and electrodeposition occurred in a charge transfer step with three electrons. In nickel, intermetallic compound formation was observed by interdiffusion. The scanning electronic microscopy (SEM-EDS) and X ray diffraction analysis indicated that layers composition depend on temperature and solute concentration in fused bath. Mainly LaNi 5 intermetallic compound was formed with LaCl 3 anhydrous concentration of 2 mol. L -1 at 750 deg C, with cathodic current density until 100 mA.cm -2 . (author)

  15. Effect of the temperature and the chlorine pressure, over the aluminium chlorides obtained by direct chlorination of the 6061 alloy

    International Nuclear Information System (INIS)

    Alvarez, Fabiola J.; Bohe, Ana E.; Pasquevich, Daniel M.

    2003-01-01

    The aluminium chloride is synthesized by direct chlorination of aluminium, in agreement with the following reaction: Al(s) + 3/2 Cl 2 AlCl 3 (s,g).The present work focuses on the preparation of aluminium chlorides by two methods: (a) Chlorination of 6061 aluminium alloy with gaseous chlorine in sealed containers, filled with different pressures of gas, from 0.8 to 74 Kpa and in the range of temperature between 200 0 and 500 0 C.(b) Chlorination of the same alloy in chlorine flow between 150 0 and 400 0 C.In the sealed systems, the hexahydrated aluminium trichloride predominated over the anhydrous form. For pressures lower than 14 Kpa and temperatures under 250 0 C, the chloride didn't appear.The residues were rich in aluminium, chlorine and magnesium.In the other systems, the anhydrous chloride was found in the areas of the reactor of temperatures above 100 0 C, for all the thermal treatments. The waste was composed by CrCl 3 and AlCl 3 .6H 2 O.The influence of the chlorine pressures and the heating temperature over the characteristics of the product, was studied.The characterization techniques were x-ray diffraction and energy dispersive spectroscopy, and the evolution of the structure was followed by scanning electron microscopy

  16. Electrochemical reactions of uranyl(VI) complexes in aqueous solution, non-aqueous solvents, and ionic liquids

    International Nuclear Information System (INIS)

    Ikeda, Yasuhisa

    2006-01-01

    Author's recent experimental results on the chemistry of U(V) in aqueous solution, non-aqueous solvents, and ionic solvents by cyclic voltametry are described. The U(V) was produced by electrochemical reduction of uranyl U(VI) ions or complexes such as carbonates, DMF(N, N-dimethylformamide), DMSO(dimethylsulfoxide), acetylacetonato, and other organic polydental ligands. The produced U(V) complexes were studied by spectrophotometry using optical-transmission thin-layer electrode. The U(V) complexes in non-aqueous solvents were found to be rather stable, they undergo ligand-dissociation reaction but not disproportionation reaction. The structure and electronic spectra as well as IR spectra of the complexes were studied. The present method was further developed to study the behavior of U(V) complexes in ionic liquids as molten salts, e.g., alkaline metals chlorides. Thus, the present research contributes to understanding the chemistry of 5fl system. Application to such nuclear technology as spent fuel reprocessing is discussed. (S. Ohno)

  17. Uranium (VI) chemistry at the interface solution/minerals (quartz and aluminium hydroxide): experiments and spectroscopic investigations of the uranyl surface species

    International Nuclear Information System (INIS)

    Froideval, A.

    2004-09-01

    This study deals with the understanding of the uranyl chemistry at the 0.1 M NaNO 3 solution/mineral (quartz and aluminium hydroxide) interface. The aims are:(i) to identify and to characterize the different uranyl surface species (mononuclear, polynuclear complexes and/or precipitates...), i.e. the coordination environments of sorbed/precipitated uranyl ions, by using X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) and time-resolved laser-induced fluorescence spectroscopy (TRLFS), and;(ii) to investigate the influence of pH, initial uranyl aqueous concentration and hydroxyl ligand concentration on the uranyl surface speciation. Our study on the speciation of uranyl ions at the quartz surface (i) confirms the formation of uranyl polynuclear/oligomers on quartz from moderate (1 μmol/m 2 ) to high (26 μmol/m 2 ) uranyl surface concentrations and (ii) show that theses polynuclear species coexist with uranyl mononuclear surface species over a pH range ≅ 5-8.5 and a wide range of initial uranyl concentration o f the solutions (10-100 μM). The uranyl concentration of these surface species depends on pH and on the initial uranyl aqueous concentration. Hydrate (surface-) precipitates and/or adsorbed polynuclear species and monomeric uranyl surface complexes are formed on aluminium hydroxide. Uranyl mononuclear complexes are predominant at acidic pH, as well as uranyl in solution or on the surface. Besides mononuclear species, precipitates and/or adsorbed polynuclear species are predominantly formed at neutral pH values on aluminium hydroxide. A main contribution of our investigations is that precipitation and/or adsorption of polynuclear species seem to occur at low uranyl surface concentrations (0.01-0.4 μmol/m 2 ). The uranyl surface speciation is mainly dependent on the pH and the aluminol ligand concentration. (author)

  18. Charge-density matching in organic-inorganic uranyl compounds

    Energy Technology Data Exchange (ETDEWEB)

    Krivovichev, S.V. [Saint Petersburg State Univ., Dept. of Crystallography, Faculty of Geology (Russian Federation); Krivovichev, S.V.; Tananaev, I.G.; Myasoedov, B.F. [Russian Academy of Sciences, A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow (Russian Federation)

    2007-10-15

    Single crystals of [C{sub 10}H{sub 26}N{sub 2}][(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}SeO{sub 4}){sub 0.85}(H{sub 2}O){sub 2} (1), [C{sub 10}H{sub 26}N{sub 2}][(UO{sub 2})(SeO{sub 4}){sub 2}] (H{sub 2}SeO{sub 4}){sub 0.50}(H{sub 2}O) (2), and [C{sub 8}H{sub 20}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (H{sub 2}O) (3) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amines. The structures of the compounds have been solved by direct methods and structural models have been obtained. The structures of the compounds 1, 2, and 3 contain U and Se atoms in pentagonal bipyramidal and tetrahedral coordinations, respectively. The UO{sub 7} and SeO{sub 4} polyhedra polymerize by sharing common O atoms to form chains (compound 1) or sheets (compounds 2 and 3). In the structure of 1, the layers consisting of hydrogen-bonded [UO{sub 2}(SeO{sub 4}){sub 2}(H{sub 2}O)]{sup 2-} chains are separated by mixed organic-inorganic layers comprising from [NH{sub 3}(CH{sub 2}){sub 10}NH{sub 3}]{sup 2+} molecules, H{sub 2}O molecules, and disordered electroneutral (H{sub 2}SeO{sub 4}) groups. The structure of 2 has a similar architecture but a purely inorganic layer is represented by a fully connected [UO{sub 2}(SeO{sub 4}){sub 2}]{sup 2-} sheet. The structure of 3 does not contain disordered (H{sub 2}SeO{sub 4}) groups but is based upon alternating [UO{sub 2}(SeO{sub 4}){sub 2}(H{sub 2}O)]{sup 2-} sheets and 1.5-nm-thick organic blocks consisting of positively charged protonated octylamine molecules, [NH{sub 3}(CH{sub 2}){sub 7}CH{sub 3}]{sup +}. The structures may be considered as composed of anionic inorganic sheets (2D blocks) and cationic organic blocks self-organized according to competing hydrophilic-hydrophobic interactions. Analysis of the structures allows us to conclude that the charge-density matching principle is observed in uranyl compounds. In order to satisfy some basic peculiarities of uranyl (in

  19. Sorption of uranyl species on zircon and zirconia

    International Nuclear Information System (INIS)

    Lomenech, C.; Drot, R.; Simoni, E.; Ehrhardt, J.J.; Mielczarski, J.

    2002-01-01

    The safety of a long-term storage of radioactive waste in deep geological repositories would be strongly affected by the migration properties of radionuclides through the different barriers to the surface of the earth. Since the main process involved in the retention of radioactive ions is their sorption at the water/ mineral interface, a quantitative description of the sorption reactions is needed. Macroscopic data have for a long time been the only source of information used to propose a modelling of sorption equilibria, although they bring no direct information on the nature of the sorbed species; a microscopic structural investigation of the surface complexes is difficult indeed, because of the small amount of matter sorbed. Thus, in this study, parallel to the macroscopic measurements, different complementary spectroscopic techniques have been used in order to determine the nature of the surface species. As the final purpose of such a study is the simulation of the experimental retention data, the precise structural identification of the sorption equilibria will then be very useful to constrain the data simulation code. In this work, we present the results of both macroscopic and microscopic studies of the sorption of uranyl species on zircon and zirconia. The first part of our macroscopic approach was the surface characterisation of the non-sorbed materials by the determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, while the second part aimed at obtaining the sorption isotherms (percentage of sorption versus pH), which was performed using alpha spectrometry, for different uranyl concentrations, media (NaClO 4 or KNO 3 ) and ionic strengths. The spectroscopic identification of the different surface complexes and sorption sites has been carried out using four different spectroscopies. Whereas tune-resolved laser spectro-fluorimetry gave a direct answer concerning the number of surface species (only for a

  20. 1H chemically induced dynamic nuclear polarization in the photodecomposition of uranyl carboxylates

    International Nuclear Information System (INIS)

    Rykov, S.V.; Khudyakov, I.V.; Skakovsky, E.D.; Burrows, H.D.; Formosinho, S.J.; Miguel, M. da G.M.

    1991-01-01

    Chemically induced dynamic nuclear polarization ( 1 H CIDNP) has been observed during photolysis of uranyl salts of pivalic, propionic, and acetic acids in D 2 O solution, [ 2 H 6 ]acetone, [ 2 H 4 ]methanol, or in some other solvent. The multiplet polarization of isobutene and isobutane protons has been found under photolysis of deoxygenated pivalate solution. The polarized compounds are formed in the triplet pairs of tert-butyl free radicals. 1 H Emission of the tert-butylperoxyl group and emission of 1 H from isobutene have been recorded under photolysis of air-saturated pivalate solutions. The CIDNP of butane protons stays as a multiplet. Such changes in the presence of air/oxygen have arisen apparently because of the formation of tert-butylperoxyl free radical and its reaction with tert-butyl radical products, i.e. hydroperoxide (peroxide) and isobutene. Isobutene probably forms a complex with molecular oxygen which has a very short proton relaxation time. During the photolysis of uranyl pivalate in the presence of p-benzoquinone (5 x 10 -2 -0.1 mol dm -3 ) we have not observed any CIDNP, whereas under p-benzoquinone concentrations of 10 -3 -10 -2 mol dm -3 the CIDNP from both hydroquinone and p-benzoquinone has been followed. Photolysis of uranyl propionate has led to CIDNP from butane protons. An emission from methyl group protons of a compound with an ethylperoxyl fragment in the presence of air/oxygen has been observed. The same polarization picture has arisen under interaction of photoexcited uranyl with propionic acid. During the photolysis of uranyl acetate at relatively low concentrations (10 -2 mol dm -3 ) a CIDNP very similar to that registered for uranyl propionate was recorded. The ethyl fragment is probably obtained in reactions for two methyl radicals formed from acetate with the parent uranyl acetate, namely hydrogen-atom abstraction and addition reactions. (author)

  1. Crystal structure of the uranyl-oxide mineral rameauite

    Energy Technology Data Exchange (ETDEWEB)

    Plasil, Jakub [ASCR, Prague (Czech Republic). Inst. of Physics; Skoda, Radek [Masaryk Univ., Brno (Czech Republic). Dept. of Geological Sciences; Cejka, Jiri [National Museum, Prague (Czech Republic). Dept. of Mineralogy and Petrology; Bourgoin, Vincent; Boulliard, Jean-Claude [Pierre et Marie Curie Univ., Paris (France). Association Jean Wyart, Collection des Mineraux de Jussieu

    2016-12-15

    Rameauite is a rare supergene uranyl-oxide hydroxy-hydrate mineral that forms during hydration-oxidation weathering of uraninite. On the basis of single-crystal X-ray diffraction data collected on a microfocus source, rameauite is monoclinic, space group Cc, with a = 13.9458(19), b = 14.3105(19), c = 13.8959(18) Aa, β = 118.477(14) , V = 2437.7(6) Aa{sup 3} and Z = 4, with D{sub calc} = 5.467 g cm{sup -3}. The structure of rameauite (R = 0.060 for 1698 unique observed reflections) contains sheets of the β-U{sub 3}O{sub 8} topology, with both UO{sub 6} and UO{sub 7} bipyramids, which is similar to the sheets found in spriggite, ianthinite and wyartite. The sheets alternate with the interlayer, which contains K{sup +}, Ca{sup 2+} and H{sub 2}O molecules. Interstitial cations are linked into infinite chains that extend along [10-1]. Adjacent sheets are linked through K-O, Ca-O and H-bonds. The structural formula of rameauite is K{sub 2} Ca(H{sub 2}{sup [3]}O){sub 1}(H{sub 2}{sup [5]}O){sub 4}[(UO{sub 2}) {sub 6}O{sub 6}(OH){sub 4}](H{sub 2}{sup [4]}O){sub 1}. The empirical formula obtained from the average of eight electron-microprobe analyses is (on the basi s of 6 U p.f.u.) K{sub 1.87}(Ca{sub 1.10}Sr{sub 0.04}){sub Σ1.14}[(UO 2){sub 6}O{sub 6}(OH){sub 4.15}].6H{sub 2}O. The Raman spectrum is dominate d by U.O and O.H vibrations. A discussion of related uranyl-oxide minerals is given.

  2. Chloride removal from vitrification offgas

    Energy Technology Data Exchange (ETDEWEB)

    Slaathaug, E.J. [Westinghouse Hanford Co., Richland, WA (United States)

    1995-06-01

    This study identified and investigated techniques of selectively purging chlorides from the low-level waste (LLW) vitrification process with the purge stream acceptable for burial on the Hanford Site. Chlorides will be present in high concentration in several individual feeds to the LLW Vitrification Plant. The chlorides are highly volatile in combustion type melters and are readily absorbed by wet scrubbing of the melter offgas. The Tank Waste Remediation System (TWRS) process flow sheets show that the resulting chloride rich scrub solution is recycled back to the melter. The chlorides must be purged from the recycle loop to prevent the buildup of excessively high chloride concentrations.

  3. Chloride removal from vitrification offgas

    International Nuclear Information System (INIS)

    Slaathaug, E.J.

    1995-01-01

    This study identified and investigated techniques of selectively purging chlorides from the low-level waste (LLW) vitrification process with the purge stream acceptable for burial on the Hanford Site. Chlorides will be present in high concentration in several individual feeds to the LLW Vitrification Plant. The chlorides are highly volatile in combustion type melters and are readily absorbed by wet scrubbing of the melter offgas. The Tank Waste Remediation System (TWRS) process flow sheets show that the resulting chloride rich scrub solution is recycled back to the melter. The chlorides must be purged from the recycle loop to prevent the buildup of excessively high chloride concentrations

  4. Using microkinetic analysis to search for novel anhydrous formaldehyde production catalysts

    DEFF Research Database (Denmark)

    Li, Han-Jung; Lausche, Adam C.; Peterson, Andrew A.

    2015-01-01

    Abstract Direct dehydrogenation of methanol to produce anhydrous formaldehyde is investigated using periodic density functional theory (DFT) and combining the microkinetic model to estimate rates and selectivities on stepped (211) surfaces under a desired reaction condition. Binding energies...... that explicitly includes the effects of adsorbate coverage on the rates and selectivities as well as the volcano plots are obtained. Our results show that most of the stepped (211) pure-metallic surfaces such as Au, Pt, Pd, Rh, Ru, Ni, Fe, and Co are located in a region of low activity and selectivity toward CH2O...

  5. Electrolysis of a nitrosyl hexafluoro-molybdate in anhydrous hydrogen fluoride

    International Nuclear Information System (INIS)

    Mougin, Jacques

    1972-01-01

    This thesis addresses the field of irradiated fuel reprocessing, and more particularly the study of the formation of molybdenum hexafluoride (MoF_6) by electrolysis of nitrosyl hexafluoro-molybdate (NOMoF_6) in solution in HF. The author presents the conditions of preparation of an electrolysis in anhydrous HF: solvent purification and control, production of a reference electrode, potential-kinetic study of the behaviour of materials selected for the electrode. The author then addresses the actual hydrolysis of the solution of nitrosyl hexafluoro-molybdate [fr

  6. Relationship between Al content and substitution mechanism of Al-bearing anhydrous bridgmanites

    Science.gov (United States)

    Noda, M.; Inoue, T.; Kakizawa, S.

    2017-12-01

    It is considered that two substitution mechanisms, Tschermak substitution and oxygen vacancy substitution, exist in MgSiO3 bridgmanite for the incorporation of Al in anhydrous condition. Kubo and Akaogi (2000) has conducted the phase equilibrium experiment in the system MgSiO3-Al2O3, and established the phase diagram up to 28 GPa. However the careful observation in the bridgmanite shows that the chemical compositions are slightly deviated from Tschermak substitution join. The same tendency can be also observed in the run products by Irifune et al. (1996). This result indicates that pure Tschermak substitution bridgmanite cannot be stable even in the MgSiO3-Al2O3 join experiment. However, the previous studies used powder samples as the starting materials, so the absorbed water may affect the results. Therefore, we tried to conduct the experiment in the join MgSiO3-Al2O3 in extremely anhydrous condition to clarify whether the pure Tschermak substitution bridgmanite can be stable or not. In addition, we also examined the stability of oxygen vacancy bridgmanite in the extremely anhydrous condition for the comparison. The high pressure synthesis experiments were conducted at 28 GPa and 1600-1700° for 1hour using a Kawai-type multi-anvil apparatus. Four different Al content samples were prepared as the starting materials along the ideal substitution line of Tschermak (Al=0.025, 0.05, 0.1, 0.15 mol) and oxygen-vacancy (Al=0.025, 0.05, 0.075, 0.1 mol) substitutions, respectively (when total cation of 2). The glass rods were used as the starting materials to eliminate the absorbed water on the sample surface. The chemical compositions of the synthesized bridgmanite could not be measured by EPMA because of small grain size less than submicron. Therefore the chemical compositions were estimated from the result of the XRD pattern by subtracting the amount of the other phases. The estimated chemical compositions of Tschermak substitution bridgmanites were consistent with the

  7. Some physical properties of anhydrous and hydrated Brownmillerite doped with NaF

    International Nuclear Information System (INIS)

    Hassaan, M.Y.; El Desoky, M.M.; Salem, S.M.; Yousif, A.A.

    2003-01-01

    Different samples of Brownmillerite (the ferrite phase of cement clinker) doped with 0, 1 or 3 wt.% NaF were prepared. At first, the oxide mixture of Brownmillerite was prepared according to the following composition: 4 mol CaO, 1 mol Al 2 O 3 and 1 mol Fe 2 O 3 in addition to 1 or 3 wt.% NaF. Each mixture was mixed very well, introduced into an electric furnace at 1300 deg. C for 1 h in a platinum crucible, and then quenched in air. The product was divided into four portions mixed with 40 wt.% distilled water to form Brownmillerite paste, except for one portion which was left dry. Each paste was molded into two molds; after 24 h, they were immersed in a distilled water and withdrawn after 1 or 3 days of hydration, respectively. The pastes were ground again. The anhydrous powders of Brownmillerites and the hydrated samples were prepared for a.c. conduction measurements by pressing it to be in pellets form. The two surfaces of each pellet were coated with silver paste. The a.c. conductivity and dielectric constant for different samples were measured using four-probe method. The data was collected from 320 up to 670 K. Moessbauer spectra and X-ray diffraction patterns were measured for each sample (anhydrous and hydrated) to confirm the formation of Brownmillerite, identify the iron states and the magnetic properties. The results showed that NaF addition to Brownmillerite expedites the hydration reaction rate. The superparamagnetic relaxation, which appeared in the anhydrous Brownmillerite spectra due to the small particle size, decreases with increasing the hydration time. Also, the Fe 3+ (Oh) state increases while Fe 3+ (Td) decreases with the time of hydration. The a.c. conductivity value at fixed frequency for anhydrous and hydrated samples was found to increase with NaF addition. The a.c. conductivity and Moessbauer measurements can be used as good tools to verify the purity of Brownmillerite phase and, accordingly, the purity of cement

  8. Ultrastructural and metabolic changes in osteoblasts exposed to uranyl nitrate

    International Nuclear Information System (INIS)

    Tasat, D.R.; Orona, N.S.; Mandalunis, P.M.; Cabrini, R.L.; Ubios, A.M.

    2007-01-01

    Exposure to uranium is an occupational hazard to workers who continually handle uranium and an environmental risk to the population at large. Since the cellular and molecular pathways of uranium toxicity in osteoblast cells are still unknown, the aim of the present work was to evaluate the adverse effects of uranyl nitrate (UN) on osteoblasts both in vivo and in vitro. Herein we studied the osteoblastic ultrastructural changes induced by UN in vivo and analyzed cell proliferation, generation of reactive oxygen species (ROS), apoptosis, and alkaline phosphatase (APh) activity in osteoblasts exposed to various UN concentrations (0.1, 1, 10, and 100 μM) in vitro. Cell proliferation was quantified by means of the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, ROS was determined using the nitro blue tetrazolium test, apoptosis was morphologically determined using Hoechst 3332 and APh activity was assayed spectrophotometrically. Electron microscopy revealed that the ultrastructure of active and inactive osteoblasts exposed to uranium presented cytoplasmic and nuclear alterations. In vitro, 1-100 μM UN failed to modify cell proliferation ratio and to induce apoptosis. ROS generation increased in a dose-dependent manner in all tested doses. APh activity was found to decrease in 1-100 μM UN-treated cells vs. controls. Our results show that UN modifies osteoblast cell metabolism by increasing ROS generation and reducing APh activity, suggesting that ROS may play a more complex role in cell physiology than simply causing oxidative damage. (orig.)

  9. Reversible uranyl fluoride nephrotoxicity in the Long Evans rat

    International Nuclear Information System (INIS)

    Diamond, G.L.; Morrow, P.E.; Panner, B.J.; Gelein, R.M.; Baggs, R.B.

    1989-01-01

    Severity and duration of renal injury produced by low levels of uranyl fluoride (UO2F2) were examined in the rat. Rats received multiple ip injections of UO2F2 (cumulative dose: 0.66 or 1.32 mg U/kg body wt). Renal injury was characterized histologically by cellular and tubular necrosis of pars recta of proximal tubule (S2 and S3), with less severe cellular injury to thick ascending limb of loop of Henle and collecting tubule. Injury was evident when renal uranium levels were between 0.7 and 1.4 micrograms U/g wet kidney and was most severe when renal uranium burden was between 3.4 and 5.6 micrograms U/g. Repair of injury was rapid, with complete restoration within 35 days after exposure. Associated with injury were abnormalities in renal function, including impaired tubular reabsorption, proteinuria, and enzymuria, which appeared temporally related, to variable degrees, to progression of renal injury. Thus, reversible renal injury occurs in the rat at levels of uranium in kidney below the present Nuclear Regulatory Commission standard of 3 micrograms U/g kidney for renal injury in humans

  10. Adsorption of uranyl in SiO2 porous glass

    International Nuclear Information System (INIS)

    Benedetto, F. E.; Prado, M. O.

    2013-01-01

    Vitreous SiO 2 porous matrices can be used in many applications involving the uptake of chemical species on its solid surface. In this work, vitreous silica sponges were prepared from a sodium borosilicate glass manufactured in our laboratory. The product obtained was then separated into phases with subsequent leaching of the soluble phase rich in B and Na. The resulting porous matrices have a specific surface of 35 m2/gr. Adsorption of uranyl ions onto the SiO 2 porous surface was studied to evaluate the use of this material as a filter for treatment of uranium containing water. The effects of contact time, adsorbent mass and equilibrium concentration of solution were studied. The porous adsorbent exhibits a pseudo-second-order kinetic behavior. The sponges with adsorbed uranium were thermally sealed as a way of U immobilization. Retention of uranium was confirmed during the matrix sealing by TGA. Uranium concentration before and after adsorption tests were made by means of ICP-OES. For uranium concentration of 800 ppm, 72 hours contact time and pH of 3.5, the amount of uranium adsorbed was 21.06 ± 0.02 mg U per gram of vitreous porous SiO 2 . (author)

  11. Tritium gettering from air with hydrogen uranyl phosphate

    International Nuclear Information System (INIS)

    Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, T.T.

    1985-08-01

    The managers of all tritium facilities now worry about their emissions into the atmosphere. The only method for cleaning tritium out of air is to catalyze the formation of tritiated water which is adsorbed, along with the overwhelming bulk of naturally occurring water vapor, on a zeolite molecular sieve. This method generally costs several million dollars for a small system, because of the necessary steel ducting, compressors and holding tanks. We have long had the dream of finding another getter that might be cheaper to use and would, hopefully, not make tritiated water (HTO). In a previous paper, we discovered that hydrogen uranyl phosphate (HUP, with the formula HUO 2 PO 4 x 4H 2 O) getters 1 ppM of tritium gas out of moist air. This makes HUP the first known ''direct'' tritium getter to work in air. However, the tritium enters a hydroxyl network within the HUP, so that it is effectively still in ''water'' form within the HUP. Worse yet, we found up to 10% tritiated water formed during the previous gettering experiments. HUP is unusual in possessing the exceptionally low vapor pressure of 0.6 torr water vapor at 298 0 K. This allows HUP to be used in fairly dry environments. 14 refs., 3 figs., 2 tabs

  12. Synthesis of uranyl ion imprinted polymer and its application in analysis

    International Nuclear Information System (INIS)

    Xiao Jingshui; Liu Huijun; Xiao Xilin; Huang Shengli

    2011-01-01

    Uranyl ion imprinted polymer beads were prepared by the copolymerization of styrene monomer and divinyl benzene as crosslinking agent in methanol solution,with the UO 2 2+ -o-dihydroxybenzene-4-vinyl pyridine ternary complex as template, the 2, 2'-azo-bis-isobutyronitrile as initiator and UO 2 2+ as the imprinting ion. The uranyl ions were removed from the polymer beads by treating with 6 mol/L HCl, leaving behind cavities that match uranyl ion in size. The treated polymer beads can preconcentrate uranyl ions from dilute aqueous solutions. The adsorption efficiency can reach 99% or above with good selectivity when pH is in the range of 5-7 and the adsorption time is more than 20 min. The elution rate can reach above 99% under the conditions of concentration of HCl being above 1.0 mol/L, elution time more than 20 min and the elution Janume more than 5 times the Janume of ion imprinted polymer. The uranyl ion imprinted polymer beads have been successfully applied to determine micro-uranium in brine samples. The results are satisfactory compared with NBS method.(authors)

  13. Electron spectra and mechanism of complexing of uranyl nitrate in water-acetone solutions

    International Nuclear Information System (INIS)

    Zazhogin, A.A.; Zazhogin, A.P.; Komyak, A.I.; Serafimovich, A.I.

    2003-01-01

    Based on the analysis of the luminescence and electronic absorption spectra, the processes of complexing in an aqueous solution of UO 2 (NO 3 ) 2 ·6H 2 O with small additions of acetone have been studied. In a pure aqueous solution, uranyl exists as the complex UO 2 ·5H 2 O. It is shown that the addition of acetone to the solution leads to the displacement of some water molecules out of the first coordination sphere of uranyl and the formation of the uranyl nitrate dihydrate complexes UO 2 (NO 3 ) 2 ·2H 2 O. It has been established that the stability of these complexes is determined by the decrease in the water activity and in the degree of hydration of uranyl and nitrate, which is the result of the local increase in the concentration of acetone molecules (due to their hydrophobicity) in the regions of the solution where uranyl and nitrate ions are found. The experimental facts supported the mechanism proposed are presented. (authors)

  14. Structural contributions to the third-law entropy of uranyl phases

    International Nuclear Information System (INIS)

    Chen, F.; Ewing, R.C.

    1999-01-01

    Entropies that are used in geochemical calculations are usually based on calorimetric measurements. However, because of the contributions of neglected residual entropies which cannot be determined by calorimetric measurements, the true third-law entropies for many phases may be quite different from those derived from thermal data. The residual entropies are caused by site-mixing, structural disorder and magnetic spin disorder and may result in a considerable contribution to the third-law entropy of solid phases. Magnetic spin-configurational entropy is not expected to be significant in uranyl phases. However, because most uranyl phases are based on sheet or chain structures and usually contain several molecular water groups, site-mixing, vacancies, as well as disorder in the orientation of hydrogen bonds and the polar H 2 O molecules may occur. Calculations of the ideal site-mixing configurational entropy for some uranyl phases indicate that the residual contributions that arise from substitution and vacancies to the third-law entropies of uranyl phases may be large. A brief examination of the crystal chemistry of water molecules in uranyl phases suggests that considerable residual entropy may be caused by the disorder of hydrogen bonds associated with interstitial H 2 O groups

  15. Time-resolved luminescence studies in hydrogen uranyl phosphate intercalated with amines

    Energy Technology Data Exchange (ETDEWEB)

    Novo, Joao Batista Marques [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil)]. E-mail: jbmnovo@quimica.ufpr.br; Batista, Fabio Roberto [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Cunha, Carlos Jorge da [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Dias, Lauro Camargo Jr. [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Teixeira Pessine, Francisco Benedito [Instituto de Quimica, Universidade Estadual de Campinas, CP 6154, 13084-971 Campinas-SP (Brazil)

    2007-05-15

    Time-resolved luminescence decays of intercalated compounds of hydrogen uranyl phosphate (HUP) with p-toluidinium (HUPPT), benzylaminium (HUPBZ), {alpha}-methylbenzylaminium (HUPMBZ) and hydroxylaminium (HUPHAM) were studied. The prepared compounds belong to the tetragonal P4/ncc space group and showed 00 l reflections shifted to lower angles relative to HUP, indicating that the intercalation increases the c parameter of the unit cell. The luminescence decays of the compounds with 100% of intercalation ratio (HUPHAM and HUPBZ) were analyzed by Global Analysis, assuming Lianos' stretched exponential as the model function, which can be applied to compounds with restricted geometry and mobile donor and quencher molecules. It was remarkable that the luminescence decays showed that the quenching of the emission of the uranyl ions by the intercalated protonated amines is not restricted by low dimensionality of the host uranyl phosphate, and that a diffusion mechanism occurs. Benzylaminium cation efficiently quenches the excited energy of the uranyl ions at close distance, but the long-range and long-lifetime quenching is hindered. A different situation is found in the case of the small hydroxylaminium cation, where the long distance diffusion of the species is fast, playing an important role in the quenching of the excited uranyl ions at longer times.

  16. Time-resolved luminescence studies in hydrogen uranyl phosphate intercalated with amines

    International Nuclear Information System (INIS)

    Novo, Joao Batista Marques; Batista, Fabio Roberto; Cunha, Carlos Jorge da; Dias, Lauro Camargo Jr.; Teixeira Pessine, Francisco Benedito

    2007-01-01

    Time-resolved luminescence decays of intercalated compounds of hydrogen uranyl phosphate (HUP) with p-toluidinium (HUPPT), benzylaminium (HUPBZ), α-methylbenzylaminium (HUPMBZ) and hydroxylaminium (HUPHAM) were studied. The prepared compounds belong to the tetragonal P4/ncc space group and showed 00 l reflections shifted to lower angles relative to HUP, indicating that the intercalation increases the c parameter of the unit cell. The luminescence decays of the compounds with 100% of intercalation ratio (HUPHAM and HUPBZ) were analyzed by Global Analysis, assuming Lianos' stretched exponential as the model function, which can be applied to compounds with restricted geometry and mobile donor and quencher molecules. It was remarkable that the luminescence decays showed that the quenching of the emission of the uranyl ions by the intercalated protonated amines is not restricted by low dimensionality of the host uranyl phosphate, and that a diffusion mechanism occurs. Benzylaminium cation efficiently quenches the excited energy of the uranyl ions at close distance, but the long-range and long-lifetime quenching is hindered. A different situation is found in the case of the small hydroxylaminium cation, where the long distance diffusion of the species is fast, playing an important role in the quenching of the excited uranyl ions at longer times

  17. Kinetic studies of uranyl ion adsorption on acrylonitrile (AN) / polyethylene glycol (PEG) interpenetrating networks (IPN)

    International Nuclear Information System (INIS)

    Aycik, G.A.; Gurellier, R.

    2004-01-01

    The kinetics of the adsorption of uranyl ions on amidoximated acrylonitrile (AN)/ polyethylene glycol (PEG) interpenetrating network (IPNs) from aqueous solutions was studied as a function of time and temperature. Adsorption analyses were performed for definite uranyl ion concentrations of 1x10 -2 M and at four different temperatures as 290K, 298K, 308K and 318K. Adsorption time was increased from zero to 48 hours. Adsorption capacities of uranyl ions by PEG/AN IPNS were determined by gamma spectrometer. The results indicate that adsorption capacity increases linearly with increasing temperature. The max adsorption capacity was found as 602 mgu/g IPN at 308K. Adsorption rate was evaluated from the curve plotted of adsorption capacity versus time, for each temperature. Rate constants for uranyl ions adsorption on amidoximated ipns were calculated for 290K, 298K, 308K and 318K at the solution concentration of 1x10 -2 M . The results showed that as the temperature increases the rate constant increases exponentially too. The mean activation energy of uranyl ions adsorption was found as 34.6 kJ/mole by using arrhenius equation. (author)

  18. Poly(vinyl chloride-grafted multi-walled carbon nanotubes via Friedel-Crafts alkylation

    Directory of Open Access Journals (Sweden)

    2010-11-01

    Full Text Available A novel approach was developed for the surface modification of the multi-walled carbon nanotubes (MWCNTs with high percentage of grafting (PG% by the grafting of polymer via the Friedel-Crafts alkylation. The graft reaction conditions, such as the amount of catalyst added, the reaction temperature, and the reaction time were optimized for the Friedel-Crafts alkylation of the MWCNTs with poly(vinyl chloride (PVC with anhydrous aluminum chloride (AlCl3 as catalyst in chloroform (CHCl3. The Fourier Transform Infrared (FT-IR, Raman, and thermogravimetric (TGA analysis showed that PVC had been successfully grafted onto MWCNTs both at the ends and on the sidewalls by the proposed Friedel-Crafts alkylation. The PVC grafted MWCNTs (PVC-MWCNTs could be dispersed well in organic solvent and the dispersion was more stable.

  19. Lithium thionyl chloride battery

    Energy Technology Data Exchange (ETDEWEB)

    Saathoff, D.J.; Venkatasetty, H.V.

    1982-10-19

    The discharge rate and internal conductivity of electrochemical cell including a lithium anode, and a cathode and an electrolyte including LiAlCl4 and SOC2 is improved by the addition of an amount of a mixture containing AlCl3 and butyl pyridinium chloride.

  20. The medical sodium chloride

    International Nuclear Information System (INIS)

    Mirsaidov, U.M.

    2002-01-01

    In the institute was investigated the chemical composition of rock salt of some deposits of Tajikistan and was show the presence in it admixture of ions of Ca 2 + , Mg 2 + a nd SO 2 - a nd absence of heavy metals, ammonium salts, iron, potassium and arsenic. Was elaborated the fundamental instrument-technologic scheme of sodium chloride receiving

  1. Quenching of excited uranyl ion during its photochemical reduction with triphenyl-phosphine : Part IV - effect of heterocyclic molecules

    International Nuclear Information System (INIS)

    Sidhu, M.S.; Bhatia, P.V.K.

    1994-01-01

    The presence of heterocyclic compounds triggers off a competition between photophysical and photochemical annihilation of excited uranyl ion during its photochemical reduction with triphenylphosphine. This competition is used to measure Stern-Volmer constant using UV visible spectrophotometer for quenching the uranyl ion luminescence with a number of heterocyclic molecules viz., pyridine, thiophene bipyridyl, tetrahydrofuran and piperidine. (author). 7 refs., 2 figs., 1 tab

  2. Aqueous uranyl complexes. 3. Potentiometric measurements of the hydrolysis of uranyl(VI) ion at 25 degrees C

    International Nuclear Information System (INIS)

    Palmer, D.A.; Nguyen-Trung, C.

    1995-01-01

    Potentiometric titrations of uranyl(VI) solutions were conducted using a standard glass/calomel electrode combination over the pH range 3 to 12 at 0.1 mol-kg -1 ionic strength with tetramethylammonium trifluoromethanesulfonate as the supporting electrolyte. The electrodes were calibrated directly on the hydrogen ion concentration scale during the initial stage of each titration. The species, UO 2 2+ , (UO 2 ) 2 (OH) 2 2+ , (UO 2 ) 3 (OH) 5 + , (UO 2 ) 3 (OH) 7 - , (UO 2 ) 3 (OH) 8 2- , and (UO 2 ) 3 (OH) 10 4- identified in an earlier Raman study were compatible with the analysis of the titration data. Based on this analysis and application of the extended Debye-Hueckel treatment, the polynuclear species indicated above were assigned overall formation constants at 25 degrees C and at infinite dilution of -5.51±0.04, -15.3±0.1, -27.77±0.09, -37.65±0.14, and -62.4±0.3, respectively. The results are discussed in reference to hydrolysis quotients reported in the literature for the first three species. Formation quotients for the last two species have not been reported previously

  3. An Efficient, Solvent-Free Process for Synthesizing Anhydrous MgCl2

    Energy Technology Data Exchange (ETDEWEB)

    Motkuri, Radha K.; Vemuri, Venkata Rama S.; Barpaga, Dushyant; Schaef, Herbert T.; Loring, John S.; Martin, Paul F.; Lao, David; Nune, Satish K.; McGrail, Bernard P.

    2018-01-02

    A new efficient and solvent-free method for the synthesis of anhydrous MgCl2 from its hexahydrate is proposed. Fluidized dehydration of MgCl2·6H2O feedstock at 200 °C in a porous bed reactor yields MgCl2·nH2O (0 < n < 1), which has a similar diffraction pattern as activated MgCl2. The MgCl2·nH2O is then ammoniated directly using liquefied NH3 in the absence of solvent to form MgCl2·6NH3. Calcination of the hexammoniate complex at 300 °C then yields anhydrous MgCl2. Both dehydration and deammoniation were thoroughly studied using in situ as well as ex situ characterization techniques. Specifically, a detailed understanding of the dehydration process was monitored by in situ PXRD and in situ FTIR techniques where formation of salt with nH2O (n = 4, 2, 1, <1) was characterized. Given the reduction in thermal energy required to produce dehydrated feedstock with this method compared with current strategies, significant cost benefits are expected. Overall, the combined effect of activation, macroporosity, and coordinated water depletion allows the formation of hexammoniate without using solvent, thus minimizing waste formation.

  4. Study of gasoline mixture with 10% of anhydrous ethanol. Physic-chemical properties evaluation

    International Nuclear Information System (INIS)

    Torres, Jaime; Molina, Daniel; Pinto, Carlos; Rueda, Fernando

    2002-01-01

    This study includes the assessment results for blends of premium and regular gasoline produced in Barrancabermeja' s refinery with 10vol% anhydrous ethanol and concentrations within this range (from 5vol% to 15vol%). The results may allow for a more precise definition of the characteristics for the desired blend. The survey basically focused on the Reid vapor pressure (RVP) and the antiknock index (RON+MON/2) properties, in order to determine the variations within these properties when 5vol%, 10vol%, and 15vol% anhydrous ethanol is added to the base fuels. Based on these results, the RVP and antiknock index were determined for the base fuels, blended with 10vol% ethanol, to comply with the quality standards required for Colombian fuels in year 2005. For the adjustment of the base fuel's RVP, light-vapors, nitrogen-dragging stripper was designed and built. As for the adjustment of the base fuel's antiknock index, blends with straight naphtha were made for lower index values, while blends with cracked naphtha and high octane alkylate were made for higher index values. Having determined the specifications for base fuels, as required to blend them with 10vol% ethanol and meet the quality standards for Colombian gasoline in year 2005, water tolerance for the blends was estimated at temperature ranges of 273 k to 313 k

  5. A new anhydrous proton conductor based on polybenzimidazole and tridecyl phosphate

    International Nuclear Information System (INIS)

    Jiang Fengjing; Pu Hongting; Meyer, Wolfgang H.; Guan Yisi; Wan Decheng

    2008-01-01

    Most of the anhydrous proton conducting membranes are based on inorganic or partially inorganic materials, like SrCeO 3 membranes or polybenzimidazole (PBI)/H 3 PO 4 composite membranes. In present work, a new kind of anhydrous proton conducting membrane based on fully organic components of PBI and tridecyl phosphate (TP) was prepared. The interaction between PBI and TP is discussed. The temperature dependence of the proton conductivity of the composite membranes can be modeled by an Arrhenius relation. Thermogravimetric analysis (TGA) illustrates that these composite membranes are chemically stable up to 145 deg. C. The weight loss appearing at 145 deg. C is attributed to the selfcondensation of phosphate, which results in the proton conductivity drop of the membranes occurring at the same temperature. The DC conductivity of the composite membranes can reach ∼10 -4 S/cm for PBI/1.8TP at 140 deg. C and increases with increasing TP content. The proton conductivity of PBI/TP and PBI/H 3 PO 4 composite membranes is compared. The former have higher proton conductivity, however, the proton conductivity of the PBI/H 3 PO 4 membranes increases with temperature more significantly. Compared with PBI/H 3 PO 4 membranes, the migration stability of TP in PBI/TP membranes is improved significantly

  6. Decomposition of uranyl peroxo-carbonato complex ion in the presence of metal oxides in carbonate media

    International Nuclear Information System (INIS)

    Dong-Yong Chung; Min-Sung Park; Keun-Young Lee; Eil-Hee Lee; Kwang-Wook Kim; Jei-Kwon Moon

    2015-01-01

    Uranium oxide was dissolved in the form of the uranyl peroxo-carbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- in carbonate solutions with hydrogen peroxide. When UO 2 (O 2 )(CO 3 ) 2 4- ions lose their peroxide component, they become a stable species of uranyl tricarbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- . The uranyl peroxo-carbonato complex self-decomposed more rapidly into the uranyl tricarbonato complex ion in the presence of a metal oxide in the carbonate solution. In this study, decomposition of the uranyl peroxo-carbonato complex in a carbonate solution was investigated in the presence of several metal oxides using absorption spectroscopy. (author)

  7. Time-resolved luminescence spectroscopy of trace uranyl in wet sand

    International Nuclear Information System (INIS)

    Freed, D.

    1993-01-01

    The objective of the project was to develop a technique to observe and characterize the behaviour of uranium in unsaturated groundwater flow systems, particularly with regard to unstable ''fingered'' flow, which could drastically reduce time of travel. The actual experimental work described was a study of the feasibility of detecting uranyl at the parts-per-billion level in aqueous solution by means of its luminescence spectrum. A high-power UV laser was used to excite aqueous uranyl in a wet sand mixture; the characteristic green phosphorescence emitted in the decay transition was detected by a photomultiplier tube; and the amplified signal was sent to an oscilloscope in communication with Macintosh data acquisition software. At the time of the conference, a more sophisticated sample configuration for imaging the flow of uranyl was already under development. 5 refs., 3 figs

  8. Time-resolved luminescence spectroscopy of trace uranyl in wet sand

    Energy Technology Data Exchange (ETDEWEB)

    Freed, D [Massachusetts Inst. of Tech., Cambridge, MA (United States)

    1994-12-31

    The objective of the project was to develop a technique to observe and characterize the behaviour of uranium in unsaturated groundwater flow systems, particularly with regard to unstable ``fingered`` flow, which could drastically reduce time of travel. The actual experimental work described was a study of the feasibility of detecting uranyl at the parts-per-billion level in aqueous solution by means of its luminescence spectrum. A high-power UV laser was used to excite aqueous uranyl in a wet sand mixture; the characteristic green phosphorescence emitted in the decay transition was detected by a photomultiplier tube; and the amplified signal was sent to an oscilloscope in communication with Macintosh data acquisition software. At the time of the conference, a more sophisticated sample configuration for imaging the flow of uranyl was already under development. 5 refs., 3 figs.

  9. Expanding the Library of Uranyl Amide Derivatives: New Complexes Featuring the tert-Butyldimethylsilylamide Ligand.

    Science.gov (United States)

    Pattenaude, Scott A; Coughlin, Ezra J; Collins, Tyler S; Zeller, Matthias; Bart, Suzanne C

    2018-04-16

    New uranyl derivatives featuring the amide ligand, -N(SiHMe 2 ) t Bu, were synthesized and characterized by X-ray crystallography, multinuclear NMR spectroscopy, and absorption spectroscopies. Steric properties of these complexes were also quantified using the computational program Solid-G. The increased basicity of the free ligand -N(SiHMe 2 ) t Bu was demonstrated by direct comparison to -N(SiMe 3 ) 2 , a popular supporting ligand for uranyl. Substitutional lability on a uranyl center was also demonstrated by exchange with the -N(SiMe 3 ) 2 ligand. The increased basicity of this ligand and diverse characterization handles discussed here will make these compounds useful synthons for future reactivity.

  10. Synthesis, X-ray crystallography, thermal studies, spectroscopic and electrochemistry investigations of uranyl Schiff base complexes.

    Science.gov (United States)

    Asadi, Zahra; Shorkaei, Mohammad Ranjkesh

    2013-03-15

    Some tetradentate salen type Schiff bases and their uranyl complexes were synthesized and characterized by UV-Vis, NMR, IR, TG, C.H.N. and X-ray crystallographic studies. From these investigations it is confirmed that a solvent molecule occupied the fifth position of the equatorial plane of the distorted pentagonal bipyramidal structure. Also, the kinetics of complex decomposition by using thermo gravimetric methods (TG) was studied. The thermal decomposition reactions are first order for the studied complexes. To examine the properties of uranyl complexes according to the substitutional groups, we have carried out the electrochemical studies. The electrochemical reactions of uranyl Schiff base complexes in acetonitrile were reversible. Copyright © 2012 Elsevier B.V. All rights reserved.

  11. Uranyl adsorption kinetics within silica gel: dependence on flow velocity and concentration

    Science.gov (United States)

    Dodd, Brandon M.; Tepper, Gary

    2017-09-01

    Trace quantities of a uranyl dissolved in water were measured using a simple optical method. A dilute solution of uranium nitrate dissolved in water was forced through nanoporous silica gel at fixed and controlled water flow rates. The uranyl ions deposited and accumulated within the silica gel and the uranyl fluorescence within the silica gel was monitored as a function of time using a light emitting diode as the excitation source and a photomultiplier tube detector. It was shown that the response time of the fluorescence output signal at a particular volumetric flow rate or average liquid velocity through the silica gel can be used to quantify the concentration of uranium in water. The response time as a function of concentration decreased with increasing flow velocity.

  12. Engineering of specific uranyl-coordination sites in the calcium-binding motif of Calmodulin

    International Nuclear Information System (INIS)

    Beccia, M.; Pardoux, R.; Sauge-Merle, S.; Bremond, N.; Lemaire, D.; Berthomieu, C.; Delangle, P.; Guilbaud, P.

    2014-01-01

    Complete text of publication follows: Characterization of heavy metals interactions with proteins is fundamental for understanding the molecular factors and mechanisms governing ions toxicity and speciation in cells. This line of research will also help in developing new molecules able to selectively and efficiently bind toxic metal ions, which could find application for bio-detection or bioremediation purposes. We have used the regulatory calcium-binding protein Calmodulin (CaM) from A. thaliana as a structural model and, starting from it, we have designed various mutants by site-directed mutagenesis. We have analysed thermodynamics of uranyl ion binding to both sites I and II of CaM N-terminal domain and we have identified structural factors governing this interaction. Selectivity for uranyl ion has been tested by studying reactions of the investigated peptides with Ca 2+ , in the same conditions used for UO 2 2+ . Spectro-fluorimetric titrations and FTIR analysis have shown that the affinity for uranyl increases by phosphorylation of a threonine in site I, especially approaching the physiological pH, where the phospho-threonine side chain is deprotonated. Based on structural models obtained by Molecular Dynamics, we tested the effect of a two residues deletion on site I properties. We obtained an almost two orders of magnitude increase in affinity for uranyl, with a sub-nanomolar dissociation constant for the uranyl complex with the non phosphorylated peptide, and an improved uranyl/calcium selectivity. Allosteric effects depending on Ca 2+ and UO 2 2+ binding have been investigated by comparing thermodynamic parameters obtained for mutants having both sites I and II able to chelate metal ions with those of mutants consisting of just one active site

  13. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Univ. of California, Berkeley, CA (United States)

    2015-01-21

    The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  14. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    International Nuclear Information System (INIS)

    Arnold, John

    2015-01-01

    The uranyl cation (UO 2 2+ ) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  15. Anhydrous proton exchange membrane of sulfonated poly(ether ether ketone) enabled by polydopamine-modified silica nanoparticles

    International Nuclear Information System (INIS)

    Wang, Jingtao; Bai, Huijuan; Zhang, Haoqin; Zhao, Liping; Chen, Huiling; Li, Yifan

    2015-01-01

    Highlights: • The concept of acid/base pairs was employed to design anhydrous PEMs. • Polydopamine-modified silica particles were uniformly dispersed in SPEEK membrane. • The membranes displayed enhancement in both stability and anhydrous proton conductivity. - Abstract: Novel anhydrous proton exchange membrane is (PEM) facilely prepared by embedding dopamine-modified silica nanoparticles (DSiOis 2 ) into sulfonated poly (ether ether ketone) (SPEEK) polymer matrix. DSiO 2 bearing -NH 2 /-NH- groups are synthesized inspired by the bioadhesion principle, which are uniformly dispersed within SPEEK membrane due to the good interfacial compatibility. The interfacial electrostatic attractions render unique rearrangement of the nanophase-separated structure and the chain packing of the resultant hybrid membranes. As a result, the thermal and mechanical stabilities as well as structural stability of the hybrid membranes are enhanced when compared to SPEEK control membrane. On the other hand, induced by the attractions, acid–base pairs are formed at the SPEEK/DSiOarewere 2 interface, where fast proton transfer via Grotthuss mechanism is expected. These features confer much higher proton conductivities on the DSiO 2 -filled membranes under both hydrated and anhydrous conditions, compared to those of the SPEEK control membrane and SiO 2 -filled membranes. Particularly, the hybrid membrane with 15 wt% DSiO 2 achieve the highest conductivities of 4.52achieveachieved × 10 −3 S cm −1 at 120 °C under anhydrous condition, which is much higher than the SPEEK control membrane and the commercial Nafion membrane (0.1iswas × 10 −3 S cm −1 ). The membrane with 9 wt% DSiO 2 show an open cell potential of 0.98showshowed V and an optimum power density of 111.7 mW cm −2 , indicative of its potential application in fuel cell under anhydrous condition

  16. The treatment of uranyl nitrate from the AMOR process for VKTA Rossendorf

    International Nuclear Information System (INIS)

    Boessert, W.; Krempl, R.; Miller, J.W.

    2003-01-01

    The blending of uranyl nitrate solutions at VKTA and its subsequent treatment at BNFL-Sellafield is a significant step towards the safe and effective treatment of these enriched uranyl nitrate solutions. Overall the integration of the expertise of the international company BNFL/Westinghouse will lead to the achievement of a successful solution. This success has involved the integration of the project management and operational facilities of BNFL Sellafield with the local planning, design and manufacture capacities of Westinghouse Reaktor GmbH. (orig.)

  17. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    International Nuclear Information System (INIS)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

    2012-01-01

    Switching on uranium(V) reactivity: The silylated uranium(V) dioxo complex [(Me_3SiOUO)_2(L)_2] (A) is inert to oxidation, but after two-electron reduction to [(Me_3SiOUO)_2(L)]"2"- (1), it can be desilylated to form [OU(μ-O)_2UO(L)_2]"2"- (2) with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U"V"I"/"V couple in dioxygen reduction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    International Nuclear Information System (INIS)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

    2012-01-01

    The silylated uranium(V) dioxo complex [(Me_3SiOUO)_2(L)_2] is inert to oxidation, but after two-electron reduction to [(Me_3SiOUO)_2(L)]"2"-, it can be desilylated to form [OU(μ-O)_2UO(L)_2]"2"- with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U"V"I"/"V couple in dioxygen reduction. [de

  19. Kinetic analysis of laser induced phosphorescence in uranyl phosphate for improved analytical measurements

    International Nuclear Information System (INIS)

    Bushaw, B.A.

    1983-10-01

    Pulsed dye-laser excitation with multichannel scaler photon counting is used to obtain time resolved emission spectra of uranyl ions in aqueous solution. Kinetic analysis of this data corrects for matrix quenching and temperature effects which reduce the quantum yield of the uranyl ion luminescence. The method gives accurate measurements without separative prechemistry or the use of internal standards. Detection limits of one part-per-trillion (pptr) have been demonstrated, and in samples with concentrations greater than 100 pptr, relative standard deviations of less than 3% are achieved routinely

  20. Extraction of rare earth metals (3) from aqueous solutions containing thorium and uranyl nitrates

    International Nuclear Information System (INIS)

    Pyartman, A.K.; Kopyrin, A.A.; Berinskij, A.E.; Keskinov, V.A.

    2000-01-01

    Isotherms of extraction of rare earth metals (3) from aqueous solutions containing thorium and uranyl nitrates by solutions of tributylphosphate (TBP) and diisooctylmethylphosphonate (DIOMP) in kerosene at 298.15 Deg C and pH 1 are presented. Equations for description of interphase distribution of components of the systems considered are suggested. These equations describe distribution of components adequately in the systems of thorium nitrate (uranyl nitrate) - rare earth nitrates - (TBP, DIOMP) in the case of wide variation of phase compositions. Dependences of separation factors on composition of aqueous phase are considered [ru

  1. Removal of uranyl ions by p-hexasulfonated calyx[6]arene acid

    Energy Technology Data Exchange (ETDEWEB)

    Popescu, Ioana-Carmen [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Petru, Filip [“C.D. Nenitescu” Institute of Organic Chemistry, Splaiul Independentei 202B, Sector 6, Bucharest 71141 (Romania); Humelnicu, Ionel [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania); Mateescu, Marina [National R and D Institute for Chemistry and Petrochemistry, Splaiul Independenţei No. 202, Bucharest 060021 (Romania); Militaru, Ecaterina [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Humelnicu, Doina, E-mail: doinah@uaic.ro [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania)

    2014-10-15

    Radioactive pollution is a significant threat for the people’s health. Therefore highly effective radioactive decontamination methods are required. Ion exchange, biotechnologies and phytoremediation in constructed wetlands have been used as radioactive decontamination technologies for uranium contaminated soil and water remediation. Recently, beside those classical methods the calix[n]arenic derivatives’ utilization as radioactive decontaminators has jogged attention. The present work aims to present the preliminary research results of uranyl ion sorption studies on the p-hexasulfonated calyx[6]arenic acid. The effect of temperature, contact time, sorbent amount and uranyl concentration variation on sorption efficiency was investigated. Isotherm models revealed that the sorption process fit better Langmuir isotherm.

  2. Ultrastructure changes produced by the action of uranyl acetate on the human erythrocyte in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Wyatt, J H

    1975-06-01

    Human erythrocytes exposed in vitro to low concentrations of uranyl ions are immediately changed in shape to stomatocytes. Electron microscope examination demonstrates that cellular damage is confined to the plasma membrane. Endocytosis of the cell membrane produces groups of inside out membrane-lined vesicles within the cell; lipid from the membrane enters the cell, giving rise to intracellular myelin figures, and breaks are seen in the cell membrane. It is proposed that the lipid fraction of the cell membrane is the primary target for damage by uranyl ions.

  3. Determination of uranium in uranyl nitrate solutions of nuclear grade quality - Gravimetric method

    International Nuclear Information System (INIS)

    1990-01-01

    This international Standard specifies a precise and accurate gravimetric method for determining the uranium content in uranyl nitrate product solutions of nuclear grade quality at concentrations above 100 g/l of uranium. Non-volatile impurities influence the accuracy of the method. Uranyl nitrate is converted into uranium octoxide (U 3 O 8 ) by ignition in air to constant mass at 900 deg. C ± 10 deg. C. Calculation of the uranium content in the sample using a gravimetric conversion factor which depends on the isotopic composition of the uranium. The isotopic composition is determined by mass spectrometry

  4. First start-up of nuclear criticality safety experiment facility for uranyl nitrate solution

    International Nuclear Information System (INIS)

    Zhu Qingfu; Shi Yongqian; Shen Leisheng; Hu Dingsheng; Zhao Shouzhi; He Tao; Sun Zheng; Lin Shenghuo; Yao Shigui

    2005-01-01

    The uranyl nitrate solution experiment facility for the research on nuclear criticality safety is described. The nuclear fuel loading steps in the first start-up for water-reflected core are presented. During the experiments, the critical volume of uranyl nitrate solution was determined as 20479.62 mL with count rate inverse extrapolation method, reactivity interpolation method, and steady power method. By calculation, critical mass of 235 U was derived as 1579.184 g from experimental data. The worth of control rods was also calibrated in the first start-up of the facility. (authors)

  5. Interaction of aluminium(3) with uranyl ions in the course of joint hydrolysis

    International Nuclear Information System (INIS)

    Yusov, A.B.; Budantseva, N.A.; Fedoseev, A.M.; Astafurova, L.N.

    2001-01-01

    By means of spectrophotometry, luminescence and IR-spectroscopy one studied interaction of uranyl ions with Al 3+ ions in solutions at pH≥2 and in precipitates at pH≥5. It is shown that within 3-4 pH range the uranyl hydrolyzed forms interact with these of aluminium. Mixed hydroxoaquacomplexes are likely to be formed in solution with U:Al = 1:1 molar ratio. Large-size mixed polymers may be formed with pH increase. Varying of precipitation pH from 5 up to 14 does not minimize the importance of the oligomer mixed compounds for precipitation formation [ru

  6. Ultrastructure changes produced by the action of uranyl acetate on the human erythrocyte in vitro

    International Nuclear Information System (INIS)

    Wyatt, J.H.

    1975-06-01

    Human erythrocytes exposed in vitro to low concentrations of uranyl ions are immediately changed in shape to stomatocytes. Electron microscope examination demonstrates that cellular damage is confined to the plasma membrane. Endocytosis of the cell membrane produces groups of inside out membrane-lined vesicles within the cell; lipid from the membrane enters the cell, giving rise to intracellular myelin figures, and breaks are seen in the cell membrane. It is proposed that the lipid fraction of the cell membrane is the primary target for damage by uranyl ions. (author)

  7. Complete removal of uranyl nitrate from tissue matrix using supercritical fluid extraction

    International Nuclear Information System (INIS)

    Kumar, R.; Sivaraman, N.; Senthil Vadivu, E.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    2003-01-01

    The removal of uranyl nitrate from tissue matrix has been studied with supercritical carbon dioxide modified with methanol alone as well as complexing reagents dissolved in methanol. A systematic study of various complexing agents led to the development of an extraction procedure for the quantitative recovery of uranium from tissue matrix with supercritical carbon dioxide modified with methanol containing small quantities of acetylacetone. The drying time and temperature employed in loading of uranyl nitrate onto tissue paper were found to influence the extraction efficiency significantly

  8. Characterization of osteopontin-uranyl interaction: role of multiple phosphorylations

    International Nuclear Information System (INIS)

    Qi, Lei

    2014-01-01

    While some metals are essential for Life, other ones are only toxicants for living organisms, tolerated below well-definite concentrations. This is the case for uranium, a natural element which has no known biological function. It is a low α emitter and its chemical toxicity rather than its radiological toxicity is a subject of concern. Once in the body, this metal reaches the blood and accumulates in the bones under the action of unknown mechanisms. Uranium mainly exists in form of uranyl ion (UO 2 2+ ) in aqueous media and particularly reacts with carboxylates, phenolates and phosphates of the proteins. Previous studies have highlighted that UO 2 2+ modulates the SPP1 expression, a gene which codes for osteopontin (OPN). This highly phosphorylated glycoprotein plays an important role in bone homeostasis. This role and its biochemical properties led us to hypothesize that OPN might be a potential target of UO 2 2+ and involved in its accumulation in bones. A simple and original purification process was optimized to produce very highly purified OPN starting from human and bovine milk. Various biophysical approaches were set up and confirmed that both bovine and human OPN display very high affinity for UO 2 2+ . Moreover, the formation of stable UO 2 -protein complexes originating from structural changes was evidenced. The major role of phosphorylations, both on the OPN's affinity for UO 2 2+ and the stability of the UO 2 -protein complexes, was confirmed. These results demonstrate that OPN presents all the characteristics to be a major UO 2 2+ binding-protein in vitro, and they open new insights in the understanding of the UO 2 2+ mineralization process mechanisms. (author) [fr

  9. Mechanism of acute renal failure after uranyl nitrate

    International Nuclear Information System (INIS)

    Blantz, R.C.; Konnen, K.

    1975-01-01

    Administration of 25 mg/kg uranyl nitrate (UN) to rats leads to a brief period of polyuria followed by progressive oliguria with death at 5 days. Factors that determine glomerular filtration rate (GFR) were examined in control Munich--Wistar rats (n = 16) and 2 h after either 15 mg/kg (n = 8) or 25 kg/kg (n = 7) of UN (i.v.) utilizing direct measurements of hydrostatic and oncotic pressures and plasma flow. Total kidney GFR was reduced to 47 percent of control in the low dose group and to 21 percent in the high dose group. The simultaneous nephron filtration rate (sngfr) was 28.6 +- 0.8 nl/min/g kidney wt in control, 29.1 +- 1.0 in the low dose group, and 18.1 +- 1.2 (P less than 0.001) in the higher dose group. Nephron plasma flow was equal to control at both doses of UN. Also directly measured hydrostatic pressure gradient across the glomerular capillary was not changed. The effective filtration pressure achieved equilibrium in control animals but became significantly positive at the efferent end of the capillary at both doses of UN and increased. Total glomerular permeability (L/sub p/A) was progressively reduced from control (0.089 +- 0.005 nl/s/g kidney wt/mm Hg) at low dose UN (0.047 +- 0.013) and high dose (0.024 +- 0.003 nl/s/g kidney wt/mm Hg). Therefore UN decreases GFR by two mechanisms: (a) tubular damage leading to back-diffusion of solutes and (b) a primary reduction in sngfr due to reduced L/sub p/A

  10. Study of the extraction mechanisms by TBP saturated by uranyl nitrate; Etude des mecanismes d'extraction du TBP sature par le nitrate d'uranyle

    Energy Technology Data Exchange (ETDEWEB)

    Meze, F

    2004-02-15

    This work deals with a particular phenomenon likely to occur in the nuclear waste reprocessing process PUREX. It was shown earlier by Russian works that the extractant molecule, tributyl phosphate (TBP), saturated by uranyl nitrate keeps its extraction capacities for nitric acid and tetravalent actinides. This study is composed of three parts. Firstly, some liquid-liquid extraction experiments were conducted to verify the ability of TBP saturated by uranyl nitrate to conserve its extraction capacities for nitric acid. Then, during these experiments, the UV and infrared spectra of both phases were recorded to obtain the organic phase speciation. At last, the informations gathered during the experimental part were used to build a general species distribution model of the H{sub 2}O/HNO{sub 3}/UO{sub 2}(NO{sub 3}){sub 2}/TBP system. (author)

  11. Syntheses and crystal structures of two novel alkaline uranyl chromates A2(UO2)(CrO4)2 (A=Rb, Cs) with bidentate coordination mode of uranyl ions by chromate anions

    International Nuclear Information System (INIS)

    Siidra, Oleg I.; Nazarchuk, Evgeny V.; Krivovichev, Sergey V.

    2012-01-01

    Single crystals of Cs 2 (UO 2 )(CrO 4 ) 2 and Rb 2 (UO 2 )(CrO 4 ) 2 were prepared by solid state reactions. The structures are based upon the [(UO 2 )(CrO 4 ) 2 ] 2− chains. Within the chains, UrO 5 pentagonal bipyramids (Ur=uranyl) form Ur 2 O 8 dimers, which are linked via CrO 4 tetrahedra into one-dimensional chains. The CrO 4 tetrahedra coordinate uranyl ions in both mono- and bidentate fashion, which is unusual for uranyl chromates. The bidentate coordination has a strong influence upon geometrical parameters of both U and Cr coordination polyhedra. The conformation of the chains in 1 and 2 is different due to the different size of the Cs + and Rb + cations. - Graphical abstract: Uranyl chromate chain with monodentate and bidentate coordination mode of uranyl cations by CrO 4 tetrahedra in Cs 2 (UO 2 )(CrO 4 ) 2 . Highlights: ► Single crystals of novel uranyl chromates were prepared by solid state reactions. ► The CrO 4 tetrahedra coordinate uranyl ions in both mono- and bidentate fashion. ►The bidentate coordination has a strong influence upon geometrical parameters.

  12. The system uranyl nitrate-dietyl ether-water. Extraction by water in spray and packed columns from uranyl nitrate-either solutions

    International Nuclear Information System (INIS)

    Perez Luina, A.; Gutierrez Jodra, L.

    1960-01-01

    This paper is a continuation of the one published in Chemical Engineering Progress. Symposium Series, 50, n. 12, 127 (1954). New runs for spray columns, are given and other concentrations in uranyl nitrate for the packed columns. New correlations for the overall H.T.U. are also given. The individual H.T.U. have been grapycally calculated and show that the film resistances have similar values, being independent of the concentration of the ether phase. (Author) 24 refs

  13. Polarographic study of Cd(2), Pb(2), Hg(1) in anhydrous acetic acid; Etude polarographique de Cd(2), Pb(2), Hg(1) dans l'acide acetique anhydre

    Energy Technology Data Exchange (ETDEWEB)

    Conesa-Botta, M C [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1966-07-01

    Anhydrous acetic acid is a solvent which can be compared to water as far as its behaviour towards acid-base reactions is concerned. It is in fact, like water both a proton acceptor (basic) - and as such it can provoke the dissociation of acids - and a proton donor (acid). This amphoteric behaviour is characterized by the equilibrium: 2 H O Ac {r_reversible} Ac OH{sub 2}{sup +} + Ac O{sup -} with K{sub i} = |Ac O H{sub 2}|{sup +} |Ac O{sup -}| = 10{sup -14.5} analogue to 2 H{sub 2}O {r_reversible} H{sub 3}O{sup +} + HO{sup -} with K{sub i} = |H{sub 3}O{sup +}| |HO{sup -}| = 10{sup -14} The acid-base reactions can in principle be characterized by a pH scale based on a definition similar to that for the pH scale in aqueous solutions. The essential difference however between aqueous and acetic acid solutions is due to the fact that acetic acid has a low dielectric constant. {epsilon} = 6.1 (at 25 deg. C) The ions therefore remain associated, almost completely, in the form of ion-pairs produced as a result of the strong electrostatic interactions. This phenomenon requires us to modify the reasoning usually applied to aqueous solutions. The new general methods of reasoning have been established and discussed by G. CHARLOT and B. TREMILLON. We will make use of them for the particular case under consideration. In the first part, we have employed the polarographic method for the study of the acetic complexes of two elements: cadmium(II) and lead (II). In the second part we have tried to show that mercurous halides are formed in acetic acid; we have attempted to determine their stability. (author) [French] L'acide acetique anhydre est un solvant qui peut etre rapproche de l'eau par son comportement envers les reactions acides-bases. Il est en effet, comme l'eau, a la fois accepteur de protons (basique) - et comme tel agit sur la dissociation des acides - et donneur de protons (acide). Ce pouvoir amphotere est caracterise par l'equilibre: 2 H O Ac {r_reversible} Ac OH{sub 2

  14. Standard test method for isotopic analysis of hydrolyzed uranium hexafluoride and uranyl nitrate solutions by thermal ionization mass spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2005-01-01

    1.1 This method applies to the determination of isotopic composition in hydrolyzed nuclear grade uranium hexafluoride. It covers isotopic abundance of 235U between 0.1 and 5.0 % mass fraction, abundance of 234U between 0.0055 and 0.05 % mass fraction, and abundance of 236U between 0.0003 and 0.5 % mass fraction. This test method may be applicable to other isotopic abundance providing that corresponding standards are available. 1.2 This test method can apply to uranyl nitrate solutions. This can be achieved either by transforming the uranyl nitrate solution to a uranyl fluoride solution prior to the deposition on the filaments or directly by depositing the uranyl nitrate solution on the filaments. In the latter case, a calibration with uranyl nitrate standards must be performed. 1.3 This test method can also apply to other nuclear grade matrices (for example, uranium oxides) by providing a chemical transformation to uranyl fluoride or uranyl nitrate solution. 1.4 This standard does not purport to address al...

  15. Mechanical properties of lunar materials under anhydrous, hard vacuum conditions: applications of lunar glass structural components

    International Nuclear Information System (INIS)

    Blacic, J.D.

    1984-01-01

    Lunar materials and derivatives such as glass may possess very high tensile strengths compared to equivalent materials on earth because of the absence of hydrolytic weakening processes on the moon and in the hard vacuum of free space. Hydrolyzation of Si-O bonds at crack tips or dislocations reduces the strength of silicates by about an order of magnitude in earth environments. However, lunar materials are extremely anhydrous and hydrolytic weakening will be suppressed in free space. Thus, the geomechanical properties of the moon and engineering properties of lunar silicate materials in space environments will be very different than equivalent materials under earth conditions where the action of water cannot be conveniently avoided. Possible substitution of lunar glass for structural metals in a variety of space engineering applications enhances the economic utilization of the moon. 26 references, 3 figures, 2 tables

  16. Controlled synthesis of porous anhydrous cobalt oxalate nanorods with high reversible capacity and excellent cycling stability

    International Nuclear Information System (INIS)

    Xu, Junmin; He, Lei; Liu, Hui; Han, Tao; Wang, Yongjian; Zhang, Changjin; Zhang, Yuheng

    2015-01-01

    Graphical abstract: Display Omitted -- Abstract: One-dimensional porous anhydrous cobalt oxalate nanorods are prepared via a facile water-controlled coprecipitate method followed by thermal annealing treatment under N 2 at 300 °C. The nanorods are characterized by using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. When evaluated as an anode material for lithium ion batteries, the nanorods exhibit high reversible specific capacity and excellent cycling stability (924 mA h g −1 at 50 mA g −1 after 100 cycles and 709 mA h g −1 at 200 mA g −1 after 220 cycles). This remarkable electrochemical performance is attributed to the one-dimensional porous nanostructure that can provide large electrode/electrolyte contact area and short lithium-ion diffusion pathway, meanwhile reduce the volume expansion during the repeated discharge/charge process

  17. Detailed kinetic and heat transport model for the hydrolysis of lignocellulose by anhydrous hydrogen fluoride vapor

    Energy Technology Data Exchange (ETDEWEB)

    Rorrer, G.L.; Mohring, W.R.; Lamport, D.T.A.; Hawley, M.C.

    1988-01-01

    Anhydrous Hydrogen Fluoride (HF) vapor at ambient conditions efficiently and rapidly hydrolyzed lignocellulose to glucose and lignin. The unsteady-state reaction of HF vapor with a single lignocellulose chip was mathematically modeled under conditions where external and internal mass-transfer resistances were minimized. The model incorporated physical adsorption of HF vapor onto the lignocellulosic matrix and solvolysis of cellulose to glucosyl fluoride by adsorbed HF into the differential material and energy balance expressions. Model predictions for the temperature distribution and global glucose yield in the HF-reacting lignocellulose chip as a function of reaction time and HF vapor stream temperature agreed reasonably with the complimentary experimental data. The model correctly predicted that even when mass-transfer resistances for the reaction of HF vapor with a single lignocellulose chip are minimized, external and internal heat-transfer resistances are still significant.

  18. SIMULATION OF THE DISTILLATION BY PRESSURE REDUCTION TO OBTAIN ANHYDROUS ETHANOL

    Directory of Open Access Journals (Sweden)

    Yeney Lauzurique Guerra

    2016-10-01

    Full Text Available In this work the distillation by pressure reduction was evaluated through the HYSYS v3.2 process simulator. Due to the lack of data in the consulted bibliography to perform the simulation, the STATGRAPHICS Centurion XVI software was used to obtain a response surface that would define optimal operating conditions. The property package selected to work was based on the Margules model. An anhydrous ethanol molar composition of 0.9917 was obtained. Temperature profiles were analyzed as well as liquid and vapor molar flows and dehydration column composition profiles. The influence of operating parameters on the efficiency of simulated technology was determined by analyzing one case study. According to economic evaluation, the implementation of this technology is not economically profitable; taking into account current prices and costs mostly due to high energy consumption and construction costs of the tower. This result contributes to the pursuit of other profitable technologies from the economic point of view.

  19. Structural study and crystallography of the major compound of anhydrous cement: tri-calcium silicate; Etude structurale et cristallographie du compose majoritaire du ciment anhydre: le silicate tricalcique

    Energy Technology Data Exchange (ETDEWEB)

    Noirfontaine, M.N. de

    2000-01-01

    Anhydrous (Portland) cement is mainly composed of a synthetic material, the clinker, whose major compound is tri-calcium silicate (Ca{sub 3}SiO{sub 5}), often referred as C{sub 3}S with the compact oxides notations, C = CaO et S = SiO{sub 2}. The polymorphism of C{sub 3}S, still not well known, is the main subject of the thesis. Various crystal structures (rhombohedral R, monoclinic M1, M2, M3 and triclinic T1, T2, T3) can be found, depending on temperature and impurities. The only known structures are T1, M1 and M3, involving large unit cells with an orientational disorder of silicate tetrahedra. The single crystal studies exhibit no clear relation between the various polymorphs. Starting from known results from literature single crystal experiments, we establish the metric and structural relations between the different structures. Averaged structures for the T1, M1 and M3 polymorphs are proposed, together with all the matrices of transformation between the unit cells. We also introduce new 1-D, 2-D, and 3-D structural units, which make easier the understanding of the structures of C{sub 3}S, with the result of a better description of the orientational disorder. The effects of impurities on the structure are discussed. In industrial clinkers, impurities stabilize mainly M1 and M3 monoclinic forms. We propose a space group (Pc) and two structural models (a superstructure and an approximate averaged structure) for the M1 form. All the models are validated on synthetic compounds (M3, M2, M1 et T1) and industrial clinkers analysed by X-Ray powder diffraction with Rietveld analysis. (author)

  20. Structural basis for the transformation pathways of the sodium naproxen anhydrate-hydrate system.

    Science.gov (United States)

    Bond, Andrew D; Cornett, Claus; Larsen, Flemming H; Qu, Haiyan; Raijada, Dhara; Rantanen, Jukka

    2014-09-01

    Crystal structures are presented for two dihydrate polymorphs (DH-I and DH-II) of the non-steroidal anti-inflammatory drug sodium (S)-naproxen. The structure of DH-I is determined from twinned single crystals obtained by solution crystallization. DH-II is obtained by solid-state routes, and its structure is derived using powder X-ray diffraction, solid-state (13)C and (23)Na MAS NMR, and molecular modelling. The validity of both structures is supported by dispersion-corrected density functional theory (DFT-D) calculations. The structures of DH-I and DH-II, and in particular their relationships to the monohydrate (MH) and anhydrate (AH) structures, provide a basis to rationalize the observed transformation pathways in the sodium (S)-naproxen anhydrate-hydrate system. All structures contain Na(+)/carboxylate/H2O sections, alternating with sections containing the naproxen molecules. The structure of DH-I is essentially identical to MH in the naproxen region, containing face-to-face arrangements of the naphthalene rings, whereas the structure of DH-II is comparable to AH in the naproxen region, containing edge-to-face arrangements of the naphthalene rings. This structural similarity permits topotactic transformation between AH and DH-II, and between MH and DH-I, but requires re-organization of the naproxen molecules for transformation between any other pair of structures. The topotactic pathways dominate at room temperature or below, while the non-topotactic pathways become active at higher temperatures. Thermochemical data for the dehydration processes are rationalized in the light of this new structural information.

  1. Composite polymer electrolyte containing ionic liquid and functionalized polyhedral oligomeric silsesquioxanes for anhydrous PEM applications.

    Science.gov (United States)

    Subianto, Surya; Mistry, Mayur K; Choudhury, Namita Roy; Dutta, Naba K; Knott, Robert

    2009-06-01

    A new type of supported liquid membrane was made by combining an ionic liquid (IL) with a Nafion membrane reinforced with multifunctional polyhedral oligomeric silsesquioxanes (POSSs) using a layer-by-layer strategy for anhydrous proton-exchange membrane (PEM) application. The POSS was functionalized by direct sulfonation, and the sulfonated POSS (S-POSS) was incorporated into Nafion 117 membranes by the infiltration method. The resultant hybrid membrane shows strong ionic interaction between the Nafion matrix and the multifunctional POSS, resulting in increased glass transition temperature and thermal stability at very low loadings of S-POSS (1%). The presence of S-POSS has also improved the proton conductivity especially at low humidities, where it shows a marked increase due to its confinement in the ionic domains and promotes water uptake by capillary condensation. In order to achieve anhydrous conductivity, the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-BTSI) was incorporated into these membranes to provide proton conduction in the absence of water. Although the incorporation of an IL shows a plasticizing effect on the Nafion membrane, the S-POSS composite membrane with an IL shows a higher modulus at high temperatures compared to Nafion 117 and a Nafion-IL membrane, with significantly higher proton conductivity (5 mS/cm at 150 degrees C with 20% IL). This shows the ability of the multifunctional POSS and IL to work symbiotically to achieve the desirable proton conductivity and mechanical properties of such membranes by enhancing the ionic interaction within the material.

  2. Effects of coffee and caffeine anhydrous on strength and sprint performance.

    Science.gov (United States)

    Trexler, Eric T; Smith-Ryan, Abbie E; Roelofs, Erica J; Hirsch, Katie R; Mock, Meredith G

    2016-09-01

    Caffeine and coffee are widely used among active individuals to enhance performance. The purpose of the current study was to compare the effects of acute coffee (COF) and caffeine anhydrous (CAF) intake on strength and sprint performance. Fifty-four resistance-trained males completed strength testing, consisting of one-rep max (1RM) and repetitions to fatigue (RTF) at 80% of 1RM for leg press (LP) and bench press (BP). Participants then completed five, 10-second cycle ergometer sprints separated by one minute of rest. Peak power (PP) and total work (TW) were recorded for each sprint. At least 48 hours later, participants returned and ingested a beverage containing CAF (300 mg flat dose; yielding 3-5 mg/kg bodyweight), COF (8.9 g; 303 mg caffeine), or placebo (PLA; 3.8 g non-caloric flavouring) 30 minutes before testing. LP 1RM was improved more by COF than CAF (p = .04), but not PLA (p = .99). Significant interactions were not observed for BP 1RM, BP RTF, or LP RTF (p > .05). There were no sprint × treatment interactions for PP or TW (p > .05). 95% confidence intervals revealed a significant improvement in sprint 1 TW for CAF, but not COF or PLA. For PLA, significant reductions were observed in sprint 4 PP, sprint 2 TW, sprint 4 TW, and average TW; significant reductions were not observed with CAF or COF. Neither COF nor CAF improved strength outcomes more than PLA, while both groups attenuated sprint power reductions to a similar degree. Coffee and caffeine anhydrous may be considered suitable pre-exercise caffeine sources for high-intensity exercise.

  3. Precipitation characteristics of uranyl ions at different pHs depending on the presence of carbonate ions and hydrogen peroxide.

    Science.gov (United States)

    Kim, Kwang-Wook; Kim, Yeon-Hwa; Lee, Se-yoon; Lee, Jae-Won; Joe, Kih-Soo; Lee, Eil-Hee; Kim, Jong-Seung; Song, Kyuseok; Song, Kee-Chan

    2009-04-01

    This work studied the dissolution of uranium dioxide and precipitation characteristics of uranyl ions in alkaline and acidic solutions depending on the presence of carbonate ions and H2O2 in the solutions at different pHs controlled by adding HNO3 or NaOH in the solution. The chemical structures of the precipitates generated in different conditions were evaluated and compared by using XRD, SEM, TG-DT, and IR analyses together. The sizes and forms of the precipitates in the solutions were evaluated, as well. The uranyl ions were precipitated in the various forms, depending on the solution pH and the presences of hydrogen peroxide and carbonate ions in the solution. In a 0.5 M Na2CO3 solution with H2O2, where the uranyl ions formed mixed uranyl peroxy-carbonato complexes, the uranyl ions were precipitated as a uranium peroxide of UO4(H20)4 at pH 3-4, and precipitated as a clarkeite of Na2U2Ox(OH)y(H2O)z above pH 13. In the same carbonate solution without H2O2, where the uranyl ions formed uranyl tris-carbonato complex, the uranyl ions were observed to be precipitated as a different form of clarkeite above pH 13. The precipitate of uranyl ions in a nitrate solution without carbonate ions and H2O2 at a high pH were studied together to compare the precipitate forms in the carbonate solutions.

  4. Crystal structure of aspartame anhydrate from powder diffraction data. Structural aspects of the dehydration process of aspartame

    NARCIS (Netherlands)

    Guguta, C.; Meekes, H.L.M.; Gelder, R. de

    2006-01-01

    Aspartame has three pseudo-polymorphic forms, two hydrates and a hemi-hydrate, for which crystal structures were determined from single-crystal diffraction data. This paper presents the crystal structure of the anhydrate, which was obtained by dehydrating the hemi-hydrate. The crystal structure of

  5. 75 FR 13441 - Hours of Service; Limited 90-Day Waiver for the Distribution of Anhydrous Ammonia in Agricultural...

    Science.gov (United States)

    2010-03-22

    ..., such as grain hauled from an elevator (or sugar beets from a cold storage facility) to a processing... delivering anhydrous ammonia; (2) none of the transportation movements within the distribution chain exceed a... chain exceed a 100 air-mile radius--whether from the retail or wholesale distribution point; and (3) the...

  6. Improved quantification of alite and belite in anhydrous Portland cements by 29Si MAS NMR: Effects of paramagnetic ions

    DEFF Research Database (Denmark)

    Poulsen, Søren Lundsted; Kocaba, Vanessa; Le Saoût, Gwenn

    2009-01-01

    The applicability, reliability, and repeatability of 29Si MAS NMR for determination of the quantities of alite (Ca3SiO5) and belite (Ca2SiO4) in anhydrous Portland cement was investigated in detail for 11 commercial Portland cements and the results compared with phase quantifications based...

  7. Anhydrous ZnCl2: A Highly Efficient Reagent for Facile and Regioselective Conversion of Epoxides to β-Chlorohydrins

    Directory of Open Access Journals (Sweden)

    Ronak Eisavi

    2016-01-01

    Full Text Available Facile conversion of structurally different epoxides to the corresponding β-chlorohydrins was carried out successfully with anhydrous ZnCl2 in CH3CN. The reactions were carried out within 10-50 min to give β-chlorohydrins with perfect regioselectivity and high yields (80-97%.

  8. Application of the NICADonnan model for proton, copper and uranyl binding to humic acid

    NARCIS (Netherlands)

    Saito, T.; Nagasaki, S.; Tanaka, S.; Koopal, L.K.

    2004-01-01

    Humic acids are natural organic materials that play an important role in the migration of heavy metal and actinide ions in aquatic and soil systems. In the present study, the binding of protons, copper ions and uranyl ions to the purified Aldrich humic acid (PAHA) is investigated and the results are

  9. Vibrational spectra of monouranates and uranium hydroxides as reaction products of alkali with uranyl nitrate

    International Nuclear Information System (INIS)

    Komyak, A.I.; Umrejko, D.S.; Posledovich, M.R.

    2013-01-01

    Vibrational (IR absorption and Raman scattering) spectra for the reaction products of uranyl nitrate hexahydrate with NaOH and KOH have been studied. As a result of exchange reactions, the uranyl-ion coordinated nitrate groups are completely replaced by hydroxyl ions and various uranium and uranyl oxides or hydrates are formed. An analysis of the vibrations has been performed in terms of the frequencies of a free or coordinated nitrate group; comparison with the vibrations of the well-known uranium oxides and of the uranyl group UO 2 2+ has been carried out. Vibrational spectra of a free nitrate group are characterized by four vibrational frequencies 1050, 724, 850, and 1380 cm -1 , among which the frequencies at 724 and 1380 cm -1 are doubly degenerate and attributed to E’ symmetry of the point group D 3h . When this group is uranium coordinated, its symmetry level is lowered to C 2v , all vibrations of this group being active both in Raman and IR spectra. The doubly degenerate vibrations are exhibited as two bands and a frequency of the out-of-plane vibration is lowered to 815 cm -1 . (authors)

  10. Identification of Uranyl Surface Complexes an Ferrihydrite: Advanced EXAFS Data Analysis and CD-MUSIC Modeling

    NARCIS (Netherlands)

    Rossberg, A.; Ulrich, K.U.; Weiss, S.; Tsushima, S.; Hiemstra, T.; Scheinost, A.C.

    2009-01-01

    Previous spectroscopic research suggested that uranium(VI) adsorption to iron oxides is dominated by ternary uranyl-carbonato surface complexes across an unexpectedly wide pH range. Formation of such complexes would have a significant impact on the sorption behavior and mobility of uranium in

  11. Modeling of critical experiments employing Raschig rings in uranyl nitrate solution

    International Nuclear Information System (INIS)

    Tanner, J.E.

    1989-01-01

    Four critical experiments employing borated glass rings in concentrated uranyl nitrate solution yielded k eff higher by 0. 04 when modeled with a flux-weighted, homogenized cross section set than when modeled with discrete rings. k eff varied by 0.014 for a 10% boron uncertainty and by up to 0.04 for a 10% packing fraction uncertainty

  12. Study of the mechanism and kinetics of the reduction of uranyl ions in phosphoric acid solutions

    International Nuclear Information System (INIS)

    El Kacemi, K.; Tyburce, B.; Belcadi, S.

    1982-01-01

    The electrochemical reduction of uranyl ions in 0.1 to 9 M phosphoric acid has been investigated by polarography, cyclic voltammetry, chronopotentiometry and potentiostatic coulometry. In concentrated phosphoric acid solutions (H 3 PO 4 3 PO 4 concentrations. So, when the concentration of U(VI) increases and/or that of H 3 PO 4 reduces, the system becomes reversible. (author)

  13. Recuperation of uranyl ions from effluents by means of microbiological collectors

    International Nuclear Information System (INIS)

    Cecal, A.; Palamaru, I.; Humelnicu, D.; Goanta, M.; Rudic, V.; Salaru, V.V.; Gulea, A.

    1997-01-01

    This paper deals with the study of bioaccumulation of uranyl ions (UO 2 2+ ) from industrial effluents, using microbiological collectors: Nostoc linkia sp., Tolipotrix sp., Spirulina sp., Porphyridium cruentum and also the glucide extract of P. cruentum. The values of retaining degree of UO 2 2+ on the biomass, for several experimental conditions, were established between 14.22 and 91.99%

  14. Surface analysis of uranyl fluoride layers with a glow discharge lamp

    International Nuclear Information System (INIS)

    Nel, J.T.; Stander, C.M.; Boehmer, R.G.

    1991-01-01

    Surface analysis with a Grimm-type glow discharge lamp was used to analyse uranyl fluoride layers that had formed on a nickel substrate after exposure to UF 6 . Narrow-band optical filters were used to isolate the intensities of three fluorine emission lines. An in-depth profile of layer composition was obtained. (author)

  15. Method of separation of uranium from contaminating ions in an aqueous feed liquid containing uranyl ions

    International Nuclear Information System (INIS)

    Sundar, P.S.; Elikan, L.; Lyon, W.L.

    1975-01-01

    A coupled cationic/anionic method for the separation of uranium from contaminated aqueous solutions which contain uranyl ions is proposed. The fluid is extracted using an organic solvent containing a reagent which, together with the uranyl ions, forms a soluble aggregate in that solvent. As an example, 0.1 - 1 Mol/l Di-2-ethyl-hexyl-phosphorous acid in kerosene is mentioned. The organic solvent is then treated with a sealing liquid (volume ratio 20 - 35). For separation, an aqueous carbonate solution or a sulfuric acid solution can be used; the most favorable pH-values and concentrations for both cases are mentioned. The U +4 -ion at the sulfuric acid separation is subsequently oxidized to the uranyl ion with air. In each case, an extraction with an amine follows; after that, the amine is separated using an ammonium-carbonate solution and the uranium aggregate is precipitated, for example as ammonium uranyl tricarbonate, and then further processed to uranium oxide. The solvents and fluids used are led back in closed circuit; a flow diagram is given. (UWI) [de

  16. Kinetic investigation of uranyl-uranophile complexation. 1. Macrocyclic kinetic effect and macrocyclic protection effect

    International Nuclear Information System (INIS)

    Tabushi, I.; Yoshizawa, A.

    1986-01-01

    Equilibria and rates of ligand-exchange reactions between uranyl tricarbonate and dithiocarbamates and between uranyl tris-(dithiocarbamates) and carbonate were studied under a variety of conditions. The dithiocarbamates used were acyclic diethyl-dithiocarbamate and macrocyclic tris(dithiocarbamate). The acyclic ligand showed a triphasic (successive three-step) equilibrium with three different equilibrium constants while the macrocyclic ligand showed a clear monophasic (one-step) equilibrium with a much larger stability constant for the dithiocarbamate-uranyl complex. The macrocyclic ligand showed the S/sub N/2-type ligand-exchange rate in the forward as well as reverse process, while the first step of the acyclic ligand-exchange reaction proceeded via the S/sub N/1-type mechanism. This kinetic macrocyclic effect on molecularity is interpreted as the result of a unique topological requirement of uranyl complexation. The macrocyclic ligand also exhibited a clear protection effect, leading to the large stability constant. 19 references, 10 figures, 2 tables

  17. Cyclic phosphopeptides to rationalize the role of phosphoamino acids in uranyl binding to biological targets

    Energy Technology Data Exchange (ETDEWEB)

    Starck, Matthieu; Laporte, Fanny A.; Oros, Stephane; Sisommay, Nathalie; Gathu, Vicky; Lebrun, Colette; Delangle, Pascale [INAC/SyMMES, UMR5819, Universite Grenoble Alpes, CEA, CNRS, Grenoble (France); Solari, Pier Lorenzo [Synchrotron SOLEIL, L' orme des Merisiers, Saint-Aubin, Gif-sur-Yvette (France); Creff, Gaelle; Den Auwer, Christophe [Institut de Chimie de Nice, UMR7272, Universite Cote d' Azur, Nice (France); Roques, Jerome [Institut de Physique Nucleaire d' Orsay, CNRS-IN2P3, Univ. Paris-Sud, Universite Paris-Saclay (France)

    2017-04-19

    The specific molecular interactions responsible for uranium toxicity are not yet understood. The uranyl binding sites in high-affinity target proteins have not been identified yet and the involvement of phosphoamino acids is still an important question. Short cyclic peptide sequences, with three glutamic acids and one phosphoamino acid, are used as simple models to mimic metal binding sites in phosphoproteins and to help understand the mechanisms involved in uranium toxicity. A combination of peptide design and synthesis, analytical chemistry, extended X-ray absorption fine structure (EXAFS) spectroscopy, and DFT calculations demonstrates the involvement of the phosphate group in the uranyl coordination sphere together with the three carboxylates of the glutamate moieties. The affinity constants measured with a reliable analytical competitive approach at physiological pH are significantly enhanced owing to the presence of the phosphorous moiety. These findings corroborate the importance of phosphoamino acids in uranyl binding in proteins and the relevance of considering phosphoproteins as potential uranyl targets in vivo. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Nuclear fuel technology - Determination of uranium in uranyl nitrate solutions of nuclear grade quality - Gravimetric method

    International Nuclear Information System (INIS)

    2003-01-01

    This International Standard specifies a precise and accurate gravimetric method for determining the mass fraction of uranium in uranyl nitrate solutions of nuclear grade quality containing more than 100 g/kg of uranium. Non-volatile impurities influence the accuracy of the method

  19. Potential New Ligand Systems for Binding Uranyl Ions in Seawater Environments

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2014-12-13

    Work began this quarter on a new project involving a combined computational and biosynthetic approach to selective recognition of uranyl ion in aqueous solution. This project exploits the results of computational studies to discover new ligand classes. Synthetic studies will follow to generate target systems for uranyl binding and determination of binding constants. The process will be iterative, with results from computation informing synthesis, and vice versa. The theme of the ligand classes to be examined initially will be biologically based. New phosphonate-containing α-amino acid N-carboxyanhydride (NCA) monomers were used recently to prepare well-defined phosphonate-containing poly-peptides and block copolypeptides. Our first approach is to utilize these phosphate- and phosphonate-containing NCAs for the coordination of uranyl. The work includes the laboratory-scale preparation of a series of NCAs and the full thermodynamic and spectroscopic characterization of the resulting uranyl complexes. We are also evaluating the sequestering activity in different physiological and environmental conditions of these copolymers as well as their biodegradability.

  20. Synthesis, structural investigation and kinetic studies of uranyl(VI) unsymmetrical Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Asadi, M.; Zeinali, A.; Ranjkeshshorkaei, M.; Fejfarová, Karla; Eigner, Václav; Dušek, Michal; Dehnokhalaji, A.

    2014-01-01

    Roč. 126, č. 6 (2014), s. 1673-1683 ISSN 0974-3626 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl schiff base complexes * kinetic study * kinetics of thermal decomposition * X-ray crystallography * cyclic voltammetry Subject RIV: CA - Inorganic Chemistry Impact factor: 1.191, year: 2014

  1. Kinetics of thermal decomposition and kinetics of substitution reaction of nano uranyl Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Zeinali, A.; Dušek, Michal; Eigner, Václav

    2014-01-01

    Roč. 46, č. 12 (2014), s. 718-729 ISSN 0538-8066 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl * Schiff base * kinetics * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.517, year: 2014

  2. Uranyl Photocleavage of Phosphopeptides Yields Truncated C-Terminally Amidated Peptide Products

    DEFF Research Database (Denmark)

    Elnegaard, Rasmus L B; Møllegaard, Niels Erik; Zhang, Qiang

    2017-01-01

    photocleavage reaction of a tetraphosphorylated β-casein model peptide. We show that the primary photocleavage products of the uranyl-catalysed reaction are C-terminally amidated. This could be of great interest to the pharmaceutical industry, as efficient peptide amidation reactions are one of the top...

  3. Criticality parameters for uranyl nitrate or plutonium nitrate systems in tributyl phosphate/kerosine and water

    International Nuclear Information System (INIS)

    Weber, W.

    1985-01-01

    This report presents the calculated values of smallest critical masses and volumina and neutron physical parameters for uranyl nitrate (3, 4, 5% U-235) or plutonium nitrate (5% Pu-240), each in a 30 per cent solution of tributyl phosphate (TBP)/kerosine. For the corresponding nitrate-water solutions, newly calculated results are presented together with a revised solution density model. A comparison of the data shows to what extent the criticality of nitrate-TBP/kerosine systems can be assessed on the basis of nitrate-water parameters, revealing that such data can be applied to uranyl nitrate/water systems, taking into account that the smallest critical mass of uranyl nitrate-TBP/kerosine systems, up to a 5 p.c. U-235 enrichment, is by 4.5 p.c. at the most smaller than that of UNH-water solutions. Plutonium nitrate (5% Pu-240) in the TBP/kerosine solution will have a smallest critical mass of up to 7 p.c. smaller, as compared with the water data. The suitability of the computing methods and cross-sections used is verified by recalculating experiments carried out to determine the lowest critical enrichment of uranyl nitrate. The calculated results are well in agreement with experimental data. The lowest critical enrichment is calculated to be 2.10 p.c. in the isotope U-235. (orig.) [de

  4. Re-evaluating neptunium in uranyl phases derived from corroded spent fuel

    International Nuclear Information System (INIS)

    Fortner, J. A.; Finch, R. J.; Kropf, A. J.; Cunnane, J. C.; Chemical Engineering

    2004-01-01

    Interest in mechanisms that may control radioelement release from corroded commercial spent nuclear fuel (CSNF) has been heightened by the selection of the Yucca Mountain site in Nevada as the repository for high-level nuclear waste in the United States. Neptunium is an important radionuclide in repository models owing to its relatively long half-life and its high aqueous mobility as neptunyl [Np(V)O+2]. The possibility of neptunium sequestration into uranyl alteration phases produced by corroding CSNF would suggest-a process for lowering neptunium concentration and subsequent migration from a geologic repository. However, there remains little experimental evidence that uranyl compounds will, in fact, serve as long-term host phases for the retention of neptunium under conditions expected in a deep geologic repository. To directly explore this possibility, we examined specimens of uranyl alteration phases derived from humid-air-corroded CSNF by X-ray absorption spectroscopy to better determine neptunium uptake in these phases. Although neptunium fluorescence was readily observed from as-received CSNF, it was not observed from the uranyl alteration rind. We establish upper limits for neptunium incorporation into CSNF alteration phases that are significantly below previously reported concentrations obtained by using electron energy loss spectroscopy (EELS). We attribute the discrepancy to a plural-scattering event that creates a spurious EELS peak at the neptunium-MV energy

  5. Inhibition Mechanism of Uranyl Reduction Induced by Calcium-Carbonato Complexes

    Science.gov (United States)

    Jones, M. E.; Bargar, J.; Fendorf, S. E.

    2015-12-01

    Uranium mobility in the subsurface is controlled by the redox state and chemical speciation, generally as minimally soluble U(IV) or soluble U(VI) species. In the presence of even low carbonate concentrations the uranyl-carbonato complex quickly becomes the dominant aqueous species; they are, in fact, the primary aqueous species in most groundwaters. Calcium in groundwater leads to ternary calcium-uranyl-carbonato complexes that limit the rate and extent of U(VI) reduction. This decrease in reduction rate has been attributed to surface processes, thermodynamic limitations, and kinetic factors. Here we present a new mechanism for the inhibition of ferrous iron reduction of uranyl-carbonato species in the presence of calcium. A series of experiments under variable Ca conditions were preformed to determine the role of Ca in the inhibition of U reduction by ferrous iron. Calcium ions in the Ca2UO2(CO3)3 complex sterically prevent the interaction of Fe(II) with U(VI), in turn preventing the Fe(II)-U(VI) distance required for electron transfer. The mechanism described here helps to predict U redox transformations in suboxic environments and clarifies the role of Ca in the fate and mobility of U. Electrochemical measurements further show the decrease of the U(VI) to U(V) redox potential of the uranyl-carbonato complex with decreasing pH suggesting the first electron transfer is critical determining the rate and extent of uranium reduction.

  6. Model investigations for trace analysis of iodine, uranium, and technetium in saturated sodium chloride leaching solutions of stored radioactive waste

    International Nuclear Information System (INIS)

    Jegle, U.

    1989-02-01

    This paper describes the development of a time and cost saving chromatographic technique, which allows the matrix to be separated and the most important species to be analyzed in a leaching solution of vitrified radioactive waste. Uranium, iodine, and technetium were chosen for the model technique to be elaborated. In a first step, iodide and pertechnetate were separated from the matrix by the strongly basic AG 1X 8 anion exchange resin and then separated from each other by selective elution. The uranyl ions eluted with the sodium chloride matrix were separated from the excess of sodium chloride in a second step, again by adsorption to the strongly basic resin. The ion-selective electrode was found to be a suitable tool for iodide analysis. Pertechnetate was analysed by means of liquid scintillation. Uranium was determined by ICP-AES. (orig./RB) [de

  7. Observation of Radiolytic Field Alteration of the Uranyl Cation in Bicarbonate Solution

    Energy Technology Data Exchange (ETDEWEB)

    Snow, Lanee A.; McNamara, Bruce K.; Sinkov, Sergey I.; Cho, Herman M.; Friese, Judah I.

    2006-12-01

    In previous work we demonstrated that radiolysis of uranyl tris carbonate in near neutral pH to alkaline carbonate solutions, could be followed by 13C NMR. Radiolysis of the complex produced novel uranyl peroxo carbonate solution state species, whose structures depended on the pH and radiolytic dose rate. In this work, we investigate speciation of the uranyl carbonate trimer which is predominant in bicarbonate solution near pH 5.9. We observe radiolytically derived speciation to different mixed peroxy carbonate species than seen in the higher pH solutions. Auto radiolysis of uranium (VI) carbonate solutions between pH 5.9 and 7.2 is shown to alter the uranium speciation over relatively short periods of time and was followed by 13C NMR and visible spectrophotometry, using dissolved 233(UO2)3(CO3)6 6- both as the radiolysis source (D= 14.9 Gy/hr) and as a trap for the newly formed hydrogen peroxide. Direct addition of hydrogen peroxide to solutions of the uranyl-carbonate trimer is shown to reproduce the 13 C NMR signatures of the complexe(s) formed by radiolysis, but additionally a variety of new complexes are revealed. Ratios of H2O2/trimer < 1.5 produced a uranyl peroxo carbonate adduct, that is shown to be common to the radiolytically produced species. Ratios of H2O2/ trimer >1 resulted in formation of stable higher order peroxo carbonate complexes. The 13C NMR signatures and visible spectra of these complexes are described here. Rigorous characterization of the species is an ongoing effort.

  8. Corrosion evaluation of uranyl nitrate solution evaporator and denitrator in Tokai reprocessing plant

    International Nuclear Information System (INIS)

    Yamanaka, Atsushi; Hashimoto, Kowa; Uchida, Toyomi; Shirato, Yoji; Isozaki, Toshihiko; Nakamura, Yoshinobu

    2011-01-01

    The Tokai reprocessing plant (TRP) adopted the PUREX method in 1977 and has reprocessed spent nuclear fuel of 1140 tHM (tons of heavy metals) since then. The reprocessing equipment suffers from various corrosion phenomena because of high nitric acidity, solution ion concentrations, such as uranium, plutonium, and fission products, and temperature. Therefore, considering corrosion performance in such a severe environment, stainless steels, titanium steel, and so forth were employed as corrosion resistant materials. The severity of the corrosive environment depends on the nitric acid concentration and the temperature of the solution, and uranium in the solution reportedly does not significantly affect the corrosion of stainless steels and controls the corrosion rates of titanium steel. The TRP equipment that handles uranyl nitrate solution operates at a low nitric acid concentration and has not experienced corrosion problems until now. However, there is a report that corrosion rates of some stainless steels increase in proportion to rising uranium concentrations. The equipment that handles the uranyl nitrate solution in the TRP includes the evaporators, which concentrate uranyl nitrate to a maximum concentration of about 1000 gU/L (grams of uranium per liter), and the denitrator, where uranyl nitrate is converted to UO 3 powder at about 320degC. These equipments are therefore required to grasp the degree of the progress of corrosion to handle high-temperature and high-concentration uranyl nitrate. The evaluation of this equipment on the basis of thickness measurement confirmed only minor corrosion and indicated that the equipment would be fully adequate for future operation. (author)

  9. Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

    Science.gov (United States)

    Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.; Fendorf, Scott; Kumar, Naresh; Lowry, Gregory V.; Brown, Gordon E.

    2017-10-01

    As part of a larger study of the reactivity and mobility of uranyl (U(VI)O22+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0-835 ppm) or Suwanee River Fulvic Acid (SRFA) (0-955 ppm). No evidence was found for reduction of uranyl by either form of NOM after 24 h of exposure. The following three size fractions were considered in this study: (1) ≥0.2 μm (Fh-NOM aggregates), (2) 0.02-0.2 μm (dispersed Fh nanoparticles and NOM macro-molecules), and (3) <0.02 μm (dissolved). The extent to which U(VI) is sorbed in aggregates or dispersed as colloids was assessed by comparing U, Fe, and NOM concentrations in these three size fractions. Partitioning of uranyl between Fh and NOM was determined in size fraction (1) using X-ray absorption spectroscopy (XAS). Uranyl sorption on Fh-NOM aggregates was affected by the presence of NOM in different ways depending on pH and type of NOM (ESHA vs. SRFA). The presence of ESHA in the uranyl-Fh-NOM ternary system at pH 4.6 enhanced uranyl uptake more than the presence of SRFA. In contrast, neither form of NOM affected uranyl sorption at pH 7.0 over most of the NOM concentration range examined (0-500 ppm); at the highest NOM concentrations (500-955 ppm) uranyl uptake in the aggregates was slightly inhibited at pH 7.0, which is interpreted as being due to the dispersion of Fh aggregates. XAS at the U LIII-edge was used to characterize molecular-level changes in uranyl complexation as a result of sorption to the Fh-NOM aggregates. In the absence of NOM, uranyl formed dominantly inner-sphere, mononuclear, bidentate sorption complexes on Fh. However, when NOM concentration was increased at pH 4.6, the

  10. Chloride Transport in Heterogeneous Formation

    Science.gov (United States)

    Mukherjee, A.; Holt, R. M.

    2017-12-01

    The chloride mass balance (CMB) is a commonly-used method for estimating groundwater recharge. Observations of the vertical distribution of pore-water chloride are related to the groundwater infiltration rates (i.e. recharge rates). In CMB method, the chloride distribution is attributed mainly to the assumption of one dimensional piston flow. In many places, however, the vertical distribution of chloride will be influenced by heterogeneity, leading to horizontal movement of infiltrating waters. The impact of heterogeneity will be particularly important when recharge is locally focused. When recharge is focused in an area, horizontal movement of chloride-bearing waters, coupled with upward movement driven by evapotranspiration, may lead to chloride bulges that could be misinterpreted if the CMB method is used to estimate recharge. We numerically simulate chloride transport and evaluate the validity of the CMB method in highly heterogeneous systems. This simulation is conducted for the unsaturated zone of Ogallala, Antlers, and Gatuna (OAG) formations in Andrews County, Texas. A two dimensional finite element model will show the movement of chloride through heterogeneous systems. We expect to see chloride bulges not only close to the surface but also at depths characterized by horizontal or upward movement. A comparative study of focused recharge estimates in this study with available recharge data will be presented.

  11. The gas-phase bis-uranyl nitrate complex ((UO2)2(NO3)5)-: infrared spectrum and structure

    International Nuclear Information System (INIS)

    Groenewold, G.S.; van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; McIlwain, Michael E.

    2011-01-01

    The infrared spectrum of the bis-uranyl nitrate complex ((UO 2 ) 2 (NO 3 ) 5 ) - was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate v 3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex ((UO 2 ) 2 (NO 3 ) 5 ) - compared to the mono-complex (UO 2 (NO 3 ) 3 ) - , as indicated by a higher O-U-O asymmetric stretching (v 3 ) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the v 3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The lowest energy structure predicted by density functional theory (B3LYP functional) calculations was one in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

  12. The gas-phase bis-uranyl nitrate complex ((UO2)2(NO3)5)-: infrared spectrum and structure

    International Nuclear Information System (INIS)

    Groenewold, Gary S.; van Stipdonk, Michael J.; Oomens, Jos; de Jong, Wibe; McIlwain, Michael E.

    2011-01-01

    The infrared spectrum of the bis-uranyl nitrate complex ((UO 2 ) 2 (NO 3 ) 5 ) - was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate nu3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex ((UO 2 ) 2 (NO 3 ) 5 ) - compared to the mono-complex (UO 2 (NO 3 ) 3 ) - , as indicated by a higher O-U-O asymmetric stretching (nu3) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the ν 3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The structure was calculated using density functional theory (B3LYP functional), which produced a structure in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

  13. The Role of Hydrogen Bonding on Laminar Burning Velocity of Hydrous and Anhydrous Ethanol Fuel with Small Addition of n-Heptane

    Directory of Open Access Journals (Sweden)

    I Made Suarta

    2016-01-01

    Full Text Available The molecular structure of mixed hydrous and anhydrous ethanol with up to 10% v n-heptane had been studied. The burning velocity was examined in a cylindrical explosion combustion chamber. The result showed that the burning velocity of hydrous ethanol is higher than anhydrous ethanol and n-heptane at stoichiometric, rich, and very rich mixtures. The burning velocity of hydrous ethanol with n-heptane drops drastically compared to the burning velocity of anhydrous ethanol with n-heptane. It is caused by two reasons. Firstly, there was a composition change of azeotropic hydrous ethanol molecules within the mixture of fuel. Secondly, at the same volume the number of ethanol molecules in hydrous ethanol was less than in anhydrous ethanol at the same composition of the n-heptane in the mixture. At the mixture of anhydrous ethanol with n-heptane, the burning velocity decreases proportionally to the addition of the n-heptane composition. The burning velocity is between the velocities of anhydrous ethanol and n-heptane. It shows that the burning velocity of anhydrous ethanol mixed with n-heptane is only influenced by the mixture composition.

  14. Formation of the second organic phase during uranyl nitrate extraction from aqueous solution by 30% tributylphosphate solution in paraffin

    International Nuclear Information System (INIS)

    Yhrkin, V.G.

    1996-01-01

    For extraction systems aqueous solution of uranyl nitrate-30% solution of tributylphosphate in individual paraffins from C 13 to C 17 the influence of the second organic phase of uranyl nitrate concentration in aqueous and organic phases, the length of hydrocarbon chain of paraffin hydrocarbon and temperature from 25 to 50 deg C on formation conditions has been defected. A special method of achieving the conditions of organic phase stratification from three-phase region, involving definition of equilibrium phases composition by density and refractive index, has been elaborated for more precise definition of organic phase homogeneity region. It has been revealed that without addition of nitric acid to uranyl nitrate solution the organic phase homogeneity limits can be achieved solely on paraffins C 15 , C 16 and C 17 and only under conditions similar to equeous phase saturation in terms of uranyl nitrate. 16 refs., 2 figs

  15. A microscopic study of the action of uranyl acetate on the erythrocyte at varying molarity and toxicity

    International Nuclear Information System (INIS)

    Wyatt, J.H.

    1977-03-01

    Phase contrast and dark field microphotographs were made to record variation of the shape and size changes seen when human erythrocytes are exposed in a number of ways to uranyl acetate in vitro. The degree of hemolysis produced by varying the toxicity of the uranyl acetate solutions was measured, and the results are discussed with particular reference to the possible influence of pH. (author)

  16. Valyl benzyl ester chloride

    Directory of Open Access Journals (Sweden)

    Grzegorz Dutkiewicz

    2010-02-01

    Full Text Available In the title compound (systematic name: 1-benzyloxy-3-methyl-1-oxobutan-2-aminium chloride, C12H18NO2+·Cl−, the ester group is approximately planar, with a maximum deviation of 0.040 (2 Å from the least-squares plane, and makes a dihedral angle of 28.92 (16° with the phenyl ring. The crystal structure is organized by N—H...Cl hydrogen bonds which join the two components into a chain along the b axis. Pairs of chains arranged antiparallel are interconnected by further N—H...Cl hydrogen bonds, forming eight-membered rings. Similar packing modes have been observed in a number of amino acid ester halides with a short unit-cell parameter of ca 5.5 Å along the direction in which the chains run.

  17. Chloride on the Move

    KAUST Repository

    Li, Bo

    2017-01-09

    Chloride (Cl−) is an essential plant nutrient but under saline conditions it can accumulate to toxic levels in leaves; limiting this accumulation improves the salt tolerance of some crops. The rate-limiting step for this process – the transfer of Cl− from root symplast to xylem apoplast, which can antagonize delivery of the macronutrient nitrate (NO3−) to shoots – is regulated by abscisic acid (ABA) and is multigenic. Until recently the molecular mechanisms underpinning this salt-tolerance trait were poorly defined. We discuss here how recent advances highlight the role of newly identified transport proteins, some that directly transfer Cl− into the xylem, and others that act on endomembranes in ‘gatekeeper’ cell types in the root stele to control root-to-shoot delivery of Cl−.

  18. Influence of Fe content on the creep properties of olivine under anhydrous and hydrous conditions

    Science.gov (United States)

    Trimmer, M. B.; Zhao, Y.; Zimmerman, M. E.; Kohlstedt, D. L.

    2007-12-01

    High-temperature, high-pressure compressive creep experiments were performed on both wet and dry aggregates of Fa75 in a gas-medium deformation apparatus. The results from these experiments are compared with those for San Carlos olivine, Fa10, and our previous results on Fa30 and Fa50 in order to provide a basis for comparing convection models for the mantle of Earth with those for the more iron-rich mantle of Mars. Samples were fabricated from powders of Fa75 that were synthesized from mixtures of Fe2O3 and SiO2 combined with San Carlos olivine. The Fa75 powders were cold-pressed into Fe capsules and then hot-pressed at 300 MPa, 1473 K for 3 h. The average grain size of the resultant hot-pressed samples was ~40 μm. For experiments under hydrous conditions, three drops of deionized water were added before sealing the sample within telescoping Fe cans for deformation. Water bubbles were present both within olivine grains and along grain boundaries, demonstrating that the samples were water-saturated. Triaxial compressive creep experiments were carried out in a servo-controlled, internally heated gas-medium apparatus at 50 K intervals between 1273 and 1423 K and a confining pressure of 300 MPa with differential stress of 10 to 300 MPa. For each sample, creep tests were performed at several differential stresses at a constant temperature to determine the stress exponent or at several temperatures to determine the activation energy for creep. Under anhydrous conditions the viscosity of samples of Fa75 is more than a factor of 10 lower than the viscosity of Fa50. Previous experiments showed a similar relationship between Fa50 and Fa30 and Fa30 and Fa10. Under hydrous conditions the viscosity of samples of Fa75 are about a factor of 5 lower than the viscosity of Fa50, which is less than that observed between Fa50 and Fa30 or Fa30 and Fa10. The viscosity of a sample of a specific Fe:Mg ratio deformed under hydrous conditions is a factor of 10 lower than its counterpart

  19. Kinetic studies of uranyl ion adsorption on acrylonitrile (AN)/polyethylene glycol (PEG) interpenetrating networks (IPN)

    International Nuclear Information System (INIS)

    Aycik, G.A.; Gurellier, R.

    2004-01-01

    Full text: The kinetics of the adsorption of uranyl ions on amidoximated acrylonitrile (AN)/ polyethylene glycol (PEG) interpenetrating network (IPNs) from aqueous solutions was studied as a function of time and temperature. The IPNs were prepared by irradiation initiated gamma polymerisation using Co-60 gamma source. Adsorption capacities were performed for definite uranyl ion concentrations of 1x10 -2 M and at four different temperatures as 290K, 298K, 308K and 318K by gamma spectrometer. Adsorption time was increased from zero to 48 hours. The results indicate that adsorption capacity increases linearly with increasing temperature. Temperature and agitation hardly influence equilibrium and kinetics and decreasing of temperature results in a slightly greater time to reach equilibrium. The adsorption of uranyl ions has been studied in a multi step mechanism processes thus comparing chemical sorption and diffusion sorption processes. The experimental data was analysed using various kinetic models to determine the best-fit equation for the adsorption mechanisms. However, it was shown that all models, in general according to the reaction time and uranyl ion concentration in the solution, could describe the adsorption of uranyl ion onto amidoximated IPN, the adsorption kinetics was best described by zeroth order and intraparticle diffusion model whereas that of in increasing time by pseudo first and pseudo second order response respectively. External-intraparticle diffusion and zeroth order process in the IPN structure is proposed as a mass transfer mechanism and the results indicate a diffusion-controlled process. The Mean Activation Energy Of Uranyl Ions Adsorption Was Found As 4,1 Kj/Mole By Using Arrhenius Equation. The Rate Constant, The Equilibrium Adsorption Capacity And The Initial Adsorption Rate Were Calculated For All Models At Each Temperature. Kinetic Parameters Of All Models And The Normalized Standard Deviations Between The Measured And Predicted

  20. Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

    International Nuclear Information System (INIS)

    Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella

    2016-01-01

    Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U V species into the stable mixed-valent star-shaped U VI /U V oxo cluster [U(UO 2 ) 5 (μ 3 -O) 5 (PhCOO) 5 (Py) 7 ]. This cluster is only the second example of a U VI /U V cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U V center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U 12 IV U 4 V O 24 cluster {[K(Py) 2 ] 2 [K(Py)] 2 [U 16 O 24 (PhCOO) 24 (Py) 2 ]}.

  1. Reactive transport of uranyl: fixation mode on silica and goethite; experiments in columns and closed reactors; simulations

    International Nuclear Information System (INIS)

    Gabriel, U.

    1998-01-01

    Uranium contaminated areas are found in mine waste disposal sites, former military areas, etc. The present study focuses on the identification or mechanisms which may lead contaminated soils to become a sudden potential threat to surface and ground waters. Mechanisms were studied on model material at two levels. On the molecular scale, the complexation of uranyl at trace metal concentrations was investigated with amorphous silica. Complexation is shown to occur via the formation of surface complexes, characterised by different time-resolved laser-induced luminescence spectra and life times and stoichiometry. On the macro-scale the transport behaviour of uranyl in a cristobalite-goethite-carbonate-uranyl system was investigated with laboratory column and batch experiments. Uranium mobility was found to be controlled by the interaction between physical transport and a reversible, rate-controlled, fixation reaction. Sorption was shown to be an ensemble of competing solution and surface complexation reactions, leading to an apparent non-linear (Langmuir-like) adsorption isotherm. Finally the impact of a sudden change in background geochemistry was studied. Conditions leading to a dramatic mobilization of uranium from mildly contaminated systems were experimentally identified. Maximal uranyl concentration are controlled by the total extractable uranyl in the system and limited by uranyl solubility. Evolution of the background geochemical conditions is thus an important part of contaminated sites risk assessment. (author)

  2. Production of U3O8 by uranyl formate precipitation and calcination in a full-scale pilot facility

    International Nuclear Information System (INIS)

    Kendrick, L.S.; Wilson, W.A.; Mosley, W.C.

    1984-08-01

    The uranyl formate process for the production of U 3 O 8 with a controlled particle size has been extensively studied on a laboratory scale. Based on this study, a pilot-scale facility (the Uranyl Formate Facility) was built to investigate the key steps of the process on a larger scale. These steps were the precipitation of a uranyl formate monohydrate salt and the calcination of this salt to U 3 O 8 . Tests of the facility and process were conducted at conditions recommended by the laboratory-scale studies for a full-scale production facility. These tests demonstrated that U 3 O 8 of the required particle size for the PM process can be produced on a plant scale by the calcination of uranyl formate crystals. The performance of the U 3 O 8 produced by the uranyl formate process in fuel tube fabrication was also investigated. Small-scale extrusion tests of U 3 O 8 -Al cores which used the U 3 O 8 produced in the Uranyl Formate Facility were conducted. These tests demonstrated that the U 3 O 8 quality was satisfactory for the PM process

  3. Determination of the stability of the uranyl ion sipped in τ-hydrogen phosphate of zirconium in sodic form

    International Nuclear Information System (INIS)

    Ordonez R, E.; Fernandez V, S.M.; Drot, R.; Simoni, E.

    2005-01-01

    The stability of the uranyl sipped in the zirconium τ-hydrogen phosphate in sodic form (τ-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10 -4 and 10 -5 of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO 4 . The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the τ-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

  4. Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella [Ecole Polytechnique Federale de Lausanne (EPFL) (Switzerland). Inst. de Sciences et Ingenierie Chimiques

    2016-11-07

    Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U{sup V} species into the stable mixed-valent star-shaped U{sup VI}/U{sup V} oxo cluster [U(UO{sub 2}){sub 5}(μ{sub 3}-O){sub 5}(PhCOO){sub 5}(Py){sub 7}]. This cluster is only the second example of a U{sup VI}/U{sup V} cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U{sup V} center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U{sub 12}{sup IV}U{sub 4}{sup V}O{sub 24} cluster {[K(Py)_2]_2[K(Py)]_2[U_1_6O_2_4(PhCOO)_2_4(Py)_2]}.

  5. Uranyl complexes as scaffolding or spacers for cucurbit[6]uril molecules in homo- and heterometallic species, including a uranyl-lanthanide complex

    Energy Technology Data Exchange (ETDEWEB)

    Thuery, Pierre [NIMBE, CEA, CNRS, Universite Paris-Saclay, CEA Saclay, Gif-sur-Yvette (France)

    2017-06-16

    The reaction of uranyl nitrate with cucurbit[6]uril (CB6) and carboxylic or sulfonic ligands under hydrothermal conditions and in the presence of additional metal cations (K{sup I} or Ce{sup III}) or cosolvents provided four complexes, which were crystallographically characterized. The compound [(UO{sub 2}){sub 2}K{sub 2}(CB6)(adc){sub 2}(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}].5H{sub 2}O (1), where H{sub 2}adc is 1,3-adamantanedicarboxylic acid, crystallizes in the form of a central K{sub 2}(CB6){sup 2+} column surrounded by two one-dimensional (1D) polymeric UO{sub 2}(adc)(NO{sub 3}){sup -} chains attached to the column by nitrate bridges, with a perfect match of the repeat lengths in the two subunits. The longer 1,3-adamantanediacetic acid (H{sub 2}adac) gives the complex [(UO{sub 2}){sub 2}(adac){sub 2}(HCOOH){sub 2}].CB6.6H{sub 2}O (2), in which the 1D uranyl-containing polymer and columns of CB6 molecules form a layered arrangement held by weak CH..O hydrogen bonds. The complex formed with the dipotassium salt of methanedisulfonic acid (K{sub 2}mds), [(UO{sub 2}){sub 2}K{sub 2}(CB6)(mds){sub 2}(OH){sub 2}(H{sub 2}O){sub 8}].4H{sub 2}O (3), is a 1D polymer, in which K{sub 2}(CB6){sup 2+} units are connected to one another by doubly hydroxide-bridged uranyl dimers in which the disulfonates are terminal, chelating ligands; connection between the two subunits is solely through potassium oxo-bonding to uranyl. The complex [(UO{sub 2}){sub 2}Ce{sub 2}(CB6)(C{sub 2}O{sub 4}){sub 3}(NO{sub 3}){sub 4}(H{sub 2}O){sub 6}].2H{sub 2}O (4) is a 1D polymer containing bridging oxalate ligands formed in situ, in which CB6 is coordinated to the lanthanide cations only; one nitrate ligand and one water ligand, hydrogen-bonded to each other, are included in the CB6 cavity, with the possible occurrence of interactions between nitrate oxygen atoms and ureido carbon atoms. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Water structure and aqueous uranyl(VI) adsorption equilibria onto external surfaces of beidellite, montmorillonite, and pyrophyllite: results from molecular simulations.

    Science.gov (United States)

    Greathouse, Jeffery A; Cygan, Randall T

    2006-06-15

    Molecular dynamics simulations were performed to provide a systematic study of aqueous uranyl adsorption onto the external surface of 2:1 dioctahedral clays. Our understanding of this key process is critical in predicting the fate of radioactive contaminants in natural groundwaters. These simulations provide atomistic detail to help explain experimental trends in uranyl adsorption onto natural media containing smectite clays. Aqueous uranyl concentrations ranged from 0.027 to 0.162 M. Sodium ions and carbonate ions (0.027-0.243 M) were also present in the aqueous regions to more faithfully model a stream of uranyl-containing groundwater contacting a mineral system comprised of Na-smectite. No adsorption occurred near the pyrophyllite surface, and there was little difference in uranyl adsorption onto the beidellite and montmorillonite, despite the difference in location of clay layer charge between the two. At low uranyl concentration, the pentaaquouranyl complex dominates in solution and readily adsorbs to the clay basal plane. At higher uranyl (and carbonate) concentrations, the mono(carbonato) complex forms in solution, and uranyl adsorption decreases. Sodium adsorption onto beidellite occurred both as inner- and outer-sphere surface complexes, again with little effect on uranyl adsorption. Uranyl surface complexes consisted primarily of the pentaaquo cation (85%) and to a lesser extent the mono(carbonato) species (15%). Speciation diagrams of the aqueous region indicate that the mono(carbonato)uranyl complex is abundant at high ionic strength. Oligomeric uranyl complexes are observed at high ionic strength, particularly near the pyrophyllite and montmorillonite surfaces. Atomic density profiles of water oxygen and hydrogen atoms are nearly identical near the beidellite and montmorillonite surfaces. Water structure therefore appears to be governed by the presence of adsorbed ions and not by the location of layer charge associated with the substrate. The water

  7. Experimental Investigation of Evolution of Pore Structure in Longmaxi Marine Shale Using an Anhydrous Pyrolysis Technique

    Directory of Open Access Journals (Sweden)

    Zhaodong Xi

    2018-05-01

    Full Text Available To better understanding the evolutionary characteristics of pore structure in marine shale with high thermal maturity, a natural Longmaxi marine shale sample from south China with a high equivalent vitrinite reflectance value (Ro = 2.03% was selected to conduct an anhydrous pyrolysis experiment (500–750 °C, and six artificial shale samples (pyrolysis products spanning a maturity range from Ro = 2.47% to 4.87% were obtained. Experimental procedures included mercury intrusion, nitrogen adsorption, and carbon dioxide adsorption, and were used to characterize the pore structure. In addition, fractal theory was applied to analyze the heterogeneous pore structure. The results showed that this sample suite had large differences in macropore, mesopore, and micropore volume (PV, as well as specific surface area (SSA and pore size distributions (PSD, at different temperatures. Micropore, mesopore, and macropore content increased, from being unheated to 600 °C, which caused the pore structure to become more complex. The content of small diameter pores (micropores and fine mesopores, <10 nm decreased and pores with large diameters (large mesopores and macropores, >10 nm slightly increased from 600 to 750 °C. Fractal analysis showed that larger pore sizes had more complicated pore structure in this stage. The variance in pore structure for samples during pyrolysis was related to the further transformation of organic matter and PSD rearrangement. According to the data in this study, two stages were proposed for the pore evolution for marine shale with high thermal maturity.

  8. Preparation and characterization of 1,6 anhydrous Β-D-Glucopyranose from starch

    International Nuclear Information System (INIS)

    Alvarez Lopez, M.S.

    1991-01-01

    In order to prepare 2-deoxi-2-fluoride-D-glucosa (2FDG) in an inert form there are several synthesis methods, but the more interesting one for our study is based in a reaction from the 1,6 anhydrous, Β-D-glucopyranose (1,6AGP), in an attempt to compare the labelling efficiency rate of 2FDG with F-18, which is highly used in nuclear medicine. In the present paper the attainment of starch from white potatoe, infrared analysis of this starch and fusion point are included. Also results are compared with an analytical reactive standard. The process of preparation of 1,6AGP by pyrolysis of starch under reduced pressure, its separation and purification by crystallization and infrared characterization of 1,6AGP, nuclear magnetic resonance and mass spectrometry are also included. 10 kg. of potatoes were used, and 93059 g. ±5.8 of starch with an efficiency rate of 9.32 ±0.631; fusion point was 272 o C and there was a 9.83 ± 1.48 % of humidity. After the pyrolysis, crystallization an purification processes, 1.71 ±0.54 % of 1,6AGP were obtained. Later results of compound characterization, nuclear magnetic resonance, infrared and mass spectrometry were compared with a commercial product and it was proved that it corresponds to such pure compound. (Author)

  9. Anhydrous formic acid and acetic anhydride as solvent or additive in nonaqueous titrations.

    Science.gov (United States)

    Buvári-Barcza, A; Tóth, I; Barcza, L

    2005-09-01

    The use and importance of formic acid and acetic anhydride (Ac2O) is increasing in nonaqueous acid-base titrations, but their interaction with the solutes is poorly understood. This paper attempts to clarify the effect of the solvents; NMR and spectrophotometric investigations were done to reveal the interactions between some bases and the mentioned solvents. Anhydrous formic acid is a typical protogenic solvent but both the relative permittivity and acidity are higher than those of acetic acid (mostly used in assays of bases). These differences originate from the different chemical structures: liquid acetic acid contains basically cyclic dimers while formic acid forms linear associates. Ac2O is obviously not an acidic but an aprotic (very slightly protophilic) solvent, which supposedly dissociates slightly into acetyl (CH3CO+) and acetate (AcO-) ions. In fact, some bases react with Ac2O forming an associate: the Ac+ group is bound to the delta- charged atom of the reactant while AcO- is associated with the delta+ group at appropriate distance.

  10. Investigation of solubility of carbon dioxide in anhydrous milk fat by lab-scale manometric method.

    Science.gov (United States)

    Truong, Tuyen; Palmer, Martin; Bansal, Nidhi; Bhandari, Bhesh

    2017-12-15

    This study aims to examine the solubility of CO 2 in anhydrous milk fat (AMF) as functions of partial pressure, temperature, chemical composition and physical state of AMF. AMF was fractionated at 21°C to obtain stearin and olein fractions. The CO 2 solubility was measured using a home-made experimental apparatus based on changes of CO 2 partial pressures. The apparatus was found to be reliable as the measured and theoretical values based on the ideal gas law were comparable. The dissolved CO 2 concentration in AMF increased with an increase in CO 2 partial pressure (0-101kPa). The apparent CO 2 solubility coefficients (molkg -1 Pa -1 ) in the AMF were 5.75±0.16×10 -7 , 3.9±0.19×10 -7 and 1.19±0.14×10 -7 at 35, 24 and 4°C, respectively. Higher liquid oil proportions resulted in higher CO 2 solubility in the AMF. There was insignificant difference in the dissolved CO 2 concentration among the AMF, stearin and olein fractions in their liquid state at 40°C. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Vapor-phase etching of InP using anhydrous HCl and PH/sub 3/ gas

    International Nuclear Information System (INIS)

    Pak, K.; Koide, Y.; Imai, K.; Yoshida, A.; Nakamura, T.; Yasuda, Y.; Nishinaga, T.

    1986-01-01

    In situ etching of the substrate surface for vapor-phase epitaxy is a useful technique for obtaining a smooth and damage-free surface prior to the growth. Previous work showed that the incorporation of in situ etching of InP substrate with anhydrous HCl gas resulted in a significant improvement in the surface morphologies for MOVPE-grown InGaAs/InP and InP epitaxial layers. However, the experiment on the HCl etching of the InP substrate for a wide temperature range has not been performed as yet. In this note, the authors describe the effect of the substrate temperature on the etching morphology of InP substrate by using the anhydrous HCl and PH/sub 3/ gases. In the experiment, they used a standard MOVPE horizontal system. A quartz reactor tube in a 60 mm ID, 60 cm long, was employed

  12. Use of X-ray diffraction to quantify amorphous supplementary cementitious materials in anhydrous and hydrated blended cements

    International Nuclear Information System (INIS)

    Snellings, R.; Salze, A.; Scrivener, K.L.

    2014-01-01

    The content of individual amorphous supplementary cementitious materials (SCMs) in anhydrous and hydrated blended cements was quantified by the PONKCS [1] X-ray diffraction (XRD) method. The analytical precision and accuracy of the method were assessed through comparison to a series of mixes of known phase composition and of increasing complexity. A 2σ precision smaller than 2–3 wt.% and an accuracy better than 2 wt.% were achieved for SCMs in mixes with quartz, anhydrous Portland cement, and hydrated Portland cement. The extent of reaction of SCMs in hydrating binders measured by XRD was 1) internally consistent as confirmed through the standard addition method and 2) showed a linear correlation to the cumulative heat release as measured independently by isothermal conduction calorimetry. The advantages, limitations and applicability of the method are discussed with reference to existing methods that measure the degree of reaction of SCMs in blended cements

  13. Biosensing for the Environment and Defence: Aqueous Uranyl Detection Using Bacterial Surface Layer Proteins

    Directory of Open Access Journals (Sweden)

    David J.R. Conroy

    2010-05-01

    Full Text Available The fabrication of novel uranyl (UO22+ binding protein based sensors is reported. The new biosensor responds to picomolar levels of aqueous uranyl ions within minutes using Lysinibacillus sphaericus JG-A12 S-layer protein tethered to gold electrodes. In comparison to traditional self assembled monolayer based biosensors the porous bioconjugated layer gave greater stability, longer electrode life span and a denser protein layer. Biosensors responded specifically to UO22+ ions and showed minor interference from Ni2+, Cs+, Cd2+ and Co2+. Chemical modification of JG-A12 protein phosphate and carboxyl groups prevented UO22+ binding, showing that both moieties are involved in the recognition to UO22+.

  14. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom)

    2012-12-07

    Switching on uranium(V) reactivity: The silylated uranium(V) dioxo complex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] (A) is inert to oxidation, but after two-electron reduction to [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-} (1), it can be desilylated to form [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} (2) with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U{sup VI/V} couple in dioxygen reduction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Interaction of uranyl ions with snake venom proteins from Lachesis muta muta

    International Nuclear Information System (INIS)

    MacCordick, H.J.; Taghva, F.

    1997-01-01

    The reaction product of uranyl nitrate with whole-protein Bushmaster snake venom in nitrate buffer at pH 3.5 has been studied. The maximum uptake of uranium was 291 μmol U x g -1 of venom. The infrared spectrum of the product showed an asymmetric O-U-O vibration at 921 cm -1 typical of complex formation with the uranyl ion. Stability measurements with the UO 2 2+ -protein complex in neutral medium indicated moderate hydrolytic stability, with 14% dissociation after 16 hours at 0 deg C. Neutron irradiation and desorption studies with a 235 U-labelled complex showed that generated fission products such as lanthanides and barium were readily lixiviated at pH 7, whereas Ru and Zr were highly retained by the protein substrate. (author)

  16. Thermometric titration of a free acid and of uranyl in spent fuel element solutions

    International Nuclear Information System (INIS)

    Zamek, M.; Strafelda, F.

    1975-01-01

    A method was elaborated of determining nitric acid in the presence of uranyl nitrate in both aqueous and non-aqueous solutions using a pyridine aqueous solution as a titration agent, and of determining excess uranyl after a hydrogen peroxide addition by a further titration using the same agent. Even a hundred-fold excess of magnesium did not disturb the titration. The method is used in operating solution analyses in the extraction fuel reprocessing in the presence of a small amount of plutonium and of fission products. The reproducibility and accuracy of the method varied in the order of tens to units per cent depending on the concentration of components to be determined. The procedure is applicable for test volumes ranging between 0.1 and 10 ml in concentrations of 1 to 10 -3 M. (author)

  17. Obtention of Uo3 by means of denitration of uranyl nitrate in a fluidized-bed

    International Nuclear Information System (INIS)

    Santos, W.R. dos; Costa, P.A.

    1990-01-01

    A fluidized-bed pilot unit for the production of UO 3 installed at IPEN-CNEN/SP is described. Its capacity is of 20 kg U/h in a continuous process. The main components of this pilot unit are: a system for the concentration of nuclearly pure uranyl nitrate (≅ 100 g U/L), a system for the denitration of the concentrated uranyl nitrate, an absorption system for NO 2 produced during the denitration reaction and, finally, a system for the dissolution of UO 3 that does not meet the specifications. The operational troubles found during the initial runs are presented. The results of the physical and chemical analysis of the UO 3 produced are discussed and a comparison is made for the UO 3 obtained by both fluidized-bed and wet processes. (author) [pt

  18. Determination of uranyl nitrate diffusion coefficients in organic and aqueous media using the porous diaphragm method

    International Nuclear Information System (INIS)

    Chierice, G.O.

    1974-01-01

    The diffusion coefficient is one of the parameters necessary for the obtention of the extraction exponential coefficients, that are contained within the H.T.U. (height of transfer unity) calculation expression, when operating with continuous organic phase. The organic phase used was tri-n-butyl-phosphate (TBP) and varsol in the 35% and 65% proportions respectively. After each experiment, the uranium content present in each compartment was spectrophotometrically determined and the quantities contained in the aqueous phases were determined by means of volumetric titration. It was found out that the uranyl ion diffusion coefficient is two and one half times less in organic phase, this just being attributed to the greater interactions of the uranyl ions in organic than in aqueous medium

  19. Crystallization characteristics of ammonium uranyl carbonate (AUC) in ammonium carbonate solutions

    International Nuclear Information System (INIS)

    Kim, T.J.; Jeong, K.C.; Park, J.H.; Chang, I.S.; Choi, C.S.

    1994-01-01

    Ammonium carbonate solutions with an excessive amount of NH 3 were produced in a commercial AUC (ammonium uranyl carbonate) conversion plant. In this study the AUC crystals, precipitated with uranyl nitrate and ammonium carbonate solutions prepared in the laboratory, were characterized to determine the feasibility of recycling ammonium carbonate solution. The AUC crystals were easily agglomerated with the increasing concentration of CO 3 2- and mole ratio of NH 4 + /CO 3 2- in ammonium carbonate solution. Effects of a mixing system for the solution in the AUC crystallizer and the feed location of the solution onthe agglomeration of AUC crystals were also studied along with the effects of agglomerated AUC powders on UO 2 powders. Finally, the feasibility of manufacturing UO 2 fuel with a sintered pellet density of 10.52 g/cm 3 , using the AUC powders generated in this experiment, was demonstrated. (orig.)

  20. Novel two-dimensional uranyl-organic assemblages in the citrate and D(-)-citramalate families

    International Nuclear Information System (INIS)

    Thuery, P.

    2008-01-01

    Uranyl nitrate reacts with D(-)-citramalic acid (H(3)citml) under mild hydrothermal conditions to give the two-dimensional polymer [UO 2 (Hcitml)] 1, in which each ligand chelates one metal atom through its hydroxyl and alpha- carboxylate groups and binds to three others in monodentate fashion. The resulting neutral layers display isolated uranyl pentagonal bipyramidal polyhedra. Whereas citric acid (H(4)cit) has been shown previously to give various three- and mono-dimensional uranyl organic assemblages, complexation under hydrothermal conditions in the presence of either NaOH/NEt 4 Cl or pyridine yields the complexes [NEt 4 ] 2 [(UO 2 ) 3 (cit) 2 (H 2 O) 2 ]· 2H 2 O 2 and [Hpy] 2 )[(UO 2 ) 3 (cit)(Hcit)(OH)] 3, respectively, which both crystallize as two- dimensional frameworks. The layers are either planar and separated by the counter ions in 2 or corrugated and hydrogen bonded to one another in 3. In both 2 and 3, [UO 2 (cit)] 2 4- dimeric subunits with edge-sharing pentagonal bipyramidal uranium coordination polyhedra are present but, in both cases and in contrast with previous structures containing [UO 2 (Hcit)] 2 2- dimers, the carboxylate group not involved in the dimer formation is coordinated to another uranyl unit, which is part of either a centrosymmetric hexagonal bipyramidal bis-aquated group or a different, [(UO 2 ) 2 (Hcit)(OH)] dimer. These examples of two- dimensional assemblages further illustrate the variety of architectures which can be obtained with citric and related acids and the important structure-directing effects of the counter ions. (author)

  1. Removal of toxic uranium from synthetic nuclear power reactor effluents using uranyl ion imprinted polymer particles.

    Science.gov (United States)

    Preetha, Chandrika Ravindran; Gladis, Joseph Mary; Rao, Talasila Prasada; Venkateswaran, Gopala

    2006-05-01

    Major quantities of uranium find use as nuclear fuel in nuclear power reactors. In view of the extreme toxicity of uranium and consequent stringent limits fixed by WHO and various national governments, it is essential to remove uranium from nuclear power reactor effluents before discharge into environment. Ion imprinted polymer (IIP) materials have traditionally been used for the recovery of uranium from dilute aqueous solutions prior to detection or from seawater. We now describe the use of IIP materials for selective removal of uranium from a typical synthetic nuclear power reactor effluent. The IIP materials were prepared for uranyl ion (imprint ion) by forming binary salicylaldoxime (SALO) or 4-vinylpyridine (VP) or ternary SALO-VP complexes in 2-methoxyethanol (porogen) and copolymerizing in the presence of styrene (monomer), divinylbenzene (cross-linking monomer), and 2,2'-azobisisobutyronitrile (initiator). The resulting materials were then ground and sieved to obtain unleached polymer particles. Leached IIP particles were obtained by leaching the imprint ions with 6.0 M HCl. Control polymer particles were also prepared analogously without the imprint ion. The IIP particles obtained with ternary complex alone gave quantitative removal of uranyl ion in the pH range 3.5-5.0 with as low as 0.08 g. The retention capacity of uranyl IIP particles was found to be 98.50 mg/g of polymer. The present study successfully demonstrates the feasibility of removing uranyl ions selectively in the range 5 microg - 300 mg present in 500 mL of synthetic nuclear power reactor effluent containing a host of other inorganic species.

  2. Stability and kinetics of uranyl ion complexation by macrocycles in propylene carbonate

    International Nuclear Information System (INIS)

    Fux, P.

    1984-06-01

    A thermodynamic study of uranyl ion complexes formation with different macrocyclic ligands was realized in propylene carbonate as solvent using spectrophotometric and potentiometric techniques. Formation kinetics of two UO 2 complexes: a crown ether (18C6) and a coronand (22) was studied by spectrophotometry in propylene carbonate with addition of tetraethylammonium chlorate 0.1M at 25 0 C. Possible structures of complexes in solution are discussed [fr

  3. Fabrication of ceramic grade UO2 by direct conversion of uranyl nitrate hexahydrate

    International Nuclear Information System (INIS)

    Lainetti, P.E.O.; Riella, H.G.

    1992-01-01

    A method of direct conversion of uranyl nitrate hexahydrate (UNH) solution to ceramic grade uranium dioxide powders by thermal denitration in a furnace that combines atomization nozzle and a gas stirred bed is described. The main purpose of this work is to show that this alternative process is technically viable, specially if the recovery of the scrap generated in the nuclear fuel pellet production is required, without further generation of new liquid wastes. (author)

  4. Crystal structure of the (REE)–uranyl carbonate mineral shabaite-(Nd)

    Czech Academy of Sciences Publication Activity Database

    Plášil, Jakub; Škoda, R.

    2017-01-01

    Roč. 62, č. 2 (2017), s. 97-105 ISSN 1802-6222 R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : shabaite-(Nd) * uranyl carbonate * rare-earth elements * crystal structure * mineral evolution Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Geology Impact factor: 0.609, year: 2016

  5. Rapid determination of fluoride in uranyl nitrate solution obtained in conversion process of uranium tetrafluoride

    International Nuclear Information System (INIS)

    Levin, R.; Feldman, R.; Sahar, E.

    1976-01-01

    In uranium production the conversion of impure uranium tetrafluoride by sodium hydroxide was chosen as a current process. A rapid method for determination of fluoride in uranyl-nitrate solution was developed. The method includes precipitation of uranium as diuranate, separation by centrifugation, and subsequent determination of fluoride in supernate by titration with thorium nitrate. Fluoride can be measured over the range 0.15-2.5 gr/gr U, with accuracy of +-5%, within 15 minutes. (author)

  6. Dehydration-driven evolution of topological complexity in ethylamonium uranyl selenates

    Energy Technology Data Exchange (ETDEWEB)

    Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru [Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg (Russian Federation); Krivovichev, Sergey V. [Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg (Russian Federation); Tananaev, Ivan G. [Far Eastern Federal University, Suhanova st. 8, 690950 Vladivostok (Russian Federation)

    2017-03-15

    Single crystals of four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules, (C{sub 2}H{sub 8}N){sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) (I), (C{sub 2}H{sub 8}N){sub 3}[(UO{sub 2})(SeO{sub 4}){sub 2}(HSeO{sub 4})] (II), (C{sub 2}H{sub 8}N)[(UO{sub 2})(SeO{sub 4})(HSeO{sub 3})] (III), and (C{sub 2}H{sub 8}N)(H{sub 3}O)[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (IV) have been prepared by isothermal evaporation from aqueous solutions. Uranyl-containing 1D and 2D units have been investigated using topological approach and information-based complexity measurements that demonstrate the evolution of structural units and the increase of topological complexity with the decrease of H{sub 2}O content. - Graphical abstract: Single crystals of four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules have been prepared by isothermal evaporation from aqueous solutions. Structural analysis and information-based topological complexity calculations points to the possible sequence of crystalline phases formation, showing both topological and structural branches of evolution. - Highlights: • Single crystals of four novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • Dehydration processes drives the evolution of topological complexity of 1D and 2D structural units.

  7. Thermodynamic properties of actinide complexes. IV. Thorium(IV)- and uranyl(VI)-malonate systems

    Energy Technology Data Exchange (ETDEWEB)

    Di Bernardo, P; Di Napoli, V; Cassol, A; Magon, L [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi

    1977-01-01

    The stability constants and the enthalpies of formation of thorium(IV)- and uranyl(VI)-malonate complexes have been determined by potentiometric and calorimetric titrations in 1.00 M solutions of Na(ClO/sub 4/) at 25/sup 0/C. All complexes formed are found to be stabilized by a large entropy gain. The values for the stability constants agree with an ionic bonding model. The malonate behaves as a bidentate ligand forming only chelate complexes.

  8. Uranyl ion complexation by the tripodal ligand nitrilo-tri-acetate

    Energy Technology Data Exchange (ETDEWEB)

    Thuery, P. [CEA Saclay, DSM/DRECAM/SCM, F-91191 Gif Sur Yvette, (France)

    2007-07-01

    Reaction of uranyl nitrate with N-(2-acetamido)iminodiacetic acid (ADA) under hydrothermal conditions resulted in the hydrolysis of the amide group and the isolation of the complex [(UO{sub 2})(HNTA)(H{sub 2}O){sub 2}], in which each nitrilo-tri-acetate ligand, protonated at the N site, bridges three metal atoms to give rise to infinite ladder-like ribbons built from 2:2 metallacycles. (author)

  9. Selectivity in Ligand Binding to Uranyl Compounds: A Synthetic, Structural, Thermodynamic and Computational Study

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Univ. of California, Berkeley, CA (United States)

    2017-12-06

    The uranyl cation (UO22+) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. We believe that the goal of developing a practical system for uranium separation from seawater will not be attained without new insights into our existing fundamental knowledge of actinide chemistry. We posit that detailed studies of the kinetic and thermodynamic factors that influence interactions between f-elements and ligands with a range of donor atoms is essential to any major advance in this important area. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. We anticipate that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials.

  10. Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

    Science.gov (United States)

    Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

    2017-11-02

    Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. A bibliographical review on the radiolysis of uranyl nitrate solutions in nitric acid medium

    International Nuclear Information System (INIS)

    Siri, Sandra; Mondino, Angel V.

    2004-01-01

    A bibliographical study on the effects of ionizing radiation on uranyl nitrate solutions in nitric acid medium was performed, and the state of knowledge on this subject is presented. The main experimental and theoretical results on water, nitric acid and uranium solutions radiolysis are reviewed and critically evaluated. This paper provides a collection of references as an aid to the development of practical applications, and to stimulate new research on fundamental processes in these systems. (author) [es

  12. Crystal structure of the (REE)-uranyl carbonate mineral kamotoite-(Y)

    Czech Academy of Sciences Publication Activity Database

    Plášil, Jakub; Petříček, Václav

    2017-01-01

    Roč. 81, č. 3 (2017), s. 653-660 ISSN 0026-461X R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : kamotoite-(Y) * uranyl carbonate * rare-earth elements * crystal structure Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Geology Impact factor: 1.285, year: 2016

  13. Synthesis, X-ray crystallography, spectroscopy, electrochemistry, thermal and kinetic study of uranyl Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Golzard, F.; Eigner, Václav; Dušek, Michal

    2013-01-01

    Roč. 66, č. 20 (2013), s. 3629-3646 ISSN 0095-8972 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : X-ray crystallography * uranyl Schiff base complex * kinetics of thermal decomposition * cyclic voltammetry * kinetics and mechanism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.224, year: 2013

  14. Anhydrous polymer-based coating with sustainable controlled release functionality for facile, efficacious impregnation, and delivery of antimicrobial peptides.

    Science.gov (United States)

    Lim, Kaiyang; Saravanan, Rathi; Chong, Kelvin K L; Goh, Sharon H M; Chua, Ray R Y; Tambyah, Paul A; Chang, Matthew W; Kline, Kimberly A; Leong, Susanna S J

    2018-04-17

    Anhydrous polymers are actively explored as alternative materials to overcome limitations of conventional hydrogel-based antibacterial coating. However, the requirement for strong organic solvent in polymerization reactions often necessitates extra protection steps for encapsulation of target biomolecules, lowering encapsulation efficiency, and increasing process complexity. This study reports a novel coating strategy that allows direct solvation and encapsulation of antimicrobial peptides (HHC36) into anhydrous polycaprolactone (PCL) polymer-based dual layer coating. A thin 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) film is layered onto the peptide-impregnated PCL as a diffusion barrier, to modulate and enhance release kinetics. The impregnated peptides are eventually released in a controlled fashion. The use of 2,2,2-trifluoroethanol (TFE), as polymerization and solvation medium, induces the impregnated peptides to adopt highly stable turned conformation, conserving peptide integrity, and functionality during both encapsulation and subsequent release processes. The dual layer coating showed sustained antibacterial functionality, lasting for 14 days. In vivo assessment using an experimental mouse wounding model demonstrated good biocompatibility and significant antimicrobial efficacy of the coating under physiological conditions. The coating was translated onto silicone urinary catheters and showed promising antibacterial efficacy, even outperforming commercial silver-based Dover cather. This anhydrous polymer-based platform holds immense potential as an effective antibacterial coating to prevent clinical device-associated infections. The simplicity of the coating process enhances its industrial viability. © 2018 Wiley Periodicals, Inc.

  15. High temperature proton exchange membranes prepared from epoxycyclohexylethyltrimethoxysilane and amino trimethylene phosphonic acid as anhydrous proton conductors

    International Nuclear Information System (INIS)

    Chen, Cheng; Shen, Chunhui; Kong, Gengjin; Gao, Shanjun

    2013-01-01

    High temperature anhydrous proton exchange membranes based on phosphonic acid were prepared from epoxycyclohexylethyltrimethoxysilane (EHTMS) and amino trimethylene phosphonic acid (ATMP) by sol–gel process. The structures and properties of membranes with different phosphonic acid content were extensively characterized by FTIR, TG-DSC and XRD. Their proton conductivity under dry condition was also investigated under different temperature. The results show that the proton conductivity of the prepared membranes strongly depends on temperature, and the proton conductivity ranges from 8.81 × 10 −5 S cm −1 at 20 °C to 4.65 × 10 −2 S cm −1 at 140 °C under anhydrous condition. It indicates that the increasing temperature is favorable for congregating of the grafted–PO 3 H 2 and increasing of the proton mobility. In addition, from the results of AFM images, it was confirmed that the continuous distribution of phosphonic acid groups is favorable for the formation of the proton transport channel, which can significantly enhance the proton conductivity of the membranes. Highlights: ► Hybrid membranes of Epoxycyclohexylethyltrimethoxysilane and Amino trimethylene phosphonic acid. ► The proton conductivity is 4.65 × 10 −2 S cm −1 at 140 °C under anhydrous condition. ► Continuous uniform distributions of phosphonic acid groups can be observed by AFM. ► There could be hydrogen bond network within high temperature membranes

  16. Anhydrate to hydrate solid-state transformations of carbamazepine and nitrofurantoin in biorelevant media studied in situ using time-resolved synchrotron X-ray diffraction

    DEFF Research Database (Denmark)

    Bøtker, Johan Peter; Rantanen, Jukka; Arnfast, Lærke

    2016-01-01

    with different biorelevant media, simulated fasted and fed state intestinal fluids containing bile salt and dioleoylphosphatidylcholine (DOPC) micelles, DOPC/sodium dodecyl sulfate (SDS) mixture, bile salt solution and water. Two anhydrate compounds (carbamazepine, CBZ and nitrofurantoin, NF) with different...

  17. Cerium(terbium, erbium)chloride-choline chloride aqueous systems

    International Nuclear Information System (INIS)

    Gajfutdinova, R.K.; Zhuravlev, E.F.; Bikbaeva, G.G.; Domrachev, V.N.; Vanskova, G.I.

    1985-01-01

    To clarify the effect of rare earth nature on mutual solubility of rare earth salts and amines the solubility of solid phases in the systems, consisting of choline chloride, water and cerium, terbium, erbium chlorides, has been studied. It is established, that solubility isotherms of all the systems, testify to the formation of new solid phases of the composition: Ce(Tb, Er)xCl 3 x2C 5 H 14 ONClx3H 2 O. Individuality of new solid phases is proved by DTA method, the composition is confirmed by chemical analysis and data of PMR spectra, for choline chloride and its complexes with rare earth chlorides of the given composition PMR and IR spectra are studied

  18. Renal hemodynamics in uranyl acetate-induced acute renal failure of rabbits

    International Nuclear Information System (INIS)

    Sudo, M.; Honda, N.; Hishida, A.; Nagase, M.

    1977-01-01

    The role of renal hemodynamic alterations in the curtailment of renal function was studied in rabbits with uranyl acetate-induced acute renal failure. The day following the i.v. injection of uranyl acetate (2 mg/kg of body wt), renal blood flow (RBF) and clearance of creatinine (Ccr) decreased to approximately 60 and 20% of controls, respectively. Intracortical fractional flow distribution, estimated by radioactive microsphere method, did not change. The extraction ratio of para-aminohippurate (EPAH) decreased and the renal extraction of sodium (CNa/Ccr) increased, with minimal structural change in the kidney. Urine output increased two to three times that of the control. After three days oliguria appeared despite complete recovery of RBF. The zonal flow redistributed toward the deep cortex. CCr and EPAH reached their minimums, concomitantly with tubular necrosis and intratubular casts. After seven days animals could be divided into the oliguric and diuretic groups. CCr and EPAH were higher in the diuretic group, while there was no significant difference in RBF and the flow distribution between groups. Regeneration of damaged tubular cells was found in the diuretic group but not in the oliguric group. The findings suggest the minor roles of RBF and the intracortical flow distribution, and a fundamental role of back leakage of filtrate across damaged tubular epithelium in the maintenance of reduced CCR and urine output during the oliguric stage in rabbits with uranyl acetate-induced renal failure

  19. A relativistic density functional study of uranyl hydrolysis and complexation by carboxylic acids in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Ray, Rupashree Shyama

    2009-02-10

    In this work, the complexation of uranium in its most stable oxidation state VI in aqueous solution was studied computationally, within the framework of density functional (DF) theory. The thesis is divided into the following parts: Chapter 2 briefly summarizes the relevant general aspects of actinide chemistry and then focuses on actinide environmental chemistry. Experimental results on hydrolysis, actinide complexation by carboxylic acids, and humic substances are presented to establish a background for the subsequent discussion. Chapter 3 describes the computational method used in this work and the relevant features of the parallel quantum chemistry code PARAGAUSS employed. First, the most relevant basics of the applied density functional approach are presented focusing on relativistic effects. Then, the treatment of solvent effects, essential for an adequate modeling of actinide species in aqueous solution, will be introduced. At the end of this chapter, computational parameters and procedures will be summarized. Chapter 4 presents the computational results including a comparison to available experimental data. In the beginning, the mononuclear hydrolysis product of UO{sub 2}{sup 2+}, [UO{sub 2}OH]{sup +}, will be discussed. The second part deals with actinide complexation by carboxylate ligands. First of all the coordination number for uranylacetate will be discussed with respect to implications for the complexation of actinides by humic substances followed by the uranyl complexation of aromatic carboxylic acids in comparison to earlier results for aliphatic ones. In the end, the ternary uranyl-hydroxo-acetate are discussed, as models of uranyl humate complexation at ambient condition.

  20. Calorimetric measurement of the enthalpy of extraction of uranyl nitrate by tri-n-amyl phosphate

    International Nuclear Information System (INIS)

    Srinivasan, T.G.; Vasudeva Rao, P.R.; Venugopal, V.; Sood, D.D.

    2002-01-01

    Enthalpy of extraction of uranyl nitrate by tri n-amyl phosphate (TAP) and its solutions in n-dodecane has been directly measured by solution calorimetry for the first time. Measurements have been made at 303±1 K, in both forward as well as the reverse extraction modes. The enthalpies of the accompanying reactions such as the dilution of the uranyl nitrate in the aqueous phase, the hydration of TAP, the mixing of TAP and n-dodecane, the mixing of the metal-solvate (UO 2 (NO 3 ) 2 ·2TAP) and n-dodecane and mixing of the metal-solvate and TAP have also been independently measured and used to derive both the equilibrium state enthalpies and the standard state enthalpies for the extraction. Two distinct standard states have been used for the organic phase, viz., 1) all solutes infinitely diluted in diluent (ΔH*) and 2) all solutes infinitely diluted in the water saturated extractant (ΔH 0 ). The results have been compared with the enthalpies of extraction measured by employing the temperature dependence of the distribution ratio as well as calorimetry reported in the literature for extraction of uranyl nitrate by TAP and TBP. (author)

  1. Enhancement of uranyl fluorescence using trimesic acid: Ligand sensitization and co-fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Maji, S. [Chemistry Group, Materials Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Viswanathan, K.S., E-mail: vish@igcar.gov.in [Chemistry Group, Materials Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)

    2011-09-15

    Trimesic acid (TMA) was shown to sensitize and enhance uranyl fluorescence in aqueous medium, with the enhancement being a maximum at pH 5.0. Fluorescence spectra and lifetime data together suggest that TMA complexes with uranyl (UO{sub 2}{sup 2+}). The fluorescence of UO{sub 2}{sup 2+} in its acid complex is further enhanced by more than two orders of magnitude following the addition of Y{sup 3+}; a process referred to as co-fluorescence, leading to the possibility of detecting uranium at sub ng/mL level. The present study demonstrates, for the first time, fluorescence enhancement of the uranyl species due to co-fluorescence. - Highlights: > Trimesic acid was shown to sensitize and enhance the fluorescence of uranium in aqueous medium. > This ligand also exhibited co-fluorescence of uranium with Y{sup 3+}. > To the best of our knowledge this is the first report of co-fluorescence in uranium. > The enhancement of uranium fluorescence, resulted in detection limits in the ng/mL regime.

  2. A relativistic density functional study of uranyl hydrolysis and complexation by carboxylic acids in aqueous solution

    International Nuclear Information System (INIS)

    Ray, Rupashree Shyama

    2009-01-01

    In this work, the complexation of uranium in its most stable oxidation state VI in aqueous solution was studied computationally, within the framework of density functional (DF) theory. The thesis is divided into the following parts: Chapter 2 briefly summarizes the relevant general aspects of actinide chemistry and then focuses on actinide environmental chemistry. Experimental results on hydrolysis, actinide complexation by carboxylic acids, and humic substances are presented to establish a background for the subsequent discussion. Chapter 3 describes the computational method used in this work and the relevant features of the parallel quantum chemistry code PARAGAUSS employed. First, the most relevant basics of the applied density functional approach are presented focusing on relativistic effects. Then, the treatment of solvent effects, essential for an adequate modeling of actinide species in aqueous solution, will be introduced. At the end of this chapter, computational parameters and procedures will be summarized. Chapter 4 presents the computational results including a comparison to available experimental data. In the beginning, the mononuclear hydrolysis product of UO_2"2"+, [UO_2OH]"+, will be discussed. The second part deals with actinide complexation by carboxylate ligands. First of all the coordination number for uranylacetate will be discussed with respect to implications for the complexation of actinides by humic substances followed by the uranyl complexation of aromatic carboxylic acids in comparison to earlier results for aliphatic ones. In the end, the ternary uranyl-hydroxo-acetate are discussed, as models of uranyl humate complexation at ambient condition.

  3. Mechanistic study of the interaction of uranyl ions with zirconium oxide and zirconium silicate

    International Nuclear Information System (INIS)

    Lomenech, C.

    2002-04-01

    This work deals with structural and thermodynamic studies of the sorption of uranyl species on zircon and zirconia. After determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, thermodynamic data were obtained using alpha spectrometry, for different uranyl concentrations, different background electrolytes (NaClO 4 or KNO 3 ) and different ionic strengths. The structural identification of the surface complexes and sorption sites was carried out using several spectroscopies: XPS spectroscopy allowed a determination of the nature of the sorption sites (≡Zr-O- on zirconia and ≡Si-O- on zircon). Whereas fluorescence decay measurements gave the number of surface species, the combined use of XPS spectroscopy and laser spectro-fluorimetry enabled us to correlate differences in bonding energies and emission wavelengths with differences in the nature of the background electrolyte or in the pH of sorption; DRIFT spectroscopy was a powerful tool for the determination of the presence of sorbed uranyl nitrate species. EXAFS results clearly showed a splitting of the equatorial oxygen atoms in two shells, corresponding to a polydentate, inner-sphere complex. EXAFS results also indicated strong similarities between dry samples and in situ experiments, which confirms the validity of all the spectroscopic measurements. Macroscopic thermodynamic data were then modeled using a surface complexation model (2 pK and constant capacitance models), the results of the structural study being used as constraints for the simulation code FITEQL. (author)

  4. Determination of parameters dissolution of yellow-cake. Production of uranyl nitrate - Gas precipitation of AUC

    International Nuclear Information System (INIS)

    Mellah, A.

    1987-07-01

    The different stages of the purification cycle of yellow-cakes have been studied thoroughly in order to obtain an ammonium uranyl carbonate (AUC) as an intermediate product of uranium dioxide (UO 2 ). The optimal parameters of yellow-cake dissolution, filtration, extraction by solvent, scrubbing and stripping were determined. An original program of thermodynamic calculation was developed for the determination of the free energies of yellow-cake dissolution reactions. Different numerical methods were used to determine the kinetic constant, the reaction order and correlation equations of uranyl nitrate density as a function of U and H + concentrations, before and after the extraction cycle. For the first time, Algerian filteraids were used for the filtration of uranyl nitrate solutions with satisfactory results. A laboratory designed installation enabled the precipitation of AUC by injection of ammonia and carbon dioxide gases. Interesting results have been obtained and further investigations should be carried out in order to optimize all the paremeters of the gas precipitation of AUC

  5. The thermal denigration in fluid-bed to make uranyl product

    International Nuclear Information System (INIS)

    Ma Zhenrong; Cui Yulin; Zhu Changbing; Fan Chuanyong; Liu Yanfeng

    2010-01-01

    Nuclear fuel reprocessing plant used the thermal denigration to high concentration of uranyl nitrate solution in fluid-bed to make uranyl product. First the uranyl nitrate solution were concentrated in evaporator, into 300 gU/L, 600 gU/L, 750 gU/L and 1000 gU/L.When the fluid-bed was in good fluidity state at 320 degree C, the solution was sprayed all over the surface of the fine crystal seeds through the dual-channel air-blast nozzles to make new crystal seed and to make them grow up. The denigration reaction occurred when the internal temperature of the fluid-bed was kept at about 300 degree C by the outside and inside heat apparatus. The product were transported crossing the valve and spiral transfer to pack. The tail gas was purified and discharged. Through the fluid-bed's running, the variation discipline of temperature and the pressure, the effect curve of the quality of product accumulated to pressure drop were determined. At the same time, the gentrification temperature, the distributed heat and the transfer mode were tested. (authors)

  6. Complexes of vanadyl and uranyl ions with the chelating groups of humic matter

    International Nuclear Information System (INIS)

    Goncalves, M.L.S.; Mota, A.M.

    1987-01-01

    The uranyl and vanadyl complexes formed with salicylic, phthalic and 3,4-dihydroxybenzoic acids have been studied by potentiometry in order to determine the stability constants of the Msub(m) Lsub(n) species formed in solution, and the constants for hydrolysis and polymeric complexes, at 25.0 0 , in 0.10, 0.40 and 0.70M sodium perchlorate. MINIQUAD was used in process the data to find the best models for the species in solution, and calculate the formation constants. The uranyl-salicylic acid sytem was also studied by spectrophotometry and the program SQUAD used to process the data obtained. The best models for these systems show that co-ordination of the uranyl ion by carboxylate groups is easier than for the vanadyl ion, whereas the vanadyl ion seems to form more stable complexes with phenolate groups. Both oxo-cations seem to tend to hydrolyse rather than form complexes when the L:M ratios are greater than unity. Although the change in the constants with ionic strength is small, the activity coefficients of the salicylate and phthalate species have been calculated at ionic strengths 0.40 and 0.70M, along with the interaction parameters with Na + , from the stability constants found for the species ML and H 2 L, according to the Bronsted-Guggenheim expression. (author)

  7. Water-Reflected 233U Uranyl Nitrate Solutions in Simple Geometry

    International Nuclear Information System (INIS)

    Elam, K.R.

    2001-01-01

    A number of critical experiments involving 233 U were performed in the Oak Ridge National Laboratory Building 9213 Critical Experiments Facility during the years 1952 and 1953. These experiments, reported in Reference 1, were directed toward determining bounding values for the minimum critical mass, minimum critical volume, and maximum safe pipe size of water-moderated solutions of 233 U. Additional information on the critical experiments was found in the experimental logbooks. Two experiments utilizing uranyl nitrate (UO 2 (NO 3 ) 2 ) solutions in simple geometry are evaluated in this report. Experiment 37 is in a 10.4-inch diameter sphere, and Experiment 39 is in a 10-inch diameter cylinder. The 233 U concentration ranges from 49 to 62 g 233 U/l. Both experiments were reflected by at least 6 inches of water in all directions. Paraffin-reflected uranyl nitrate experiments, also reported in Reference 1, are evaluated elsewhere. Experiments with smaller paraffin reflected 5-, 6-, and 7.5-inch diameter cylinders are evaluated in U233-SOL-THERM-004. Experiments with paraffin reflected 8-, 8.5-, 9-, 10-, and 12-inch diameter cylinders are evaluated in U233-SOL-THERM-002. Later experiments with highly-enriched 235 U uranyl fluoride solution in the same 10.4-inch diameter sphere are reported in HEU-SOL-THERM-010. Both experiments were judged acceptable for use as criticality-safety benchmark experiments

  8. Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

    International Nuclear Information System (INIS)

    Medvedkov, Ya. A.; Serezhkina, L. B.; Grigor’ev, M. S.; Serezhkin, V. N.

    2016-01-01

    Two new malonate-containing uranyl complexes with carbamide of the formulas [UO 2 (C 3 H 2 O 4 )(Urea) 2 ] (I) and [UO 2 (C 3 H 2 O 4 )(Urea) 3 ] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO 2 (C 2 O 4 )(Urea) 3 ] (III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO 2 (C 3 H 2 O 4 )(Urea) 2 ] ∞ belonging to the crystal-chemical group AT 11 M 2 1 (A = UO 2 2+ , T 11 = C 3 H 2 O 4 2- , M 1 = Urea) of uranyl complexes. Crystals II and III are composed of the molecular complexes [UO 2 (L)(Urea) 3 ], where L = C 3 H 2 O 4 2- or C 2 O 4 2- , belonging to the crystal-chemical group AB 01 M 3 1 (A = UO 2 2+ , B 01 = C 3 H 2 O 4 2- or C 2 O 4 2- , M 1 = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi–Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.

  9. Electrocarboxylation of benzyl chlorides at silver cathode at the preparative scale level

    Energy Technology Data Exchange (ETDEWEB)

    Scialdone, Onofrio [Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita di Palermo, Viale delle Scienze, 90128 Palermo (Italy)], E-mail: scialdone@dicpm.unipa.it; Galia, Alessandro; Errante, Giuseppina [Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita di Palermo, Viale delle Scienze, 90128 Palermo (Italy); Isse, Abdirisak Ahmed; Gennaro, Armando [Dipartimento di Scienze Chimiche, Universita di Padova, Via Marzolo 1, 35131 Padova (Italy); Filardo, Giuseppe [Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita di Palermo, Viale delle Scienze, 90128 Palermo (Italy)

    2008-01-01

    The electrocarboxylation of benzyl chlorides to the corresponding carboxylic acids performed at silver cathodes was investigated both theoretically and experimentally in order to find the influence of the operative parameters on the selectivity and on the Faradic efficiency of the process. Theoretical considerations were confirmed by the electrocarboxylation of 1-phenyl-1-chloroethane performed in undivided cells equipped with sacrificial anodes both in a bench-scale electrochemical batch reactor and in a continuous batch recirculation reaction system equipped with a parallel plate electrochemical cell. Selectivity and Faradic yields higher than 80% and 70%, respectively, were obtained by working under anhydrous conditions both under amperostatic and potentiostatic alimentation at appropriate values of either current density or applied potential.

  10. Chloride removal from plutonium alloy

    International Nuclear Information System (INIS)

    Holcomb, H.P.

    1983-01-01

    SRP is evaluating a program to recover plutonium from a metallic alloy that will contain chloride salt impurities. Removal of chloride to sufficiently low levels to prevent damaging corrosion to canyon equipment is feasible as a head-end step following dissolution. Silver nitrate and mercurous nitrate were each successfully used in laboratory tests to remove chloride from simulated alloy dissolver solution containing plutonium. Levels less than 10 ppM chloride were achieved in the supernates over the precipitated and centrifuged insoluble salts. Also, less than 0.05% loss of plutonium in the +3, +4, or +6 oxidation states was incurred via precipitate carrying. These results provide impetus for further study and development of a plant-scale process to recover plutonium from metal alloy at SRP

  11. Series of mixed uranyl-lanthanide (Ce, Nd) organic coordination polymers with aromatic polycarboxylates linkers.

    Science.gov (United States)

    Mihalcea, Ionut; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

    2012-09-17

    Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.

  12. Hydrothermal synthesis of uranyl squarates and squarate-oxalates: hydrolysis trends and in situ oxalate formation.

    Science.gov (United States)

    Rowland, Clare E; Cahill, Christopher L

    2010-07-19

    We report the synthesis of two uranyl squarates and two mixed-ligand uranyl squarate-oxalates from aqueous solutions under hydrothermal conditions. These products exhibit a range of uranyl building units from squarates with monomers in (UO(2))(2)(C(4)O(4))(5).6NH(4).4H(2)O (1; a = 16.731(17) A, b = 7.280(8) A, c = 15.872(16) A, beta = 113.294(16) degrees , monoclinic, P2(1)/c) and chains in (UO(2))(2)(OH)(2)(H(2)O)(2)(C(4)O(4)) (2; a = 12.909(5) A, b = 8.400(3) A, c = 10.322(4) A, beta = 100.056(7) degrees , monoclinic, C2/c) to two squarate-oxalate polymorphs with dimers in (UO(2))(2)(OH)(C(4)O(4))(C(2)O(4)).NH(4).H(2)O (3; a = 9.0601(7) A, b = 15.7299(12) A, c = 10.5108(8) A, beta = 106.394(1) degrees , monoclinic, P2(1)/n; and 4; a = 8.4469(6) A, b = 7.7589(5) A, c = 10.5257(7) A, beta = 105.696(1) degrees , monoclinic, P2(1)/m). The dominance at low pH of monomeric species and the increasing occurrence of oligomeric species with increasing pH suggests that uranyl hydrolysis, mUO(2)(2+) + nH(2)O right harpoon over left harpoon [(UO(2))(m)(OH)(n)](2m-n) + nH(+), has a significant role in the identity of the inorganic building unit. Additional factors that influence product assembly include in situ hydrolysis of squaric acid to oxalic acid, dynamic metal to ligand concentration, and additional binding modes resulting from the introduction of oxalate anions. These points and the effects of uranyl hydrolysis with changing pH are discussed in the context of the compounds presented herein.

  13. Structural evolution of a uranyl peroxide nano-cage fullerene: U60, at elevated pressures

    Science.gov (United States)

    Turner, K. M.; Lin, Y.; Zhang, F.; McGrail, B.; Burns, P. C.; Mao, W. L.; Ewing, R. C.

    2015-12-01

    U60 is a uranyl peroxide nano-cage that adopts a highly symmetric fullerene topology; it is topologically identical to C60. Several studies on the aqueous-phase of U60 clusters, [UO2(O2)(OH)]6060-, have shown its persistence in complex solutions and over lengthy time scales. Peroxide enhances corrosion of nuclear fuel in a reactor accident-uranyl peroxides often form near contaminated sites. U60 (Fm-3) crystallizes with approximate formula: Li68K12(OH)20[UO2(O2)(OH)]60(H2O)310. Here, we have used the diamond anvil cell (DAC) to examine U60 to understand the stability of this cluster at high pressures. We used a symmetric DAC with 300 μm culet diamonds and two different pressure-transmitting media: a mixture of methanol+ethanol and silicone oil. Using a combination of in situ Raman spectroscopy and synchrotron XRD, and electrospray ionization mass spectroscopy (ESI-MS) ex situ, we have determined the pressure-induced evolution of U60. Crystalline U60 undergoes an irreversible phase transition to a tetragonal structure at 4.1 GPa, and irreversibly amorphizes at 13 GPa. The amorphous phase likely consists of clusters of U60. Above 15 GPa, the U60 cluster is irreversibly destroyed. ESI-MS shows that this phase consists of species that likely have between 10-20 uranium atoms. Raman spectroscopy complements the diffraction measurements. U60 shows two dominant vibrational modes: a symmetric stretch of the uranyl U-O triple bond (810 cm-1), and a symmetric stretch of the U-O2-U peroxide bond (820 cm-1). As pressure is increased, these modes shift to higher wavenumbers, and overlap at 4 GPa. At 15 GPa, their intensity decreases below detection. These experiments reveal several novel behaviors including a new phase of U60. Notably, the amorphization of U60 occurs before the collapse of its cluster topology. This is different from the behavior of solvated C60 at high pressure, which maintains a hcp structure up to 30 GPa, while the clusters disorder. These results suggest

  14. Crystal chemistry of uranyl carboxylate coordination networks obtained in the presence of organic amine molecules

    Energy Technology Data Exchange (ETDEWEB)

    Mihalcea, Ionut; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS) - UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

    2014-03-15

    Three uranyl isophthalates (1,3-bdc) and two uranyl pyromellitates (btec) of coordination-polymer type were hydrothermally synthesized (200 C for 24 h) in the presence of different amine-based molecules [1,3-diaminopropane (dap) or dimethylamine (dma) originating from the in situ decomposition of N,N-dimethylformamide]. (UO{sub 2}){sub 2}(OH){sub 2}(H{sub 2}O)(1,3-bdc).H{sub 2}O (1) is composed of inorganic tetranuclear cores, which are linked to each other through the isophthalato ligand to generate infinite neutral ribbons, which are intercalated by free H{sub 2}O molecules. The compounds (UO{sub 2}){sub 1.5}(H{sub 2}O)(1,3-bdc){sub 2}.0.5H{sub 2}dap.1.5H{sub 2}O (2) and UO{sub 2}(1,3-bdc){sub 1.5}.0.5H{sub 2}dap.2H{sub 2}O (3) consist of discrete uranyl-centered hexagonal bipyramids connected to each other by a ditopic linker to form a single-layer network for 2 or a double-layer network for 3. The protonated diamine molecules are located between the uranyl-organic sheets and balance the negative charge of the layered sub-networks. The phase (UO{sub 2}){sub 2}O(btec).2Hdma.H{sub 2}O (4) presents a 2D structure built up from tetranuclear units, which consist of two central sevenfold coordinated uranium centers and two peripheral eightfold coordinated uranium centers. The connection of the resulting tetramers through the pyromellitate molecules generates an anionic layerlike structure, in which the protonated dimethylammonium species are inserted. The compound UO{sub 2}(btec).2Hdma (5) is also a lamellar coordination polymer, which contains isolated eightfold coordinated uranium cations linked through pyromellitate molecules and intercalated by protonated dimethylammonium species. In both phases 4 and 5, the btec linker has non-bonded carboxyl oxygen atoms, which preferentially interact with the protonated amine molecules through a hydrogen-bond network. The different illustrations show the structural diversity of uranyl-organic coordination polymers with organic

  15. Dynamic electrochemical measurement of chloride ions

    NARCIS (Netherlands)

    Abbas, Yawar; de Graaf, Derk B.; Olthuis, Wouter; van den Berg, Albert

    2016-01-01

    This protocol describes the dynamic measurement of chloride ions using the transition time of a silver silver chloride (Ag/AgCl) electrode. Silver silver chloride electrode is used extensively for potentiometric measurement of chloride ions concentration in electrolyte. In this measurement,

  16. Producing ammonium chloride from coal or shale

    Energy Technology Data Exchange (ETDEWEB)

    Christenson, O L

    1921-02-25

    Process of producing ammonium chloride consists of mixing the substance to be treated with a chloride of an alkali or alkaline earth metal, free silica, water and free hydrochloric acid, heating the mixture until ammonium chloride distills off and collecting the ammonium chloride.

  17. 21 CFR 184.1138 - Ammonium chloride.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ammonium chloride. 184.1138 Section 184.1138 Food... Specific Substances Affirmed as GRAS § 184.1138 Ammonium chloride. (a) Ammonium chloride (NH4Cl, CAS Reg. No. 12125-02-9) is produced by the reaction of sodium chloride and an ammonium salt in solution. The...

  18. 21 CFR 173.375 - Cetylpyridinium chloride.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Cetylpyridinium chloride. 173.375 Section 173.375... CONSUMPTION Specific Usage Additives § 173.375 Cetylpyridinium chloride. Cetylpyridinium chloride (CAS Reg. No....1666 of this chapter, at a concentration of 1.5 times that of cetylpyridinium chloride. (c) The...

  19. 21 CFR 184.1622 - Potassium chloride.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Potassium chloride. 184.1622 Section 184.1622 Food... Specific Substances Affirmed as GRAS § 184.1622 Potassium chloride. (a) Potassium chloride (KCl, CAS Reg... levels not to exceed current good manufacturing practice. Potassium chloride may be used in infant...

  20. 21 CFR 184.1426 - Magnesium chloride.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Magnesium chloride. 184.1426 Section 184.1426 Food... Specific Substances Affirmed as GRAS § 184.1426 Magnesium chloride. (a) Magnesium chloride (MgC12·6H2O, CAS... hydrochloric acid solution and crystallizing out magnesium chloride hexahydrate. (b) The ingredient meets the...

  1. 46 CFR 151.50-34 - Vinyl chloride (vinyl chloride monomer).

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Vinyl chloride (vinyl chloride monomer). 151.50-34... chloride (vinyl chloride monomer). (a) Copper, aluminum, magnesium, mercury, silver, and their alloys shall... equipment that may come in contact with vinyl chloride liquid or vapor. (b) Valves, flanges, and pipe...

  2. 40 CFR 61.65 - Emission standard for ethylene dichloride, vinyl chloride and polyvinyl chloride plants.

    Science.gov (United States)

    2010-07-01

    ... dichloride, vinyl chloride and polyvinyl chloride plants. 61.65 Section 61.65 Protection of Environment... AIR POLLUTANTS National Emission Standard for Vinyl Chloride § 61.65 Emission standard for ethylene dichloride, vinyl chloride and polyvinyl chloride plants. An owner or operator of an ethylene dichloride...

  3. Electrochemical studies on the reduction of uranyl ions in nitric acid-hydrazine media at platinum electrode

    International Nuclear Information System (INIS)

    Mishra, Satyabrata; Sini, K.; Mallika, C.; Kamachi Mudali, U.; Jagadeeswara Rao, Ch.

    2015-01-01

    Production of uranous nitrate with good conversion efficiency is one of the major steps in the aqueous reprocessing of spent fuels of nuclear reactors, as U(IV) is used for the separation of Pu from U by the selective reduction of Pu(IV) into practically non-extractable Pu(III) in aqueous streams. Electro-reduction of uranyl ions has the advantage of not introducing corrosive chemicals into the process stream. High current efficiency with maximum conversion of U(VI) to U(IV) can be achieved in continuous as well as batch mode electro-reduction, if the process is voltage-controlled rather than current controlled. As potentiostatic studies reveal the mechanism of reduction of uranyl ions in potential controlled electrolysis, the reduction behavior of uranyl ions (UO 2 2+ ) in nitric acid and nitric acid-hydrazine media were investigated by Cyclic Voltammetric (CV) and Chronopotentiometric (CP) techniques using platinum working electrode at 298 K. Heterogeneous electron transfer rate constant (ks) for uranyl reduction was estimated at a very low concentration of nitric acid (0.05 M) using Klinger and Kochi equation. Values of the diffusion coefficients were determined as a function of acidity with and without hydrazine. Reduction of uranyl ions was found to be under kinetic as well as diffusion control when the concentration of nitric acid was 0.05 M and in the absence of hydrazine. However, as the acidity of the supporting electrolyte increased, the reduction was purely under kinetic control. (author)

  4. Uranyl sensor based on a N,N?-bis(salicylidene)-2-hydroxy-phenylmethanediamine and multiwall carbon nanotube electrode

    International Nuclear Information System (INIS)

    Sayed Mehdi Ghoreishi; Mohsen Behpour; Samaneh Mazaheri; Hossein Naeimi

    2012-01-01

    The electrochemical determination of uranyl was investigated by using carbon paste electrode modified with a Schiff base namely N,N'-bis(salicylidene)-2-hydroxy-phenylmethanediamine (SHPMD/CPE) and also in the presence of carbon nanotube (SHPMD/CNT/CPE). The both modified electrodes displayed an irreversible peak at E pa = 0.798 V versus Ag/AgCl. The electrocatalytic reduction of uranyl has been studied on SHPMD/CNT/CPE, using cyclic and differential pulse voltammetry, chronocoulometry and linear sweep techniques. Electrochemical parameters including the diffusion coefficient (D), the electron transfer coefficient (α), the ionic exchange current (i) and the redox reaction rate constant (K) were determined for the reduction of uranyl on the surface of the modified electrodes. Linear range concentration is 0.002-0.6 μmol L -1 and the detection limit of uranyl is 0.206 nmol L -1 . The proposed method was used to detect uranyl in natural waters and good recovery was achieved. (author)

  5. 21 CFR 184.1297 - Ferric chloride.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ferric chloride. 184.1297 Section 184.1297 Food and... Substances Affirmed as GRAS § 184.1297 Ferric chloride. (a) Ferric chloride (iron (III) chloride, FeC13, CAS Reg. No. 7705-08-0) may be prepared from iron and chlorine or from ferric oxide and hydrogen chloride...

  6. Reaction of calcium chloride with alkali metal chlorides in melts

    International Nuclear Information System (INIS)

    Savin, V.D.; Mikhajlova, N.P.

    1984-01-01

    Thermochemical characteristics of CaCl 2 reaction with sodium, potassium, rubidium and cesium chlorides in melts at 890 deg C are determined. The values of formation enthalpies of infinitely diluted by CaCl 2 solutions (ΔH) in the chloride row increase from -22 in NaCl to -47 kJ/mol of CaCl 2 in CsCl. With increasing the concentration of calcium chloride in the solution the ΔH values decrease. The regularities of separation from the solution of the CaCl 2 -CsCl system at 890 deg C of the CaCl 2 x CsCl in solid are studied. Formation enthalpies under the given conditions constitutes -70+-3 kJ/mol

  7. Thermal decomposition of uranyl nitrate hexahydrate. Study of intermediate reaction products; Decomposition thermique du nitrate d'uranyle hexahydrate etude des intermediaires de cette decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Chottard, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1970-07-01

    The thermal decomposition of uranyl nitrate hexahydrate has been carried but at constant pressure and constant rate of reaction. The following intermediary products have been shown to exist and isolated: UO{sub 2}(NO{sub 3}){sub 2}.3H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}. 2H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}. H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2} and UO{sub 3}. These products, together with the hexahydrate UO{sub 2} (NO{sub 3}){sub 2}.6H{sub 2}O, have been studied by: - X-ray diffraction, using the Debye-Scherrer method.- infra-red spectrography: determination of the type of bonding for the water and the nitrate groups. - nuclear magnetic resonance: study of the mobility of water molecules. The main results concern: - the water molecule bonds in the series of hydrates with 6.3 and 2 H{sub 2}O. - isolation and characterization of uranyl nitrate monohydrate, together with the determination of its molecular structure. - the mobility of the water molecules in the series of the hydrates with 6.3 and 2 H{sub 2}O. An analysis is made of the complementary results given by infra-red spectroscopy and nuclear magnetic resonance; they are interpreted for the whole of the hydrate series. [French] La decomposition thermique du nitrate d'uranyle hexahydrate a ete effectuee en operant a pression et vitesse de decomposition constantes. Les produits intermediaires suivants ont ete mis en evidence et isoles: UO{sub 2}(NO{sub 3}){sub 2}, 3H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}, 2H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2},H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2} et UO{sub 3}. Ces composes, ainsi que l'hexahydrate UO{sub 2}(NO{sub 3} ){sub 2}, 6H{sub 2}O ont ete etudies par: - diffraction des rayons X, selon la methode Debye-Scherrer.- spectrographie infra-rouge: determination des modes de liaison de l'eau et des groupements nitrate. - resonance magnetique nucleaire: etude de la mobilite des molecules d'eau. Les principaux resultats portent sur: - les liaisons des molecules d'eau dans la

  8. U(VI) speciation and reduction in acid chloride fluids in hydrothermal conditions: from transport to deposition of uranium in unconformity-related deposits

    International Nuclear Information System (INIS)

    Dargent, Maxime

    2014-01-01

    Circulations of acidic chloride brines in the earth's crust are associated with several types of uranium deposits, particularly unconformity-related uranium (URU) deposits. The spectacular high grade combined with the large tonnage of these deposits is at the origin of the key questions concerning the geological processes responsible for U transport and precipitation. The aim of this work is to performed experimental studies of U(VI) speciation and its reduction to U(IV) subsequently precipitation to uraninite under hydrothermal condition. About uranium transport, the study of U(VI) speciation in acidic brines at high temperature is performed by Raman and XAS spectroscopy, showing the coexistence of several uranyl chloride complexes UO 2 Cl n 2-n (n = 0 - 5). From this study, complexation constants are proposed. The strong capability of chloride to complex uranyl is at the origin of the transport of U(VI) at high concentration in acidic chloride brines. Concerning uranium precipitation, the reactivity of four potential reductants under conditions relevant for URU deposits genesis is investigated: H 2 , CH 4 , Fe(II) and the C-graphite. The kinetics of reduction reaction is measured as a function of temperature, salinity, pH and concentration of reductant. H 2 , CH 4 , and the C-graphite are very efficient while Fe(II) is not able to reduce U(VI) in same conditions. The duration of the mineralizing event is controlled by (i) the U concentration in the ore-forming fluids and (ii) by the generation of gaseous reductants, and not by the reduction kinetics. These mobile and efficient gaseous reductant could be at the origin of the extremely focus and massive character of ore in URU deposits. Finally, first partition coefficients uraninite/fluid of trace elements are obtained. This last part opens-up new perspectives on (i) REE signatures interpretation for a given type of uranium deposit (ii) and reconstruction of mineralizing fluids composition. (author) [fr

  9. Constraining the Timescales of Rehydration in Nominally Anhydrous Minerals Using 3D Numerical Diffusion Models

    Science.gov (United States)

    Lynn, K. J.; Warren, J. M.

    2017-12-01

    Nominally anhydrous minerals (NAMs) are important for characterizing deep-Earth water reservoirs, but the water contents of olivine (ol), orthopyroxene (opx), and clinopyroxene (cpx) in peridotites generally do not reflect mantle equilibrium conditions. Ol is typically "dry" and decoupled from H in cpx and opx, which is inconsistent with models of partial melting and/or diffusive loss of H during upwelling beneath mid-ocean ridges. The rehydration of mantle pyroxenes via late-stage re-fertilization has been invoked to explain their relatively high water contents. Here, we use sophisticated 3D diffusion models (after Shea et al., 2015, Am Min) of H in ol, opx, and cpx to investigate the timescales of rehydration across a range of conditions relevant for melt-rock interaction and serpentinization of peridotites. Numerical crystals with 1 mm c-axis lengths and realistic crystal morphologies are modeled using recent H diffusivities that account for compositional variation and diffusion anisotropy. Models were run over timescales of minutes to millions of years and temperatures from 300 to 1200°C. Our 3D models show that, at the high-T end of the range, H concentrations in the cores of NAMs are partially re-equilibrated in as little as a few minutes, and completely re-equilibrated within hours to weeks. At low-T (300°C), serpentinization can induce considerable diffusion in cpx and opx. H contents are 30% re-equilibrated after continuous exposure to hydrothermal fluids for 102 and 105 years, respectively, which is inconsistent with previous interpretations that there is no effect on H in opx under similar conditions. Ol is unaffected after 1 Myr due to the slower diffusivity of the proton-vacancy mechanism at 300°C (2-4 log units lower than for opx). In the middle of the T range (700-1000°C), rehydration of opx and cpx occurs over hours to days, while ol is somewhat slower to respond (days to weeks), potentially allowing the decoupling observed in natural samples to

  10. High temperature proton exchange membranes prepared from epoxycyclohexylethyltrimethoxysilane and amino trimethylene phosphonic acid as anhydrous proton conductors

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Cheng [Department of Polymer Materials and Engineering, School of Material Science and Engineering, Wuhan University of Technology, No. 122 Luoshi Road, Wuhan 430070 (China); Shen, Chunhui, E-mail: shenchunhui@whut.edu.cn [Department of Polymer Materials and Engineering, School of Material Science and Engineering, Wuhan University of Technology, No. 122 Luoshi Road, Wuhan 430070 (China); Kong, Gengjin; Gao, Shanjun [Department of Polymer Materials and Engineering, School of Material Science and Engineering, Wuhan University of Technology, No. 122 Luoshi Road, Wuhan 430070 (China)

    2013-06-15

    High temperature anhydrous proton exchange membranes based on phosphonic acid were prepared from epoxycyclohexylethyltrimethoxysilane (EHTMS) and amino trimethylene phosphonic acid (ATMP) by sol–gel process. The structures and properties of membranes with different phosphonic acid content were extensively characterized by FTIR, TG-DSC and XRD. Their proton conductivity under dry condition was also investigated under different temperature. The results show that the proton conductivity of the prepared membranes strongly depends on temperature, and the proton conductivity ranges from 8.81 × 10{sup −5} S cm{sup −1} at 20 °C to 4.65 × 10{sup −2} S cm{sup −1} at 140 °C under anhydrous condition. It indicates that the increasing temperature is favorable for congregating of the grafted–PO{sub 3}H{sub 2} and increasing of the proton mobility. In addition, from the results of AFM images, it was confirmed that the continuous distribution of phosphonic acid groups is favorable for the formation of the proton transport channel, which can significantly enhance the proton conductivity of the membranes. Highlights: ► Hybrid membranes of Epoxycyclohexylethyltrimethoxysilane and Amino trimethylene phosphonic acid. ► The proton conductivity is 4.65 × 10{sup −2} S cm{sup −1} at 140 °C under anhydrous condition. ► Continuous uniform distributions of phosphonic acid groups can be observed by AFM. ► There could be hydrogen bond network within high temperature membranes.

  11. Derivation of an empirical formula for determining water content of mixed uranyl nitrate-thorium nitrate solutions

    International Nuclear Information System (INIS)

    Min, Duck Kee; Choi, Byung Il; Ro, Seung Gy; Eom, Tae Yoon; Kim, Zong Goo

    1986-01-01

    Densities of a large number of mixed uranyl nitrate-thorium nitrate solutions were measured with pycnometer. By the least squares analysis of the experimental result, an empirical formula for determining water content of mixed uranyl nitrate-thorium nitrate solutions as functions of uranium concentration, thorium concentration and nitric acid normality is derived; W=1.0-0.3580 C u -0.4538 C Th -0.0307H + where W, C u , C Th , and H + stand for water content(g/cc), uranium concentration (g/cc), thorium concentration(g/cc), and nitric acid normality, respectively. Water contents of the mixed uranyl nitrate-thorium nitrate solutions are calculated by using the empirical formular, and compared with the values calculated by Bouly's equation in which an additional data, solution density, is required. The two results show good agreements within 2.7%. (Author)

  12. Application of membrane LaF3 electrode in the determination of stability constants of Uranyl Fluoride complex in solution

    International Nuclear Information System (INIS)

    Muzakky; Iswani GS; Mintolo

    1996-01-01

    A membrane electrode LaF 3 has been applied in the determination of uranyl fluoride complex stability constant in solution. The determination is based on the detection of free F ion in solution as a result of hydrolysis reaction (process) of uranyl ions into the uranyl hydroxide form at low pH. The experiment results showed that there was no effect of ammonium carbonate 2 M titran, flow rate on the electrode response. The F release is optimum at pH 1. The free F ion in solution is calculated from the standard curve at pH 1, after the fluoride concentration at the same pH has been corrected. Using the plot of average number of ligand binding (n) versus minus log of free ligand (-log F) the value of β1 = 4.4, β2 = 7.48, β3=9.73, and β4 = 11.67

  13. Electrochemical Chloride extraction using external electrodes?

    DEFF Research Database (Denmark)

    Ottosen, Lisbeth M.; Pedersen, Anne Juul

    2006-01-01

    Electrochemical methods for the removal of chloride from concrete have been developed and the methods are primarily designed for situations where corrosion has started due to an increased chloride concentration in the vicinity of the reinforcement. In these methods the reinforcement is used...... as the cathode. However, some unwanted side effects can occur, including alkali-silica reaction and in some cases hydrogen embrittlement. It is also suggested also to use electrochemical chloride extraction in a preventive way in constructions where chloride induced corrosion is likely to be a problem after...... a period of time, i.e. remove the chlorides before the chloride front reaches the reinforcement. If the chlorides are removed from outer few centimetres from the surface, the chloride will not reach the reinforcement and cause damage. By using the electrochemical chloride removal in this preventive way...

  14. Effect of uranyl nitrate and free acid concentration in feed solution of gelation on UO2 kernel quality

    International Nuclear Information System (INIS)

    Masduki, B.; Wardaya; Widarmoko, A.

    1996-01-01

    An investigation on the effect of uranium and free nitric acid concentration of uranyl nitrate as feed of gelation process on quality of UO 2 kernel was done.The investigation is to look for some concentration of uranyl nitrate solutions those are optimum as feed for preparation of gelled UO 3 . Uranyl nitrate solution of various concentration of uranium (450; 500; 550; 600; 650; 700 g/l) and free nitric acid of (0.9; 1.0; 1.1 N) was made into feed solutions by adding urea and HMTA with mole ratio of urea/uranium and HMTA/uranium 2.1 and 2.0. The feed solutions were changed into spherical gelled UO 3 by dropping was done to get the optimum concentrations of uranyl nitrate solutions. The gelled UO 3 was soaked and washed with 2.5% ammonia solution for 17 hours, dried at 70 o C, calcined at 350 o C for 3 hours then reduced at 850 o C for 3 hours. At every step of the steps process the colour and percentage of well product of gelled UO 3 were noticed. The density and O/U ratio of end product (UO 2 kernel) was determined, the percentage of well product of all steps process was also determined. The three factor were used to chose the optimum concentration of uranyl nitrate solution. From this investigation it was concluded that the optimum concentration of uranyl nitrate was 600 g/l uranium with free nitric acid 0,9 - 1,0 N, the percentage of well product was 97% density of 6.12 - 4.8 g/cc and O/U ratio of 2.15 - 2.06. (author)

  15. DFT study of uranyl peroxo complexes with H2O, F-, OH-, CO3(2-), and NO3(-).

    Science.gov (United States)

    Odoh, Samuel O; Schreckenbach, Georg

    2013-05-06

    The structural and electronic properties of monoperoxo and diperoxo uranyl complexes with aquo, fluoride, hydroxo, carbonate, and nitrate ligands have been studied using scalar relativistic density functional theory (DFT). Only the complexes in which the peroxo ligands are coordinated to the uranyl moiety in a bidentate mode were considered. The calculated binding energies confirm that the affinity of the peroxo ligand for the uranyl group far exceeds that of the F(-), OH(-), CO3(2-), NO3(-), and H2O ligands. The formation of the monoperoxo complexes from UO2(H2O)5(2+) and HO2(-) were found to be exothermic in solution. In contrast, the formation of the monouranyl-diperoxo, UO2(O2)2X2(4-) or UO2(O2)2X(4-/3-) (where X is any of F(-), OH(-), CO3(2-), or NO3(-)), complexes were all found to be endothermic in aqueous solution. This suggests that the monoperoxo species are the terminal monouranyl peroxo complexes in solution, in agreement with recent experimental work. Overall, we find that the properties of the uranyl-peroxo complexes conform to well-known trends: the coordination of the peroxo ligand weakens the U-O(yl) bonds, stabilizes the σ(d) orbitals and causes a mixing between the uranyl π- and peroxo σ- and π-orbitals. The weakening of the U-O(yl) bonds upon peroxide coordination results in uranyl stretching vibrational frequencies that are much lower than those obtained after the coordination of carbonato or hydroxo ligands.

  16. The research of technology and equipment for a microwave denitration process of the uranyl nitrate solution

    International Nuclear Information System (INIS)

    Bao Weimin; Wang Xuejun; Ma Xuquan; Shi Miaoyi; Zhang Zhicheng; Bao Zhu Tian.

    1991-01-01

    In order to improve the present process of converting the plutonium nitrate into oxide powder in the nuclear fuel cycle, a new conversion process for the direct denitration using microwave heating has been developed. Microwave denitration is based on intramolecular polarization of a material in electric field and has no need of a process of heat transfer during microwave heating, so that the whole material can be heated quickly and uniformly. The thermal decomposition reactions of Pu, U, Th and RE nitrate have been analyzed and compared. The uranyl nitrate solution was chosen as imitative plutonium nitrate solution. The performance parameters ε r tanδ of U, Th and RE nitrate and oxide in microwave field were measured. The data obtained show that all of them could absorb microwave energy well and cause heating decomposition reactions. The microwave denitration test unit was designed and made. Denitration tests for rare-earths nitrate and uranyl nitrate solutions were performed. It could be completed in one step that the uranyl nitrate solution was evaporated, dryed and denitrated in a vessel. The denitrated products are a porous lump and easy to scrape off from the denitration vessel. The main forms of the products UO 3 ·0.8H 2 O and U 3 O 8 which have excellent powder properties. The capacity of the denitration unit is 1.3 kg UO 3 /h. According to the experimental results the simplicity, feasibility and good repeatability of the process have been fully proved. The unit operates easily and is adaptable to conversion of nitrate in nuclear fuel cycle. (author)

  17. Structural variability in uranyl-lanthanide hetero-metallic complexes with DOTA and oxalato ligands

    International Nuclear Information System (INIS)

    Thuery, P.

    2009-01-01

    Four novel 4f-5f hetero-metallic complexes could be obtained from the reaction of uranyl and lanthanide nitrates with DOTA (H 4 L) under hydrothermal conditions. In all cases, as in the previous examples reported, additional oxalato ligands are formed in situ. Variations in the stoichiometry of the final products and the presence of hydroxo ions in some cases appear to result in a large structural variability. In the two isomorphous complexes [(UO 2 ) 2 Ln 2 (L) 2 (C 2 O 4 )] with Ln = Sm(1) or Eu(2), the lanthanide ion is located in the N 4 O 4 site and is also bound to a carboxylate oxygen atom from a neighbouring unit, to give zigzag chains which are further linked to one another by [(UO 2 ) 2 (C 2 O 4 )] 2+ di-cations, resulting in the formation of a 3D framework. In [(UO 2 ) 4 Gd 2 (L) 2 (C 2 O 4 ) 3 (H 2 O) 6 ].2H 2 O (3), 2D bilayer subunits of the 'double floor' type with uranyl oxalate pillars are assembled into a 3D framework by other, disordered uranyl ions. [(UO 2 ) 2 Gd(L)(C 2 O 4 )(OH)].H 2 O (4) is a 2D assembly in which cationic {[(UO 2 ) 2 (C 2 O 4 )(OH)] + } n chains are linked to one another by the [Gd(L)] - groups. The most notable feature of this compound is the environment of the 4f ion, which is eight-coordinate and twisted square anti-prismatic (TSA'), instead of nine-coordinate mono-capped square anti-prismatic (SA), as generally observed in DOTA complexes of gadolinium(III) and similarly-sized ions. (author)

  18. Effect of temperature on the mechanisms of interaction between uranyl ion and zirconium oxo-phosphate

    International Nuclear Information System (INIS)

    Almazan Torres, Maria Guadalupe

    2007-01-01

    Uranium sorption onto Zr 2 O(PO 4 ) 2 has been studied between 298 K and 363 K, in 0.1 M NaClO 4 medium. Potentiometric titrations were realized to determine temperature dependency of the acid-base properties (pH pcn , acidity constants). Classical batch experiments were performed at different temperatures. The sorption experiments revealed that the uranium sorption onto Zr 2 O(PO 4 ) 2 is favoured with the temperature. Structural characterization of the surface complexes was performed by both Time-Resolved Laser-Induced Fluorescence (TRLIF) and EXAFS spectroscopy. The TRLIF measurements vs. temperature revealed two uranyl surface complexes. No influence of the temperature onto the nature surface complex was observed. The EXAFS analysis showed a splitting of the equatorial oxygen atoms in two shells, corresponding to uranyl bidentate, inner-sphere complexes. The obtained structural uranyl surface complex information was used to simulate (using a constant capacitance model) the sorption edges. The proposed complexes equilibrium model consists of the following surface complexes: (≡ZrOH) 2 UO 2 2+ and (≡PO) 2 UO 2 . Besides the stability constants for the surface complexes, the thermodynamic parameters ΔH 0 and ΔS 0 were determined using the van't Hoff equation. The enthalpy values associated to the U(VI) retention onto Zr 2 O(PO 4 ) 2 , determined by the temperature dependence of the stability constants, testify that the formation of the complex (≡PO) 2 UO 2 (55 kJ/mol) is endothermic, while no influence of the temperature was observed for the formation of the complex (≡ZrOH) 2 UO 2 2+ . The adsorption reaction of the last complex is then driven by entropy. In addition, calorimetric measurements of uranium sorption onto Zr 2 O(PO 4 ) 2 were carried out to directly quantify the enthalpy associated to the retention processes. (author)

  19. Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

    Energy Technology Data Exchange (ETDEWEB)

    Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L. [Department of Chemistry, The George Washington University, Washington, DC (United States)

    2016-01-15

    The syntheses and crystal structures of six new compounds containing the UO{sub 2}{sup 2+} cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2{sup '}:6{sup '},2''-terpyridine (terpy), 4{sup '}-chloro-2,2{sup '}:6{sup '},2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

    Energy Technology Data Exchange (ETDEWEB)

    Medvedkov, Ya. A.; Serezhkina, L. B., E-mail: Lserezh@samsu.ru [Samara State University (Russian Federation); Grigor’ev, M. S. [Russian Academy of Sciences, Frumkin Institute of Physical Chemistry and Electrochemistry (Russian Federation); Serezhkin, V. N. [Samara State University (Russian Federation)

    2016-05-15

    Two new malonate-containing uranyl complexes with carbamide of the formulas [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}] (I) and [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 3}] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO{sub 2}(C{sub 2}O{sub 4})(Urea){sub 3}] (III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}]{sub ∞} belonging to the crystal-chemical group AT{sup 11}M{sub 2}{sup 1} (A = UO{sub 2}{sup 2+}, T{sup 11} = C{sub 3}H{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea) of uranyl complexes. Crystals II and III are composed of the molecular complexes [UO{sub 2}(L)(Urea){sub 3}], where L = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, belonging to the crystal-chemical group AB{sup 01}M{sub 3}{sup 1} (A = UO{sub 2}{sup 2+}, B{sup 01} = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi–Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.

  1. Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

    International Nuclear Information System (INIS)

    Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L.

    2016-01-01

    The syntheses and crystal structures of six new compounds containing the UO 2 2+ cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2 ' :6 ' ,2''-terpyridine (terpy), 4 ' -chloro-2,2 ' :6 ' ,2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Spectropolarimetric analysis. Communication 14. Determination of uranyl with d-tartaric acid

    Energy Technology Data Exchange (ETDEWEB)

    Bakalov, V D; Dunina, V V; Potapov, V M [Moskovskij Gosudarstvennyj Univ. (USSR)

    1982-02-01

    The possibility has been shown of improving the sensitivity and precision of determination of uranium (6) in the form of its tartrate complex by using spectropolarimetry instead of polarimetry and circular dichroism instead of optical rotatory dispersion. The method makes it possible to reduce reagent consumption, to expand a range of uranium(6) concentration, which could be determined, due to changes of the cell length and reading range. On the basis of the circular dichroism spectrum of the uranyl-tartrate complex, its symmetry has been estimated to be Dsub(4h) with the coordination number of four on the equatorial plane.

  3. Study on the transport behavior of uranyl nitrate in aqueous and non-aqueous systems

    International Nuclear Information System (INIS)

    Roesel, B.

    1985-01-01

    The analytical ultracentrifuge has proven itself through diffusion measurements to be well suited for studying radioactive compounds. In the framework of this paper the extent to which the UV and schlieren optics of an analytical ultracentrifuge can be used for extraction-kinetic tests was tested. With this method there is also the possibility of determining the distribution coefficients right at the phase boundary. The results show the good possibility of application of the absorption and schlieren optics to the study of the transport behavior of uranyl nitrate in practice oriented solutions. (orig.) [de

  4. Skin contamination resulting from an uranyl nitrate burn. An incident study

    International Nuclear Information System (INIS)

    Quesne, B.; Auriol, B.; Berard, P.; Chalabreysse, J.

    1993-01-01

    The authors describe the circumstances of a burn incident on hand by a mixture of diluted nitric acid and uranyl nitrate. The burn is located on the left hand fingers. After important washings uranium remains on the fingers. During about ten days, the worker is examined and the therapy is going on till the total radioactivity disappearance. Urine collection of twenty four hours is prescribed during the treatment. The whole activity is kept on the burnt skin. The quick desquamation is the elimination way of the skin retention. 6 refs., 3 figs., 4 tabs

  5. Development of a reduction process of ammonium uranyl carbonate to uranium dioxide in a fluidized bed

    International Nuclear Information System (INIS)

    Gomes, R.P.; Riella, H.G.

    1990-07-01

    Laboratory development of ammonium uranyl carbonate (AUC) reduction to uranium dioxide (UO 2 ) using fluidized bed furnace technique is described. The reaction is carried out at 500-550 0 C using hydrogen, liberated from cracking of ammonia, as a reducing agent. As the AUC used is obtained from uranium hexafluoride (UF 6 ) it contains considerable amount of fluoride (approx. 500μg/g) as contaminant. The presence of fluoride leads to high corrosion rates and hence the fluoride concentration is reduced by pyrohydrolisis of UO 2 . Physical and Chemical properties of the final product (UO 2 ) obtained were characterized. (author) [pt

  6. U3O8 powder from uranyl-loaded cation exchange resin

    International Nuclear Information System (INIS)

    Mosley, W.C.

    1985-01-01

    Large batches of U 3 O 8 , suitable for powder metallurgy fabrication of Al-U 3 O 8 cores for reactor fuel tubes, have been produced by deep-bed calcination of granular uranyl-loaded macroporous sulfonate cation exchange resin at 900 to 950 0 C in air. Deep-bed calcination is the backup process for the reference process of rotary calcination and sintering. These processes are to be used for recycling uranium, and to produce U 3 O 8 in the Fuel Production Facility to be built at the Savannah River Plant. 2 refs., 6 figs

  7. Interfacial Interaction of Titania Nanoparticles and Ligated Uranyl Species: A Relativistic DFT Investigation.

    Science.gov (United States)

    Zhao, Hong-Bo; Zheng, Ming; Schreckenbach, Georg; Pan, Qing-Jiang

    2017-03-06

    To understand interfacial behavior of actinides adsorbed onto mineral surfaces and unravel their structure-property relationship, the structures, electronic properties, and energetics of various ligated uranyl species adsorbed onto TiO 2 surface nanoparticle clusters (SNCs) were examined using relativistic density functional theory. Rutile (110) and anatase (101) titania surfaces, experimentally known to be stable, were fully optimized. For the former, models studied include clean and water-free Ti 27 O 64 H 20 (dry), partially hydrated (Ti 27 O 64 H 20 )(H 2 O) 8 (sol) and proton-saturated [(Ti 27 O 64 H 20 )(H 2 O) 8 (H) 2 ] 2+ (sat), while defect-free and defected anatase SNCs involving more than 38 TiO 2 units were considered. The aquouranyl sorption onto rutile SNCs is energetically preferred, with interaction energies of -8.54, -10.36, and -2.39 eV, respectively. Energy decomposition demonstrates that the sorption is dominated by orbital attractive interactions and modified by steric effects. Greater hydrogen-bonding involvement leads to increased orbital interactions (i.e., more negative energy) from dry to sol/sat complexes, while much larger steric interaction in the sat complex significantly reduces the sorption interaction (i.e., more positive energy). For dry SNC, adsorbates were varied from aquo to aquo-carbonato, to carbonato, to hydroxo uranyl species. Longer U-O surf /U-Ti distances and more positive sorption energies were calculated upon introducing carbonato and hydroxo ligands, indicative of weaker uranyl sorption onto the substrate. This is consistent with experimental observations that the uranyl sorption rate decreases upon raising solution pH value or adding carbon dioxide. Anatase SNCs adsorbing aquouranyl are even more exothermic, because more bonds are formed than in the case of rutile. Moreover, the anatase sorption can be tuned by surface defects as well as its Ti and O stoichiometry. All the aquouranyl-SNC complexes show similar

  8. Development of fluidized-bed furnace for thermal treatment of ammonium uranyl carbonate

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, U C; Anuradha, M; Meena, R [Nuclear Fuel Complex, Hyderabad (India)

    1994-06-01

    At present the ammonium uranyl carbonate (AUC) route is developed at a scale of 10 kg/day of UO{sub 2}. This UO{sub 2} is directly compactible and sinterable to densities of 10.55-10.65 gm/cc. The equipment developed include precipitation tank with filtration and methanol washing and fluidized bed furnaces for thermal treatment of AUC and U{sub 3}O{sub 8}. During the design and development of these furnaces many experiments were conducted to study fluidization of AUC powder. In this paper the findings of these studies are presented. (author). 3 refs., 4 figs., 3 tabs.

  9. Effect of n-octanol on -uranyl extraction by tri-n-octylammonium sulfate

    International Nuclear Information System (INIS)

    Ochkin, A.V.; Kudrov, A.N.

    1984-01-01

    The effect of n-octanol on the extraction of uranyl sulfate by solutions of tri-n-octylamine sulfate in benzene has been studied. With the increase of alcohol concentration the coefficient of uranium distribution passes through the maximum. At low alcohol concentrations a decrease in water content in the organic phase is observed. It is shown that the increase in ammonium salt activity in replacement of part of hydrate At high alcohol concentration the decrease in uranium distribution coefficients is observed, which is related to TOA sulfate solvation by alcohol

  10. Benchmark calculation for water reflected STACY cores containing low enriched uranyl nitrate solution

    International Nuclear Information System (INIS)

    Miyoshi, Yoshinori; Yamamoto, Toshihiro; Nakamura, Takemi

    2001-01-01

    In order to validate the availability of criticality calculation codes and related nuclear data library, a series of fundamental benchmark experiments on low enriched uranyl nitrate solution have been performed with a Static Experiment Criticality Facility, STACY in JAERI. The basic core composed of a single tank with water reflector was used for accumulating the systematic data with well-known experimental uncertainties. This paper presents the outline of the core configurations of STACY, the standard calculation model, and calculation results with a Monte Carlo code and JENDL 3.2 nuclear data library. (author)

  11. Thermal Analysis of the Decomposition of Ammonium Uranyl Carbonate (AUC) in Different Atmospheres

    DEFF Research Database (Denmark)

    Hälldahl, L.; Sørensen, Ole Toft

    1979-01-01

    The intermediate products formed during thermal decomposition of ammonium uranyl carbonate (AUC) in different atmospheres, (air, helium and hydrogen) have been determined by thermal analysis, (TG, and DTA) and X-ray analysis. The endproducts observed are U3O8 and UO2 in air/He and hydrogen, respe......, respectively. The following intermediate products were observed in all atmospheres: http://www.sciencedirect.com.globalproxy.cvt.dk/cache/MiamiImageURL/B6THV-44K80TV-FB-1/0?wchp=dGLzVlz-zSkWW X-ray diffraction analysis showed that these phases were amorphous....

  12. Recovery of uranium from uranyl nitrate raffinate. Contributed Paper PE-06

    International Nuclear Information System (INIS)

    Anilkumar Reddy, A.M.; Shiva Kumar, M.; Varadan, K.M.K.; Babaji, P.; Sairam, S. Sheela; Saibaba, N.

    2014-01-01

    At New Uranium Oxide Fuel Plant, NUOFP(O) of Nuclear Fuel Complex (NFC), the Uranyl Nitrate Raffinate (UNR) generated during solvent extraction process is washed with Treated Lean Solvent(TLS) to recover residual U. Earlier this UNR consisting of 0.5-1 gm/l and 2.5 FA was neutralised with vapour ammonia. The slurry was then filtered over pre coat drum filter and the resultant Uranyl Nitrate Raffinate cake (UNRC) was stored in polyethylene lined MS drums. The valuable U was thus being locked up in UNRC. Also, the storage of UNRC drums required lot of floor space which have to be repacked frequently to contain the radioactivity. Hence the need has come to avoid the generation of UNRC and the recovery of U from the already generated UNRC. The generation of UNRC was avoided by developing alternate process of UNR treatment with Treated Lean Solvent for the removal of residual U and the resulting Acidic Raffinate Slurry (ARS) is disposed. The Uranium recovery from UNRC is done by dissolving the cake in Uranyl Nitrate Raffinate solution to leach the hexavalent Uranium by utilizing the free acidity in UNR. The leaching time is about six hours and the uranium forms uranyl nitrate. The resulting leach solutions are relatively dilute but complex acidic nitrate solutions containing wide variety of ions. Metallic ions commonly present include uranium, iron, magnesium, aluminium, sodium, calcium etc. The uranium concentration is normally 1-1.5 g/L. This uranium is separated by solvent extraction. The active agent in solvent extraction is Tri Butyl Phosphate in kerosene that can selectively extract uranium into an organic complex which is insoluble in aqueous. The organic used for extraction is Treated Lean Solvent in the quality of freshly prepared solvent and the resulting Acidic Raffinate Slurry is disposed by sale. The leaching of Uranium from UNRC was done in plant scale and about 1200 kgs of UNRC was successfully processed in trial batch. The paper deals with details of

  13. Uranyl(VI)-acetylacetonate coordination compounds with various N-heterocyclic ligands

    International Nuclear Information System (INIS)

    Kawasaki, Takeshi; Nishimura, Tatsuru; Kitazawa, Takafumi

    2010-01-01

    Seven uranyl(VI) complexes, [UO 2 (acac) 2 (L)] [L=4-methylpyridine (1), 4-ethylpyridine (2), 2,4-dimethylpyridine (3), (-)-nicotine (4), and imidazole (5)], [{UO 2 (acac) 2 } 2 -(4,4'-bipyridine)] (6), and [(2,2'-bipyridine) 2 H][UO 2 (acac)(NO 3 ) 2 ] (7) have been synthesized and characterized crystallographically. The coordination geometry of U has a UNO 6 pentagonal-bipyramidal coordination in 1-6, and a UO 8 hexagonal-bipyramidal coordination in 7. (author)

  14. Investigations on uranyl nitrate solubility in nitric acid in different concentrations at temperatures of 50C

    International Nuclear Information System (INIS)

    Deigele, E.

    1983-01-01

    The solubility of uranyl nitrate was studied in nitric acid solutions of different concentrations at a temperature of 5 0 C. This temperature was chosen with a view to using water as coolant and to facilitate the handling of the strong acid solutions. Accurate curves were established by a multitude of accurate measurements in the high concentration range. Further solubility curves can be derived from this basic curve. Some of the precipitates in the interesting regions of the solubility curve were analyzed. (orig./EF) [de

  15. Beryllium(II), manganese(II) and uranyl(VI)-salicylamide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Maurya, P L; Agarwala, B V; Dey, A K [Allahabad Univ. (India)

    1977-01-01

    The preparation, composition, general properties and i.r. absorption spectra of the solid chelates formed by salicylamide with beryllium(II), manganese(II) and uranyl(VI) are described. The complexes have been synthesized by refluxing a mixture of ethanolic solutions of the reactants (metal:ligand :: 1:2) for several hours in the presence of alkali. Attempts to isolate the complexes by the interaction of ethanolic solutions of the metal salts and the ligand in the absence of alkali did not succeed.

  16. Experience with a uranyl nitrate/uranium dioxide conversion pilot plant

    International Nuclear Information System (INIS)

    Arcuri, L.; Pietrelli, L.

    1984-01-01

    A plant for the precipitation of sinterable nuclear grade UO 2 powders is described in this report. The plant has been designed, built and set up by SNIA TECHINT. ENEA has been involved in the job as nuclear consultant. Main process steps are: dissolution of UO 2 powder or sintered UO 2 pellets, adjustment of uranyl nitrate solutions, precipitation of uranium peroxide by means of hydrogen peroxide, centrifugation of the precipitate, drying, calcination and reduction to uranium dioxide. The report is divided in two main section: the process description and the ''hot test'' report. Some laboratory data on precipitation of ammonium diuranate by means of NH 4 OH, are also reported

  17. Quenching of excited uranyl ion during its photochemical reduction by triphenylphosphine: Part III

    International Nuclear Information System (INIS)

    Sidhu, M.S.; Chahal, P.; Singh, R.J.

    1993-01-01

    Relative rates of bimolecular quenching of excited uranyl ion by some mono and di-substituted benzene derivatives have been measured during its photochemical reduction with triphenylphosphine. For the related compounds in a series it has been found that substituent groups enriching the aromatic π-electron cloud due to resonance stabilization, show an enhanced photophysical quenching action. The substituents decreasing the π-electron cloud and delocalization of positive charger over the benzene ring decrease the quenching action. (author). 16 refs., 2 figs., 1 tab

  18. Development of ammonium uranyl carbonate reduction to uranium dioxide using fluidized bed

    International Nuclear Information System (INIS)

    Gomes, R.P.; Riella, H.G.

    1988-01-01

    Laboratory development of Ammonium Uranyl Carbonate (AUC) reduction to uranium dioxide (UO 2 ) using fluidized bed furnace technique is described. The reaction is carried out at 500-550 0 C using hydrogen, liberated from cracking of ammonia, as a reducing agent. As the AUC used is obtained from uranium hexafluoride (UF 6 ) it contains considerable amounts of fluoride ( - 500μgF - /gTCAU) as contaminant. The presence of fluoride leads to high corrosion rates and hence the fluoride concentrations is reduced by pyrohydrolisis of UO 2 . Physical and Chemical proterties of the final product (UO 2 ) obtained were characterized. (author) [pt

  19. Photochemical methodologies for organic waste treatment: advanced oxidation process using uranyl ion with H2O2

    International Nuclear Information System (INIS)

    Naik, D.B.; Sarkar, S.K.; Mukherjee, T.

    2009-01-01

    Excited uranyl ion is able to degrade dyes such as thionine and methylene blue on irradiation with 254 nm/300 nm light. By adding H 2 O 2 along with uranyl ion, photodegradation takes place with visible light and also with enhanced rate. The hydroxyl radicals generated in the reoxidation of U(IV)/UO 2 + to UO 2 2+ are responsible for this enhanced degradation. The above advanced oxidation process (AOP) was applied to study the oxidation of 2-propanol to acetone. (author)

  20. Uranyl complexes of ν-polyketonates. Crystal and molecular structure of a mononuclear uranyl 1,3,5-triketonate and a novel trinuclear uranyl 1,3,5-triketonate with a trigonal-planar bridging oxide

    International Nuclear Information System (INIS)

    Lintvedt, R.L.; Heeg, M.J.; Ahmad, N.; Glick, M.D.

    1982-01-01

    Two uranyl complexes of 1,3,5-triketonate ligands have been crystallized and examined by X-ray diffraction techniques. The first is the mononuclear bis[1,5-diphenyl-1,3,5-pentanetrionato(1-)](methanol)dioxouranium(VI)-methanol,[UO 2 -(C 35 H 30 O 7 )(CH 3 OH)],UO 2 (H(DBA)) 2 (CH 3 OH).CH 3 OH, in which the uranium atom is bound to four enolic oxygens, two uranyl oxygens, and one methanolic oxygen. The triketonate ligands are in a cis configuration presumably due to the steric constraints of the methanol coordination. Crystal data are as follows: P2 1 /c, a = 9.932 (4), b = 30.29 (4), c = 11.671 (4) angstrom; ν = 103.03 0 , V = 3421 (2) angstrom 3 ; Z = 4, R 1 = 0.048, R 2 = 0.050. The second is a trinuclear UO 2 2 + anion containing a trigonal, tribridging oxide ion that results during attempts to prepare binuclear UO 2 2 + complexes of 1,3,5-triketonates. The compound bis(triethylammonium) tris(2,2',8,8'-tetramethyl-3,5,7-nonanetrionato)-μ 3 -oxo-tris(dioxo-uranate)(2-), [(C 2 H 5 ) 3 NH] 2 [U 3 O 6 (C 39 H 60 O 9 )O], [(C 2 H 5 ) 3 NH] 2 [(UO 2 ) 3 (DPA) 3 O], contains a nearly equilateral triangle of UO 2 2 + ions with a central O 2 - ion trigonally bonded to the three U atoms. One triketonate occupies each edge of the trangle with the central enolic oxygen bridging two U atoms and the terminal oxygens bound to one U atom. Each U is seven-coordinate in nearly pentagonal-bipyramidal geometry. Crystal data are as follows: C2/c, a = 27.90 (2), b = 15.65 (2), c = 31.81 (3) angstrom; ν = 107.8 (1) 0 , V = 13220 (20), angstrom 3 ; Z = 8, R 1 = 0.062, R 2 = 0.078

  1. Preparation and Characterization of High Purity Anhydrous β-Lactose from α-Lactose Monohydrate at Mild Temperature

    Directory of Open Access Journals (Sweden)

    Ana L. López-Pablos

    2018-01-01

    Full Text Available Lactose is a disaccharide of importance in humans dietary, food products, and the pharmaceutical industry. From the existing isomeric forms, β-lactose is rarely found in nature. Thus, in this work, a simple methodology to obtain anhydrous β-lactose (βL from α-lactose monohydrate (αL·H2O is presented. The αL·H2O powder was dispersed into a basic alcoholic solution (72 hours, at controlled conditions of temperature (27, 29, 31, and 32°C, without stirring. The slurry was dried at room temperature and characterized. Fourier transform infrared spectroscopy showed the formation of βL for the samples prepared at 29 and 32°C. Raman spectroscopy confirmed this result and suggested the occurrence of crystalline βL. Rietveld refinement of the X-ray diffraction patterns was employed to identify and quantify the composition of the isomers. The samples prepared at 29 and 31°C showed the formation of pure βL, while those at 27 and 32°C showed the presence of αL·H2O and a mixture of the two isomers, respectively. The morphology of the powders was studied by scanning electron microscopy, observing the formation of irregular shape αL·H2O particles and axe-like βL particles. Clearly, with this methodology, it was possible to obtain pure, crystalline, and anhydrous βL at mild temperature.

  2. Rhenium corrosion in chloride melts

    International Nuclear Information System (INIS)

    Stepanov, A.D.; Shkol'nikov, S.N.; Vetyukov, M.M.

    1989-01-01

    The results investigating rhenium corrosion in chloride melts containing sodium, potassium and chromium ions by a gravimetry potentials in argon atmosphere in a sealing quarth cell are described. Rhenium corrosion is shown to be rather considerable in melts containing CrCl 2 . The value of corrosion rate depending on temperature is determined

  3. Elicitation threshold of cobalt chloride

    DEFF Research Database (Denmark)

    Fischer, Louise A; Johansen, Jeanne D; Voelund, Aage

    2016-01-01

    : On the basis of five included studies, the ED10 values of aqueous cobalt chloride ranged between 0.0663 and 1.95 µg cobalt/cm(2), corresponding to 30.8-259 ppm. CONCLUSIONS: Our analysis provides an overview of the doses of cobalt that are required to elicit allergic cobalt contactdermatitis in sensitized...

  4. Mixed sodium nickel-manganese sulfates: Crystal structure relationships between hydrates and anhydrous salts

    Energy Technology Data Exchange (ETDEWEB)

    Marinova, Delyana M.; Zhecheva, Ekaterina N.; Kukeva, Rositsa R.; Markov, Pavel V. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Nihtianova, Diana D. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Stoyanova, Radostina K., E-mail: radstoy@svr.igic.bas.bg [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria)

    2017-06-15

    The present contribution provides new structural and spectroscopic data on the formation of solid solutions between hydrated and dehydrated sulfate salts of sodium-nickel and sodium-manganese in a whole concentration range: Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·yH{sub 2}O, 0≤ x≤1.0. Using powder XRD, electron paramagnetic resonance spectroscopy (EPR), IR and Raman spectroscopy it has been found that double sodium-nickel and sodium-manganese salts form solid solutions Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·4H{sub 2}O with a blödite-type of structure within a broad concentration range of 0≤x≤0.49, while the manganese rich compositions Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·2H{sub 2}O (0.97≤x≤1.0) crystallize in the kröhnkite-type of structure. The Ni-based blödites Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·4H{sub 2}O dehydrate between 140 and 260 °C into anhydrous salts Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}, 0≤ x≤0.44, with a structure where Ni{sub 1−x}Mn{sub x}O{sub 6} octahedra are bridged into pairs by edge- and corner sharing SO{sub 4}{sup 2−} groups. Both TEM and EPR methods show that the Ni{sup 2+} and Mn{sup 2+} ions are homogenously distributed over three crystallographic positions of the large monoclinic cell. The dehydration of the kröhnkite phase Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·2H{sub 2}O yields the alluaudite phase Na{sub 2+δ}Mn{sub 2-δ/2}(SO{sub 4}){sub 3}, where the Na-to-Mn ratio decreases and all Ni{sup 2+} dopants are released from the structure. The process of the dehydration is discussed in terms of structural aspects taking into account the distortion degree of the Ni,MnO{sub 6} and SO{sub 4} polyhedra. - Graphical abstract: Thermal dehydration of the blödite phase Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·4H{sub 2}O (0≤ x≤0.49) yields nickel-manganese sulfates Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2} (0≤ x≤0.44) with

  5. Sulfur Concentration at Sulfide Saturation in Anhydrous Silicate Melts at Crustal Conditions

    Science.gov (United States)

    Liu, Y.; Samaha, N.; Baker, D. R.

    2006-05-01

    The sulfur concentration in silicate melts at sulfide saturation (SCSS) was experimentally investigated in a temperature range from 1250°C to 1450°C and a pressure range from 500 MPa to 1 GPa in a piston-cylinder apparatus. The investigated melt compositions varied from rhyolitic to basaltic. All experiments were saturated with a FeS melt. Temperature was confirmed to have a positive effect on the SCSS and no measurable pressure effect was observed. Oxygen fugacity was controlled to be either near the carbon-carbon monoxide buffer or one log unit above the nickel-nickel oxide buffer, and found to positively affect the SCSS. A series of models were constructed to predict the SCSS as a function of temperature, pressure, melt composition, oxygen fugacity and sulfur fugacity of the system. The coefficients were obtained by the regression of experimental data from this study and from data in the literature. The best model found for the prediction of the SCSS is: ln S (ppm) = 996/T + 9.875 + 0.997 ln MFM + 0.1901 ln fO2 - 0.0722 (P/T) -0.115 ln f S2, where P is in bar, T is in K, and MFM is a compositional parameter describing the melt based upon cation mole fractions: MFM = [Na + K + 2 (Ca + Mg+ Fe2+)]/[Si × (Al + Fe3+)]. This model predicts the SCSS in anhydrous silicate melts from rhyolitic to basaltic compositions at crustal conditions from 1 bar to 1.25 GPa, temperatures from ~1200 to 1400 C, and oxygen fugacities between approximately two log units below the fayalite-quartz-magnetite buffer and one log unit above the nickel-nickel oxide buffer. For cases where the oxygen and sulfur fugacities can not be adequately estimated a simpler model also works acceptably: ln S (ppm) = -5328/T + 8.431 + 1.244 ln MFM - 0.01704(P/T) + ln aFeS, where aFeS is the activity of FeS in the sulfide melt and is well approximated by a value of 1. Additional experiments were performed on other basalts in a temperature range from 1250 C to 1450 C at 1 GPa to test the models. The model

  6. Contribution to the study of the evaporation of aqueous uranyl nitrate solutions; Contribution a l'etude de l'evaporation des solutions aqueuses de nitrate d'uranyle

    Energy Technology Data Exchange (ETDEWEB)

    Billy, J [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1967-05-15

    This work was carried out with a view to define the conditions under which is affected the concentration of aqueous uranyl nitrate solutions one of the steps in uranium extraction metallurgy. The first port is devoted to the experimental determination of the physical characteristics of aqueous uranyl nitrate solutions, from dilute to concentrated solutions. The second part of this work is devoted to the isothermal evaporation of solution a west ted-wall column; this chemical engineering study has been more particularly devoted to the definition of the influence of the dynamics of the liquid phase on the exchange of matter between the two phases in contact. (author) [French] La concentration par evaporation des solutions aqueuses de nitrate d'uranyle constitue une etape de la metallurgie de l'uranium dont ce travail a voulu preciser la connaissance. Dans ce but, une premiere partie a ete consacree a la determination experimentale de caracteristiques physiques des solutions aqueuses de nitrate d'uranyle, des solutions diluees aux solutions saturees. Dans une deuxieme partie, ce travail a porte sur l'evaporation isotherme des solutions dans une colonne a paroi mouillee; cette etude de genie chimique a ete plus particulierement orientee de facon a preciser l'influence de la dynamique de la phase liquide sur l'echange de matiere entre les deux phases en contact. (auteur)

  7. Surface Chloride Levels in Colorado Structural Concrete

    Science.gov (United States)

    2018-01-01

    This project focused on the chloride-induced corrosion of reinforcing steel in structural concrete. The primary goal of this project is to analyze the surface chloride concentration level of the concrete bridge decks throughout Colorado. The study in...

  8. Pharmacokinetics of vinyl chloride in the rat

    International Nuclear Information System (INIS)

    Bolt, H.M.; Laib, R.J.; Kappus, H.; Buchter, A.

    1977-01-01

    When rats are exposed to [ 14 C]vinyl chloride in a closed system, the vinyl chloride present in the atmosphere equilibrates with the animals' organism within 15 min. The course of equilibration could be determined using rats which had been given 6-nitro-1,2,3-benzothiadiazole. This compound completely blocks metabolism of vinyl chloride. The enzymes responsible for metabolism of vinyl chloride are saturated at an atmospheric concentration of vinyl chloride of 250 ppm. Pharmacokinetic analysis shows that no significant cumulation of vinyl chloride or its major metabolites is to be expected on repeated administration of vinyl chlorides. This may be consistent with the theory that a reactive, shortly living metabolite which occurs in low concentration only, may be responsible for the toxic effects of vinyl chloride

  9. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [Edinburgh Univ. (United Kingdom). EaStCHEM School of Chemistry

    2012-12-07

    The silylated uranium(V) dioxo complex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] is inert to oxidation, but after two-electron reduction to [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-}, it can be desilylated to form [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U{sup VI/V} couple in dioxygen reduction. [German] Der silylierte Dioxouran(V)-Komplex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] (A) ist inert gegen Oxidation, kann aber nach Zweielektronenreduktion zu [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-} (1) zu [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} (2) mit wiederhergestelltem Uranylcharakter desilyliert werden. Beim Entfernen der Silylgruppe zeigt sich eine neue Redox- und Oxoumlagerungschemie des Urans unter Rueckbildung des Uranylmotivs sowie der Beteiligung des U{sup VI/V}-Paars an einer Disauerstoffreduktion.

  10. Thermodynamic parameters of the complexation of uranyl(VI) by diethylenetriamine in dimethyl sulfoxide

    International Nuclear Information System (INIS)

    Cassol, A.; Bernardo, P. di; Portanova, R.; Tolazzi, M.; Tomat, G.; Zanonato, P.L.

    1993-01-01

    The changes in free energy, enthalpy, and entropy for the complex formation reactions between uranyl(VI) ion and diethylenetriamine (dien) in dimethyl sulfoxide have been determined by potentiometric and calorimetric measurements at 25 C in a medium of ionic strength 0.1 mol dm -3 . The amine forms a very stable 1:1 complex which results stabilized only by the highly favourable enthalpy change. Entropy change is negative and opposes the reaction. The comparison of the thermodynamic data concerning complexation of uranyl(VI) by charged and uncharged ligands reveals that in this case (uncharged ligand) the enthalpy contribution is mainly related to the formation of the metal-ligand bonds while the entropy term might be associated with the decrease in the translational and conformational entropy occurring in the complexation of the ligand. FTIR and calorimetric measurements have been carried out to study the effect of traces of water on the equilibria in solution. It has been found that water can interfere in the complexation reaction giving rise to the formation of a dinuclear hydroxo complex in which probably two μ 2 -OH bridges link two monomer moieties. (orig.)

  11. New insight into the ternary complexes of uranyl carbonate in seawater.

    Science.gov (United States)

    Beccia, M R; Matara-Aho, M; Reeves, B; Roques, J; Solari, P L; Monfort, M; Moulin, C; Den Auwer, C

    2017-11-01

    Uranium is naturally present in seawater at trace levels and may in some cases be present at higher concentrations, due to anthropogenic nuclear activities. Understanding uranium speciation in seawater is thus essential for predicting and controlling its behavior in this specific environmental compartment and consequently, its possible impact on living organisms. The carbonato calcic complex Ca 2 UO 2 (CO 3 ) 3 was previously identified as the main uranium species in natural seawater, together with CaUO 2 (CO 3 ) 3 2- . In this work, we further investigate the role of the alkaline earth cation in the structure of the ternary uranyl-carbonate complexes. For this purpose, artificial seawater, free of Mg 2+ and Ca 2+ , using Sr 2+ as a spectroscopic probe was prepared. Combining TRLIF and EXAFS spectroscopy, together with DFT and theoretical thermodynamic calculations, evidence for the presence of Sr alkaline earth counter ion in the complex structure can be asserted. Furthermore, data suggest that when Ca 2+ is replaced by Sr 2+ , SrUO 2 (CO 3 ) 3 2- is the main complex in solution and it occurs with the presence of at least one monodentate carbonate in the uranyl coordination sphere. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Oxo-exchange of gas-phase uranyl, neptunyl, and plutonyl with water and methanol.

    Science.gov (United States)

    Lucena, Ana F; Odoh, Samuel O; Zhao, Jing; Marçalo, Joaquim; Schreckenbach, Georg; Gibson, John K

    2014-02-17

    A challenge in actinide chemistry is activation of the strong bonds in the actinyl ions, AnO2(+) and AnO2(2+), where An = U, Np, or Pu. Actinyl activation in oxo-exchange with water in solution is well established, but the exchange mechanisms are unknown. Gas-phase actinyl oxo-exchange is a means to probe these processes in detail for simple systems, which are amenable to computational modeling. Gas-phase exchange reactions of UO2(+), NpO2(+), PuO2(+), and UO2(2+) with water and methanol were studied by experiment and density functional theory (DFT); reported for the first time are experimental results for UO2(2+) and for methanol exchange, as well as exchange rate constants. Key findings are faster exchange of UO2(2+) versus UO2(+) and faster exchange with methanol versus water; faster exchange of UO2(+) versus PuO2(+) was quantified. Computed potential energy profiles (PEPs) are in accord with the observed kinetics, validating the utility of DFT to model these exchange processes. The seemingly enigmatic result of faster exchange for uranyl, which has the strongest oxo-bonds, may reflect reduced covalency in uranyl as compared with plutonyl.

  13. New thermo-sensitive chelating surfactants for selective solvent-free extraction of uranyl nitrate

    International Nuclear Information System (INIS)

    Prevost, S.; Larpent, C.; Testard, F.; Coulombeau, H.; Baczko, K.; Berthon, L.; Desvaux, H.; Madic, C.; Zemb, T.

    2004-01-01

    Functional surfactants were synthesised by grafting a chelating group (amino-acid residue) to the tip of a poly-ethoxylated nonionic surfactant chain (C i E j : C i H 2i +1(OCH 2 CH 2 ) j OH)) or in a branched position. C i E j nonionic surfactants are known to be thermo-reversible and to exhibit a clouding phenomenon associated to phase separation of micelles. The functional surfactants retain both surface-active properties, characteristic thermo-reversible behaviour and have efficient complexing properties toward uranyl. In the presence of uranyl nitrate, small micelles are formed at ambient temperature and the de-mixing leads to a separation of the target ion trapped by the functional surfactant (cloud point extraction). Those surfactants are more efficient than mixture of classical C i E j and complexing agent solubilized in the micelles. This reveals a synergistic effect of the covalent bond between the chelating group and the nonionic surfactant C i E j . This paper presents a systematic study of the extraction and aggregation properties and the influence of the nature of the ions. (authors)

  14. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660{plus_minus}0.092 at 25 C, and extraction enthalpy is -5. 46{plus_minus}0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 {times} 10{sup 6}{plus_minus}3.56 {times} 10{sup 4} at 25 C; reaction enthalpy was -9.610{plus_minus}0.594 kcal/mol. Nitration complexation constant is 8.412{plus_minus}0.579, with an enthalpy of -10.72{plus_minus}1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured.

  15. PMR spectra and proton magnetic relaxation in uranyl nitrate-hexamethylenetetramine-urea-water gel forming system

    International Nuclear Information System (INIS)

    Vashman, A.A.; Pronin, I.S.; Brylkina, T.V.; Makarov, V.M.

    1979-01-01

    PMR spectra and proton relaxation in the nitrate-hexamethylenetetramine (HMTA)-urea-water gelling system are studied. According to PMR spectra products of HMTA chemical decomposition, which are supposed to be formed in the gelling process, have not been detected. Effect of hydrogen exchange upon PMR spectra of urea and water in the presence of HMTA and uranyl nitrate is studied. Periods of spin-lattice and spin-spin relaxations of water and HMTA protons in gels on the base of uranyl nitrate are found. Data on relaxation permitted to make qualitative conclusions upon the gel structure and HMTA molecule distribution over ''phases''. Nonproducibility of the results of period measurements in gels is the result of nonproducibility of the gel structure in the course of transformation of liquid solution into gel. Temperature dependences of proton relaxation in the gels are impossible yet to interpret on the basis of temperature behaviour of one correlation period, controlling dipole-dipole nuclear magnetic relaxation, and obeying Arrhenius dependence on the temperature

  16. Uranyl ion transport across tri-n-butyl phosphate/n-dodecane liquid membranes

    International Nuclear Information System (INIS)

    Shukla, J.P.; Misra, S.K.

    1991-01-01

    Carrier-facilitated transport of uranium (VI) against its concentration gradient from aqueous nitrate acidic solutions across organic bulk liquid membranes (BLM) and supported liquid membranes (SLM) containing TBP as the mobile carrier and n-dodecane as the membrane solvent was investigated. Extremely dilute uranyl nitrate solutions in about 2.5 M nitric acid generally constituted as the source phase. Uranyl transport appreciably increased with both stirring of the receiving phase and the carrier concentration in the organic membrane, while enhanced acidity of the strip side adversely affected the partioning of the cation into this phase. Among the several reagents tested, diluted ammonium carbonate (∼1M) solutions served efficiently as the stripant. Besides Accurel polypropylene (PP) film as the solid support for SLM, some silicon flat-sheet membranes with different inorganic fillers like silica, calcium silicate, calcium carbonate, chromium oxide, zinc oxide etc. and teflon membranes transported about 70% of uranium in nearly 7-8 hr employing 1 M ammonium carbonate as the strippant. Specifically, 30% TBP supported on Accurel flat-sheet supports transfered better than 70% of uranium from moderate acid feeds (2.5M) under similar conditions. Membranes supporting Aliquat-336, TLA, TOPO etc. yielded somewhat poor uranium recoveries. The feed : strip volume ratio showed an inverse relationship to the fraction of cation transported. (author). 9 refs., 2 tab s

  17. Weathering of natural uranyl oxide hydrates: Schoepite polytypes and dehydration effects

    International Nuclear Information System (INIS)

    Finch, R.J.; Miller, M.L.; Ewing, R.C.

    1992-01-01

    Partial dehydration of schoepite, UO 3 x2H 2 O, is reported to produce three discrete schoepite polytypes with characteristic unit cell parameters, but this has not been confirmed. The loss of structural water from the schoepite interlayer results in progressive modification to the structure; expansion parallel to schoepite cleavage planes, and extensive fracturing. Dehydration of schoepite commences at grain boundaries and progresses inward until the entire grain is converted to dehydrated schoepite, UO 3 x0.8H 2 O. The volume decrease associated with dehydration results in expanded grain boundaries. These gaps can provide pathways for the access of groundwater, and uranyl silicates and uranyl carbonates have precipitated within these gaps, replacing both schoepite and dehydrated schoepite. Schoepite, however, is not observed to re-precipitate where in contact with dehydrated schoepite. Thus, while the formation of schoepite early during the corrosion of uraninite may be favored, schoepite is not a long-term solubility limiting phase for oxidized uranium in natural ground waters containing dissolved silica or carbonate. (orig.)

  18. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    International Nuclear Information System (INIS)

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660±0.092 at 25 C, and extraction enthalpy is -5. 46±0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 x 10 6 ±3.56 x 10 4 at 25 C; reaction enthalpy was -9.610±0.594 kcal/mol. Nitration complexation constant is 8.412±0.579, with an enthalpy of -10.72±1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured

  19. Efficient tetracycline adsorption and photocatalytic degradation of rhodamine B by uranyl coordination polymer

    Science.gov (United States)

    Ren, Ya-Nan; Xu, Wei; Zhou, Lin-Xia; Zheng, Yue-Qing

    2017-07-01

    Two mixed uranyl-cadmium malonate coordination polymers [(UO2)2Cd(H-bipy)2(mal)4(H2O)2]·4H2O 1 and [(UO2)Cd(bipy)(mal)2]·H2O 2 (H2mal = malonic acid, bipy =4,4‧-bipyridine) have been synthesized in room temperature. Compound 1 represents a one-dimensional (1D) chain assembly of Cd(II) ions, uranyl centers and malonate ligands. Compound 2 exhibits a two-dimensional (2D) 2D +2D → 3D polycatenated framework based on inclined interlocked 2D 44 sql grids. The two compounds have been characterized by elemental analysis, IR and UV-vis spectroscopy, thermal analysis, powder X-ray diffraction and photoluminescence spectroscopy. And the ferroelectric property of 2 also has been studied. Moreover, compound 2 exhibits good photocatalytic activity for dye degradation under UV light and is excellent adsorbent for removing tetracycline antibiotics in the aqueous solution.

  20. TG/DTA and X ray Diffraction Studies on Ammonium Uranyl Nitrate

    International Nuclear Information System (INIS)

    Kim, Byung Ho; Lee, Young Bum; Jeong, Ji Young; Choi, Jong Hyun; Kim, Tae Joon; Nam, Ho Yun; Kim, Jong Man

    2011-01-01

    Ammonium uranyl nitrate (AUN) is an important intermediate product during conversion of a uranyl nitrate[UO 2 (NO 3 ) 2 ] solution to UO 2 powder for the fabrication of nuclear fuels, the so-called modified direct denitration (MDD) process. The MDD process involves the thermal decomposition of AUN double salts, which are prepared from a mixture consisting of a UO 2 (NO 3 ) 2 solution and NH 4 NO 3 . The physical and chemical properties of an oxide powder depend upon its thermal treatment. Three double salts are known for the UO 2 (NO 3 ) 2 - NH 4 NO 3 -H 2 O system, but there have been only a few studies done on thermal decomposition of these salts. Therefore, the objective of this study is to investigate the reaction pathways during a thermal decomposition and reduction of AUN to achieve a better knowledge of the influence of an AUN preparation process and thermal decomposition procedures on uranium oxides under a nitrogen, air, or hydrogen atmosphere